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Chemiluminescence of organometallics in solution
Journal of Organometallic Chemistry, 387 (1990) 11-64 Elsevier Sequoia S-A., Lausanne - Printed in the Netherlands JOM 20689
11
Review
CHEMILUMINESCENCE Bulgakov
R.G.
institute of USSR Acad.Sci.
OF ORGANOMETALLICS
, Kazakov
V.P.,
IN SOLUTION
and Tolstikov
Chemistry, .Bashkirian Ural Department,
G.A.
Research Centre, Ufa, SU-450054
(Received January 3rd, 1990) CONTENTS 0. 1.
2.
3.
4.
5.
6.
*
The
introduction Chemiluminescence of Organo~tal~i~s of First Group Metals of the Periodic Table. 1.1 Reactions of lithium and sodium alkyls, cyclopentadienyls, and aryl s wi th oxygen, xenon difluoride, and organic peroxides. 1.2 Reactions of polycyclic hydrocarbon adducts of alkali metals and their ketyls with electron acceptors and oxygen. 1.3 Reactions of alkali metal solutions with chloronorbornene derivatives in liquid ammonia. Chemiluminescence of Organometallics of Second Group Metals of the Periodic Table . 2.1 Reactions of Grignard reagents with haloidpicrines. 2.2 Reactions of Grignard compounds with oxygen. The effect of Imagnetic field. Electrochemi luminescence. 2.3 Reactions of Grignard reagents with organic peroxides, benzene triozonide, and carbon tetrachloride. 2.4 Reactions of (CH3CH~CH*)~Mg and (CSHs)zMg with oxygen. 2.5 Reactions of Ca organics with oxygen. Oxidation of (CZH5f2Zn by oxygen and xenon difluoride. Chemi luminescence of Organometal 1 its of Thi rd Group Metals of the Periodic Table. 3.1 Reactions of organoaluminium compounds (OAC) with oxygen. 3.2 Thermolysis and hydrolysis of organoaluminium peroxides. 3.3 Reactions of OAC with dioxetan, molybdenum peroxy complex, and organic peroxides. 3.4 Reactions of OAC with xenon difluoride. 3.5 Reactions of boralkylhydrides with oxygen. 3.6 Reactions of organoboron peroxides with water. 3.7 Reactions of cyclopentadienyls of Yb, Sm, EU with and xenon difluoride. oxygen, water, 3.8 Reactions of boron hydride complexes of lanthanides with oxygen. 3.9 Reactions of cyclopentadienyls of uranium (IV) with oxygen and xenon difluoride. Chemi 1 umi nescence of Organometal I i cs of Fourth Group Metals of the Periodic Table. 4.1 Reactions of silicon organics with oxygen and xenon difluoride. 4.2 Reactions of germanium, titanium and tin organics with oxygen xenon difluoride. Chemiluminescence of Organometallics of Fifth Group Metals of the Periodic Table. 5.1 Reactions of (C2H5j3Bi and (C2H5)2BiF with oxygen and xenon difluoride. Chemiluminescence of Organometallics of Sixth Group Metals of the Periodic Table.
author
to whom correspondence
OOZZ-328X/90/$18.90
should
be addressed.
01990 Elsevier Sequoia S.A.
12 13 13 16 21 22 22 22 24 25 26 26 26 29 30 31 36 38 38 40 42 43 43 44 44 44 44
12
6.1
Reactions of chromium cyclopentadienyls with oxygen and xenon difluoride. of Mo(C0)6 and its derivatives with oxygen 6.2 Reactions and xenon difluoride. of W(CO)6 with xenon difluoride. 6.3 Reactions Chemiluminescence of 0;ganometallics of Seventh Group Metals of the Periodic Table. 7.1 Reactions of manganese organics with oxygen, xenon difluoride, and benzoyl peroxide. 7.2 Electrochemiluminescence (ECL) of fat-ClRe(C0)3L. 7.3 Reactions of Re(phen) (CO)3C! with tetralinyl hydroperoxide of (CO)5Re-Re(CO)3(phen) wr th chlorine. Chemiluminescence of Organometallics of Eighth Group Metals of the Periodic Table. 8.1 Reactions of Fe, Ni, Rh organics with oxygen and xenon difluoride. 8.2 Electrochemiluminescence of ortho-metallated platinum (II) complex. The Effect of Luminescent Additions upon CL OMC. Low-Temperature CL. Possible Uses of Application of OMC Chemiluminescence in Solution. Conclusions. Classification of Liquid-Phase Chemi luminescent Reactions of OMC.
7.
a.
9. 10. 11.
44 45 46 47 47 48 48 49 49 50 51 55 56
INTRODUCTION Among numerous with
chemical
most
unusual
energy and
luminescence in
1306,
reactions transformed
the
chemistry
This
review
studies
into
CL of
OMC in
the
information
pub1 ications,
Grignard
Since
with
that
are
reactions
with
research
excited coworkers the
on CL of few in
[2],
analyzed
amount
[3].
both of
liquid
its reported
inclusive.
of
metal
reported
in
[5,6],
formation
ions
luminous
the of
abi 1 ity
of
[4]
was
phases.
have
luminescent
and
reactions
review
free
isolat-
metals
gaseous
and
early
rather
alkali
previous
“child-
In
by
of
and
[l]
all
new CL reactions
states
subsequent
two
Our
exhibiting
through
cover
adducts
the
by Wedekind
represented
of
and onyl in
in
1988
to
OMC was
reactions
to
those
considered
OMC reactions
was going
1906
(OMC),
are
discovered
account
from
proceeding a fair
exhibiting
was
organometallics
very
radiation
chemical (CL)
of
described
publication,
those
first
solution
compounds
luminous
first
OMC are
reactions
As we and our redox
the
thus,
amd platinum
concerned
vered,
is
[2,3];
reagents
rhenium
into
chemiluminescence
hood”.
ed examples
organometallic
The
interesting.
called
when
of
been
dico-
radicals. of
OMC to
excited
enter
states
13 can
be regarded
formation should
a new common feature
and deactivation be considered
inherent
processes
to
gain
of
to
OMC.
Therefore,
electron-excited
up-to-date
insight
the
reaction
into
chemical
products
transformat-
ions. 1.
CHEMILIMINESCENCE OF THE PERIODIC
1.1
Reactions aryls
Gilman
alkyls
320-600
eye
result
of
butyl
that
been
or
in
by excited Cp-ring.
luminescence
intermediate
radical partially
both
more
emitter
is
(Ph3C’)*
tion
bands
the
CL and
and e.p.r.
(Fig.1)
tives
between
the
radical
CL and
exhibiting
for
reaction
the
the
scheme
Ph3CyNa+
or
FL at
basis
of “dark is
spectra
as by the
of
longer
CL and
but
of the
of
was
Ph3C’
of
02
is
as a
the
(Fig.21
the
notable
excited 02
and toluene
110,
solutions
have
been
by Gomberg by reac-
of
those
absorp-
by a match
prepared
described
a partially
the
was found
it
identified
solution
[5]
Ph3CNa with
by disappearance
for
in oxidized
with
by
[12,13]
(Fig.3).
Ph3CNa solu-
Ph C’ can be rationalyzed either 3 formation of radical substituted
in
terms
deriva-
wavelength. FL studies
chemistry”
of
[lO,ll] the
reaction
suggested.
+ O2 ____c
molecule
signals
FL spectrum
FL spectrum
FL spectra
complexation
On the [14,15]
(FL)
as well
161,
was synthesized
followed
intensely with
a new type
(THF)
and e.p.r.
CL
by oxidating
in
reaction
The CL emitter
signals.
fluorescence method
The difference and
from
solid
by an
formed
CL of
tetrahydrofuran
of that
CL visible
and CpNa with
CL reported
an organic
formed
oxidized
Ph CC1 with zing 3 Further oxidation by O2 is
tion
to
not
BuLi
recently,
as opposed
fact
effect-
lithium
band was obtained
Recently,
and ketones
Ph C’ which 3 dust.
of
Gomberg’s
of
the
CL absorption
[9].
PhLi for
oxidation
(a wide
due to
of
techniques
stated
CL spectrum
peroxides.
solution
with
just
reactions
Still
Ph CNa absorption bands 3 recorded matching those of
tion
reported
aldehydes
of
of
the
ether
synthetic
was also
[PhLi]=10m3M
observed
111.
In
with
OMC autoxidation;
the
CL with
publications
detect
cyclopentadienyls, and organic
optimal
was unsuccessful
even
emission
radical with
to
nm region)
has
of
Both
alkyls,
difluoride,
observe
Luminescence
solution
naked
to
designing
An attempt
colored
and sodium xenon
happened
their
and aryls.
occurred.
out
lithium
oxygen,
al.
in
GROUP METALS
TABLE.
, PhNa, and PhK [8].
PhLi
in
et
[7]
ed by 02
of
with
OF ORGANOMETALLICS OF FIRST
and of
the
Ph3CNa +
data O2’
reported the
following Scheme
Ph3C’
+ O;(Na202]
in
1 (1)
*
14
8-
.O
6
I.8 4I. 6 / I.4 21.2 0_
I 320
Fig.1
Absorption
(l-3).
(I)
400
360
spectra
by partial
of
440
triphenylmethyl
480
prepared
A ,nm
by different
techniques
02 oxidation
of 0.03M solution of triphenylmethylso-4 -3 dium in THF [ll]; (2,Z’) by d-radiation of 10 and 5.10 M solutions, respectively, of triphenylrnethylchloride [12]; (3,3’) with 0.0002M and O.OOZM solutions, respectively, of the radical synthesized by Gomberg’s reaction in THF, 300 K [ll]; (4) 0.0005M triphenylmethyl cation in 98.3% furic acid, 300 K [II). Ph3C’ Ph3COi
+ 02
+ Ph3CNa
Ph3CO;
-
+ Ph3:’
-
ph3c
.:
Reactions
(6)
and
(8)
are
Ph3COOCPh
(4)
3
+
2
(5)
(Ph3C’)+
inferred
(6)
Ph3C+ +;,
(7)
(Ph3C’)
(8)
+ Ph3C’
Ph C + h3 (523 3 Ph3C’ + Na”
3 Ph3CiNa+
emitter
(3)
Ph3C02
+ Ph3Cf; +(P;3:]
(2)
Ph3COONa + Ph3C’
Ph3C02. :+o
ph3c’ + O2_ Ph3CO; * Ph3C: Ph3C;
Ph3CO;
as the
most
sul-
nm)
(9) (10)
obvious
source
of
the
excited
(Ph3C’)4. Weak CL observable
reactions
of
solvents
by FL,
BuLi
only
with
PMR,
IR,
with
benzoyl,
a photomultiplier lauryl,
UV spectral
and
methods
tert-butyl [l6].
(PEM) was
investigated
peroxides The energy
in
in organic released
in
15
Fig.2
EPR spectra
phenylmethyl different THF.
(1)
of
prepared techniques
with
triby in
partially
O2 oxidized
triphenylme-
thylsodium;
(2)
by Gom-
berg’sreaction.
Fig.3 Spectra of CL(l),fL(2-6),and excited FL(7,8) for the triphenylmethyl radical. (1)0.2MtriphehylmethyIsodiumwith O2 in THF,300 K [11];(2)0.002M species synthesized by Gomberg’s method,300 K [11];(3) as in (2),77 K; (4)reported measurements [12];(5) partially oxidized triphenylmethylsodium, 300 K [11];(5’,5”)with further oxidized triphetiylmethylsodium;(6) 0.0005M solution of triphenylmethyl cation in sulfuric acid [11];(7) A (excitation)= 350 nm; (8) reported data [12].
16
the
first
reaction
step
Ph-i-0-0-C-Ph
accepted
by
BuLi
-
from
which
butyl
vinyl
Ph-i-Bu
ketone
BuOLi
+
,
+ BuLi--cPh-$-OLi II 0
0 in
but
+
the
the
second
0
reaction
primarily
is
Bu-0-Cn-Ph
0 step
excited
Ph-ti-o-Bu 0
product
+
0
formed
energy
in
butyl
the
third
phenyl
mainly
with
the
FL
spectrum
for
The
second
emitter
1.2.
with
with
electron
cyclic electron the
acceptors
The
the
electron
nic
and
[17,18]. of
first acceptor
was
reaction
results
for
diphenyl
anthracene)
latter the
with
the
-
as
FL
to
be
emitter
of
alkali
spectra
of
a CL emitter did
not
close
to
(Amax=
the nm).
metals
and
bright
CL
elimination
the
to
their
a
all
these as
to
DPACI’ intermediate electron ion
to
If
(DPA
+
DPAC12
_
DPA
+
cl-
___c
DPA
+
DPA”
DPACl +
orga-
stands reacts
from lead
the thus
to
Scheme
DPA’
the
acceptors,
(2).
+
allow
of
reactions.
electron
That
chlorine
to
moieties
OMC anion-radical
act
an
poly-
inorganic
enough
organic the
accepts
of
bright
reactions
with
and
radical 2).
and
metals
organic
from
chlorine
(Scheme
of
were
as
common
+
DPACI’
class
with
intermediate (1)
be
was
alkali
new
transfer
OMC anion-radical
Cl
where
in
of
adducts
containing
unstable
a
species
electron
complex
unidentified.
reaction
CL and
shown
concomitant
CL
DPA’ DPACl
in
another
excited
of
it BuLi
are
oxygen.
of
upon
CL emitting
compounds
the!
with
number
The
the
stage
inorganic
further
a
The to
but and
adducts
discovered
hydrocarbons
identification
adducts.
for
aromatic
products
nm region)
ketones
remained
and
final
recognized
400-600
acetonitrile
nm)
acceptors
transfer
and
in
phenyl
540
originally
al.
was
bands
of
The
Ph-CBu2-OLi .
-
hydrocarbon
electron et
BuLi
alkyl
at
polycyclic
identified.
alcohoiate
solution
(emission
not
+
(wide
for
heptane
of
Chandross
1 i thium
spectrum
spectrum
a
Reactions ketyls
CL
was
I! Ph-C-Bu
with
the
FL
transferred
step
ketone
because
agree
was
*
2
(1)
Cl-
(2)
Ph
is
- J< The
transfer
electron logous the
of enters
CL
same
scheme oxidant.
an
electron
the
lowest
was
assumed
CL arises
from
DPA’
antibonding for only
the upon
into level oxidation
DPACI’ of
can the
yield
radical
of
sodium
OMC oxidation
with
DPACl
if
the
DPACI’.
An
ana-
naphthalenide an
aromatic
with peroxide.
17
lA, 1
Fig.4
2
(I)
for
the
0.03M
CL
DPA and
peroxide 1181;
(2)
adduct
of
the
and
O.OlM
DPA;
of
nescence chanism
the
impelled CL for
of
DPA-
+
(4)
The
above
+
nature
of
the
the
authors
of
the
reaction
(C6H5C02)2
scheme is
benzoate
radical
the
higher
radical
is
(2).
they
bonding
orbital
The
absence
with
react
CL spectra
Thus,
of
in
(5) phosphorescence
N-phenylcarbazole,
C6H5C02
-
DPA”
in
that
80 K, nm [IS].
of of
sodium
to and
form
Scheme
(3)
transfer
radicals excited
potassium
to
into
with
explained than might molecules
adducts
of
the
to
by that of
ion
transfer the
aliphatic
that
peroxide
benzoate
by electron
OMC anion-radical
is
me-
(2)
latter
excited
much higher
alkylcarboxy DPA’
is
lumi-
(1)
electron the
of
different
peroxide.
CL upon oxidation
is
a somewhat
C6H5CO;
of
radicals
presence
+ C6H5CO;
+
another
or
(C6H5C02);
the
CL emitter
absence
advance
benzoyl
-
radical
with
to
DPA +
to arylcarboxylate
radical. could
The
on the
[17,18]
by decomposition
an arylcarboxylate
xylate
peroxide
-
unusual
followed
(3).
as opposed of
’
C6H5C02
acceptor
BP0 in FL of
A ,nm
(C6H5C02), DPA;
CL
N-phenyl-
h (excitation)=300
The effect
(3)
N-phenylcarbazole
dioxane;
420
benzoyl
dioxane
0.04M
[18];
of
potassium
0.05M
carbazole dioxane
in
FL of
of
adduct
0.04M
(BPO)
spectrum
of
spectrum
potassium
and from
benzoate peroxides
the
stability
an alkylcarbo-
decarboxylate
before
DPA*. N-phenylcarbazole
with
3
18 the
exception
component were
of
at
N-phenylcarbazole
410
and
considered
to
[18].
preferred emitter;
upon The
the
positively
that
of
charged of
powdered
mixture
for
the
the
glass
FL spectra
of
aromatic
1 ,2_benzanthracene, bands
and
tively.
The
cient
to
enough viously 3Ar
thermal even
generated
blue
that
an argon
bright are
given
CL was
in
form
be seen in
reaction
while
Fig.5.
The
(ArO-)”
which
the
is
the
to
through
Ar’
-
to
picene,
pyrene,
phosphorescence
in
anions,
all
+ Na
where The
radical
At-’
which
(2). orbital [22]
Ar=
The to
+ Na+C,OHB
z C,OHB
cases
CL emitters,
observed
___c
-%
-
while
CL emitter
is
being
most
3Ar7: + WB
ob-
and
CH3CN solution
of
daylight.
of
di-9-anthranoyl
O2
in
CL and
emission
ArCO;
ArO;
--+-
the
peroxide
diglyme
solution
FL spectral
by anthrone following
+ Arc02
ArOOOOAr
Na+ + C,OHB f
formed with
CL emitter that
insuffi-
a
assignments
in
its
anthra-
scheme. 4
(ArO-1;:
+ Na+ + C,0H8
------c -
2ArO’
(1)
+ O2
(2)
CL
(3)
@&
Arc02 react
respec-
L
CO2 + At-’
+
a
be similar
pyrene
+ WB+ --c
At-’
OMC with
Scheme
0 II Ar-CO-OC-Ar Arc02
anion,
An ethereal
flow
0
II
CL
cation:
and
a homogeneous
in
[20].
let
found
the
[21].
as
al.
Besides,
NaC ,BHB wj th
from
excited
the
their
as chrysene,
of
presence
of
+ WB* was
bright
identified
CL arises
were
Ar-
in too
being of
carbazole
blue
chrysene
steps:
of
in
visually
et was
such
states
also
latter
reactions
Therefore,
not
of
tetracene. for
reaction
consecutive
upon
atmosphere,
yellow
nolate
found
(At-)
singlet
perceived
in
CL spectra
molecules.
CL can
being
No CL was
lower
triplet through 1 Ar f Ar.
+ 3Ar:c A bright
the
the
possibilities
[19].
Wurster’s
recorded
in
the
emission
by Weller
perylene,
were
effect
generate
WB+ClO&
in
emission
excite
to
the
wavelength
interpretation
anion-radicals
hydrocarbons
anthracene,
eximer
by the
and crystalline
(CH3),NC6H4N(CH3)hC10~(WB+C10~); the
CL,
that
hydrocarbons
aromatic
show a long phosphorescence
wavelength
rejected
was demonstrated of
nm and
decomposition
polycyclic
adducts of
long
CL was caused
ions
365
Eximer
Chandross
on,
phenylcarbazole
excitation
solution
FL at
nm (Fig.4).
account
Later
he assumed
formed
430
of
in
oxygen is
then
the to
first
stage
give
peroxyl
generated
9-oxyanthracene
no CL when oxygen
(3). reacted
(1)
is
decarboxylated
and oxyl
by electron
radicals transfer
As reported with
Na+C,BHi.
in
of from
[2a], This
to
the is
radicals
anthracene anti-bonding authors
surprising,
of
19
300
500
400
A.nm.
400
300
500
A\,
1
\. \ \‘
f
00
-Na+
1
s .f
-jI 0
i(
._ I
J
1
-
0
,C
1
-
300
-----
to
solid
the
lower that
sodium
CL observed and
its
sotvent.
peroxide
sodium is
is added
two orders
We have
poured
on autoxidation
spectrum
metallic
a CL which
A ,nm
A,nm
FL spectra of aromatic hydrocarbons in THF, 300 K 123,241; CL spectra registered upon autoxidation of sodium adducts of aromatic hydrocarbons in THF, 300 K [23,24]; FL spectra (77 K) and electrochemiluminescence (ECL) spectra for aromatic hydrocarbon eximers (ECL only for phenanthrene and anthracene, 300 K 1241).
-*-*-
Thus,
1
LO
0
Fig.6
1
attributed
ihto of
reproducible to of
THF gives sodium only
OMC, but with
argon-saturated magnitude
that
CL to
to
(with
02
of
is
intensity
fi Iters.
when air
ionization
CL which
its
glass
TtiF
brighter the
rise
is
is much
it
traces)
appears also
bubbled
sodium
close
with
yields
through ether
the
20
Fig.5 (1) CL spectrum for 0.0004M di-9-anthranoyl peroxide and O.OlM sodium naphthalenide with oxygen in dimethoxyethane (DME) [21]; (2) FL spectrum for the above solution (3) FL spectrum after reaction: for 0.0004M anthrone in KOBu(t) solution in DME [21]; (4) CL spectrum for O,DlM sodium naphthalenide and oxygen in THF [23,24].
480
since
CL was easily
dicals the
of
many aromatic
ketyl
which
in
states
autoxidation
is widely of
of
aromatic
the
CL spectra
agree
generated
either
Fig.6).
Both
vibrational
that
Na’Ar’ ArO’
In can
the
as
well
with
blue
02
adducts
[23,24].
solution
of
of
anion-ra-
Further, sodium
benzophe-
experimentally, unambiguously
with
are
the
not
indicates
CL emitters,
known emission
electrochemically emissions
[24a] reveal
This
their
provides
of
or
that but
those
singlet-
maximum bands
hydrocarbons’
upon photoirradiation wide
a basis
band maxima for
the
without
ass~pt~on
the
’ (ArAr)*. similar
in
to
The alternative anthrone
in
its
suggestion anthranolate
has form
+ Na’Ar’
autoxidation
(ArO-)* of
in
sodium
reaction
be and
(ArO-)“,
which Scheme 5
At-’ -!-% -
can
been made that
Scheme 5.
+ 02 -
be observed
the
sodium
‘(ArAr)+c which emission of aromatic eximers 1 ArJ: + Ar --c T(ArAr)J: or ion-ion annihilation and as
from
a species
excited
reacted of
FL spectra
structures.
exe i ted by impact + as Ar + Ar- -
is
when the
hydrocarbons
CL and eximer
CL results
CL is
used
CL and
eximers
detailed
visually
hydrocarbons
in
A comparison excited
Jt ,nm
identified
CL is observed
none
560
of
ArOO’
-
--c
ArOOOOAr ---_*
+ 02
(1)
CL
(2)
anion-radicals different
2ArO’
of other
hydrocarbons, components
of
light the
emission
system.
the
21 to
form
oxygen:
the
related
Na’
+ S -
aromatic er
with
02
alkali
in
ammonia.
An interesting
Na,
and
K in
CL.
XeF2
metal
type
derivatives
following
CL through The
gives
its
further
oxidation
a visible
of
reaction
wit h
sodi urn adducts
CL which
is
still
of
much bri ght-
[5]. of
norbornene
gives
02
with
Reactions liquid
which
(Na+S-)
hydrocarbons
than
1.3.
adduct
of
visible
(THF
liquid
solutions
ammonia
with
green
solutions) [25].
CL was
with
The
chloronorbornene
reported
derivatives
for
various
electron-donating
CL mechanism
chloro-
solutions
suggested
here
of
Li,
the
scheme.
x
_
x
x
Cl
94
Scheme
6
I
L&l
(Na+-NH:)
B
i:l
Cl
c,
Cl
c\
x
A
Cl
\
B
Cl
A
(1) x
x
/
Cl
$6
Cl Cl1
Cl
+
I
H
where
h3
6
\
M -
A
2
metal;
X,
A,
subst i tuents
B -
such
H,
as Cl,
OMe,
OBu and OAc,
C02Et. The
first
molecule
to
The
basic
[lg]
is
rather to
give
the
that
its
to
ground
The
vinyl
geometric
between
an organic state
anion
which the
above
CL was assigned
2z
(2.2-2.5
alternative
involj Jf3s electron
here
an anion-radical
difference that
luminescence 2rl
stage
radical adiabatic
(pyramidalization
to
That 2.4
releases
is
vinyl
route
of
the
2n olefinic
-
given in
radical
for
its upon
corresponding transformation
i.e.
nonadiabatic,
transition
that
radical
eV energy
The main
eV).
a chloride
and
vinyl
the
to
eliminates scheme
the
molecule.
transfer
radiationless 2E
carbon
(2)
is
atom)
acceptor anion. by Chandross 2n -state transition to of
green the
(1). favoured
by both
and electronic
OH,
22 (substituent)
factors.
The
substituent.
CL reveals
6-H
in
involved In
addition
ed CL with
2.
the
its
to
2.1.
The
almost
well
of
history
of
iodides
from
authors
exhibiting
caused
the
vacua
Birch
required
X-OMe,
A-OH,
transformations
started
the
report
the
yield-
published
brightest
CL.
and
a photoelectron
[44].
The mechanism
In
Later
on,
as of
lumines-
is
iodopicrine.The
CL
multiplier
was different
from
the
nd reaction”
remains
of
‘Wedeki
the
[34-361,
CL intensity
with
by the
honour
compounds
contrary,
than
cited [27-471
[28].
Grignard
On the
bromopicrine
book
made
Unfortunately,
reagents
reactions”.
some other
observations
inadequately
Grignard
‘Wedekind
with
the
[l ,261.
were
CL with
recently
from
chloropicrine
pioneer
called
using
by oxygen
that
observed
chlropicrine
in
substituents
the
haloidpicrines.
PhMgBr with
concerninc
of
CL was were
with
recorded
of
works
that
with
OMC chemiluminescence
research
reactions
higher
of
[25].
reagents
abstracts
discoverer,
with
presence
OF ORGANOMETALLICS OF SECOND GROUP METALS OF THE
reactions
as by the
cent
brightness
chloroderivatives,
too
Grignard of
for
all
authors
by the
TABLE.
Reactions
by Wedekind
displayed
substrate.
norbornene
CHEMILUMINESCENCE
is
highest
initial
bromoanalogues
PERIODIC
latter
that
unstudied.
2.2.
Reactions field.
of
Wedekind,
reagents
a Grianard that
reagent
was
was
Extremely
bright
H MgBr with 6 4 luciferin, and
of
this
in
[35]
reaction” bright It reported mount acyclic attached
both
somewhat
can in
and, enough
to
do.
first
That
in
a printed
that
For
both
an unsaturated
the the
a 0.5
nature
carbon
pyrometric
paper
CL is
atom.
the
the
reaction in
of
oxidation of
p-BrC6H4MgBr,
the
name “Moeller-Evans
emitted
greenish-blue
[35].
organic emission
brighter
The
Later,
board.
than
of
the
with
the
experiment,
measurements
oxidation
favour
the
in
brighter
1 flask,
of
black
by Spatch CL was
the
his
of
[47].
CL regularities
radicals types,
In
CL was given
for
lsocyciic
magnetic
[28,29].
by the
as observed
works
of
CL upon contact
a sloping
blue
In
This
from
effect
observed
observed dark
reading
The
to Wedekind
[36].
[36].
air onto
was confirmed
be concluded early
with
poured
reactions
oxygen.
(ECL).
ascribed
[3l].
fainter
importance. ones
slowly
CL was
02
light
with
originally
PhMgl)
wrongly
p-CIC
brightness
Heczko
(PhMgBr,
discovery
CL was
compounds
Electrochemiluminescence
Following Grignard
Grignard
Grignard
reagents
fragment
is
of
more
when magnesium
substitution
of
one
of
light
parathan
is hydrogen
23 in
the
of
luminescence.
ness
benzene
ring
brighter
any other
in of
the
the
series
substi
luminescence.
intensity
reduces
species
the
[37]
as
bacteria.
and organomagnesium a substituent
those of
in
the
pub1 ished
oxidation
different
Grignard
species
papers
[9,461,
CL and
FL spectra,
to
since
[g]:
the
form
it
starting into
of
CL,
the
radicals (X)
brightnature
exhibit
in ArMgX,
CL and most
Grignard
the
photographs
the
the
CL
the
In some early
The
initial
448 and 518
and Hercules reacts
bands nm for
(blue)
the
wrong
of
in
recent
similarly
following
in
reaction
which
in
course
[36,39,43]
positioned
p-terphenyl
CL
as
the
C6H5Mg!3r and p-ClC6H4MgBr,
suggested with
natural
wavelength
as well
assignments
are
with
during
FL emitterswereconsidered
intense
only
CL wavelength
works
to grow
03
CL with
longer
wavelength
ring,
was found
with
of
were
showed
shorter
benzene
[36].
reagents
recordings
chlorides
showed
in
FL intensity
the
C6H5MgBr
intensity
same chemical
weight
experimental
iodides
the
a radical
the the
the
substituent
reaction
first
reagents.
e.g.
Bardsley
pestively,
the
luminescence
m->o->pthe
later,
of
the
the
position
series
in
affects
With
higher
Organomagnesium
(green)CL,
increases
1391,
increases
Cl>CH3>Br>l.
of
gave
[37].
With
also
change
Previous
species.
such
position
OMC with
series
CL spectra
hs exposure)
synthesized
radical
p->o->m-
tuent,
With
in
Photographic (3-12
atom or
The substitution
decreasing
and position
for
is
the
resmechanism
produced
to
trans-
anion. 1
C6H5MgBr + C6H5-C6H4-C6H5 which pheny
is
1,
then which
identification An attempt of
and
native
to
suggested
made to
inhibitors
molecular
by 03 or
oxidized
was believed
chose
upon
schemes
to
these
biphenyls
to
for
and
be the
to
rule
CL excitation,
p-ter-
Kearns
questioned
emitters
by observing
appeared the
MgBr
singlet-excited
Bolton
possibilities
brightness
mechanism
generate
CL emitter.
brominated
luminescence
were
peroxide
be the
between
and free-radical
C6H5 + [C6H5-C6H4-C6H5]
-
out
[46]. the
both
effect the
and two alter-
suggested. Scheme 7 Ph02MgX -
PhHgX + 02
-
Ph’
+ MgX2
-
PhMgX + X’
+ PhMgX
-
XPhMgX’ R
-
XPh02MgX
-
XPh-Ph*
X’
XPhMgX + 03 XPh02MgX + PhMgX XPh-Ph* XPh02MgX + PhMgX
Ph’
+ Mg02X
R’ + XPhMgX
+ 2MgOX
-
XPh-Ph
-
XPhMgX + PhOMgX
+ h$
24
Scheme 8 PhMgX + 02 Ph02MgX + PhMgX
PhO2MgX
-
2PhOMgX i
X-Ph-Ph:: Both ion is
schemes source,
assume but
reactions
there
is
X-Ph-Ph
of
Ph-Ph-X”
+ MgO + MgOX
peroxide
to
+ h$
organomagnesium
no experimental
evidence
as to
be the
stage
at
excitat-
which
light
emitted. The effect
of
magnetic
field
02 was originally
found
gauss
to a solution
was applied
was visible to occur
in
authors
clearly:
there
the
most
intense
that
field
assumed
responsible
for
the
Electrochemi Dafford
[40]
nescence seen lysis
Those
with
trolysis
of to
providing
impurities
six
of that
1401,
under
Grignard
for
by 02.
most of
near
labile
reagents
by
strong field of 1500
oxidized
field,
with
of
the
One effect
the
pole
paramagnetic
contours
from
that
of
the
of
emission
which
is
the
of
emission
pieces.
The
species
were
the
confirmed
by the
after
anodic
of
organic
peroxides,
Grignard [4l].
luminescence Upon elec-
a period the
with
of
reaction
of
[44].
This
upon electrolysis occur
be
electro-
reported
ECL to
ECL can
lumi-
could
[44,45].
electrolysis
by
The
during
reaction
was also
of
reported
emission
opinion
released
“pure”
was
C6H5MgBr.
Pt electrodes
the
disappeared
assignment
on whether
of
during
later
conditions
reagents
solution
an opposite
the
oxygen
doubt
Grignard
The nature
ECL were
in vacua, for
of
the
while
milder
support
casts
the
an ether
be different
containing
observation
being
tendency
of
(ECL)
metres.
observations (PEM)
conducted
time,
regions
of
when a
effect.
oxygen
visual
registered
[40]
C6H5MgBr
interactions
much bright
was assumed
reagents
oxidation
al.
was a distinct
luminescence
a distance
et
of
upon electrolysis
wasso
at
upon the
by Dufford
Grignard
reagents. 2.3.
Reactions nide,
of
and carbon
A somewhat Grignard
less
reagents
with
reagents
with
benzene
triozo-
tetrachloride. bright
CL was visually
benzoyl,
ethyl,
identified
in
reactions
and diacetyl
peroxides
C6H5MgBr,
p-ClC6H4MgBr,
of
than
with
f38.l.
oxygen
Bright p-CHjC6H4MgBr ether
Grignard
or
aliphatic
red
CL in
with
the
benzoyl
reactions peroxide
THF was discovered Grignard
A good match
and studied
compounds between
of
and tert-butyl
nor
the
by Bol ton and Kearns
diphenylmagnesium
CL and
the
FL spectra
and
peroxybenzoate
exhibited obtained
[47].
in diethyl Neither
similar for
CL [47]. the
solut-
25
2
h 0
500 Fig.7
ion
Ph3C’
emitter
is
data
4 ,nm
FL at [49-511.
region
SG2,
with
CO,
Ng2,
violently
benzene
CO2,
mentioned in
the
Reactions
less
than
Grignard
oxidation,
ketone
duction
that
proved
formed
determine
the of
of
is
440 further
the
to
of
radicals
galvinoxyl
of
free as an
the
inhibitor,
those the
while
a few
the
is
mixed
Bright
[44].
red
However,
vacuum
[44].
with
starting
O2 is
(C5H5)2Mg
impurities);
long
follow-
wavelength
a stable possibly
An attempt processes, of
reagents
high
The
Thus,
rate
H20,N,0,
(C5H5)2Mg
with
into
OMC Cp-ring. in
and
nm. this
red
oxygen.
[6,52].
and
CL emitter,
role
560
peroxemission
as
1361.
Ccl4
under
with
connected
transformed
by oxidation
removed
reagents
CL maximum at
be the
PhMgBr with
(n-C3H7)2Mg
nm (propably
eye
the
wavelength
species
the
77 K)
benzoyl
longer
CL
with
by the
Grignard
to
(CG2Mg of
the
different
CL visible
and
(300,
CL was observed,
was
for
in
the
-
institute
agreement
be excited
[32,33,35].
reaction
that
maximum matching
with
O2 which
oxidation
its
is
of
the
ing
product
the
in
can
as
in our
by PhMgBr with
it
no visual
for
FL at
(Ph3C’);b
in good
radiate
much heat
(CH3CH,CH2L2Mg
displays
e.g.
reagents
resulted for
radical
[lO,ll]
CL exhibited
which
Na2g2_,
absence
of
CL found
bright
solution
red
nature,
liberate
triotonide
no CL arose
The
The
nm (Fig.7)
Grignard
to
CL was also
2.4.
523
different
of
the
the
Ph C’ derivatives 3 [SO].
Upon contact
reacted
identified
Ph C’ solution prepared 3 no FL in the red spectral region
revealed
of
substituted
H,g,,
However,
distinct
probably
spectral
by Gomberg
(Fig.7).
same method
showed
Ii terature
of
prepared
[47]
by the
ide
700
(I) CL spectrum measured with boundary filters for phenylmagnesium bromide peroxide with BP0 in diethyl ether [47]; (2,3) FL spectrum for triphenylmethyl prepared in reaction of triphenylmethylchloride with zinc dust, 300 K, A(excitation)=447 nm; (2) [47]; (3) [lO,ll]. of
and
600
but
FL with
autoxidation an excited
was made to after
O2 absorption
the by
intro(C5H5)2Mg
26 was
not
2.5.
decreased
Reactions oxygen
the
of and
PhCal with
and
is
xenon
nescence
comparable
observed
for
solution.
The
to
of
of
Hg-
(C2$.)2Zn
by
(C,H5)2Hg. , OMC which exhibited
by 02,
that
of
of
“nonmagnesium”
intensity
PhCal
PhMgI.
displays CL was
CL seen
yellow not
lumi-
visually
[38]. in
oxidation [45],
C6H5ZnBr,
and mercury
oxidized
by 0,
1 .O~lOy
CL much
(1=1.4.106
low
and
and
Zn-organic
C6H5Znl,
OMC are XeF,
photonTS.ml,
(ca.lml
of
broad
maxima
appears
of
02
of
less
the
CL maxima products
per
glass
at
470,
after
in
compounds
p-BrC6H4ZnBr
capable
of
toluene
by
CL in
rather
rapidly
such
[43]
exhibiting
reveals
rezpectively),
the
PERIODIC 3.1.
530,
bright
fading
w th
CL was
and
coordination
the
majority
in
a darkened
registered
with
the
slow
K).
be
The
in
the
starting
then
the
emission
of
of
5*10-‘M
55°C)
of
CL spectrum
nm. The in
in at
rate
region
The on
was measured
400-600
of
T HF solu-
[53]
autoxidat
OMC gives
region
ketones
with
nm with no FL;
the
formed
OF THIRD
with
compound of
those
room.
-
diffusion point
the and
For is
due
cyclic
short
its
it
wavelength
as oxidation
GROUP METALS OF THE
number
of
to
and carbon
atoms
as well
Ru(bpy)3C12.
display
feature
ranging
from
and
consumption
falling
rate
of of
of
of
the
the
solved
to
at
iso-
with
Ii thium
M solutions, visually
formation
three
main
intermediate
OAC oxidation the
two
CL identified
OAC (C,-C8),
OAC.
trialkyl-
norbornene,
as OAC complexes -1 In 10 -1
by a combination
of
OAC [54-631:
bluish-green
oxidized
consumption
oxygen.
derivatives,
derivatives, ruthenium
with
acyclic
of
rapidly
rapid
(OAC)
a characteristic
halide-substituted
conditioned
abruptly
considered
both
compounds
accumulation -
compounds
is for
cyclohexene
CL maxima
reaction
bubbling
OF ORGANOMETALLICS
hydride-
and
kinetic
the
organoaluminium
compounds
, their
kinetic
and
(C5H5)2Hg
air
TABLE.
luminescence”
camphene,
298
of
hour
Cp-ring.
of
twenty
at
to
of
Reactions
aluminium
0.5
and 580
“Chemical Indeed,
Ih
oxidation,
CHEMI LUMINESCENCE
3.
autoxidation
connected
filters
characteristic of
in after
CL is
absorbed
boundary
only
bright
photon/S.ml
brightness
a set
(ii)
Oxidation
Autoxidation
first
p-CH3C6H4HgBr
atd
oxygen.
[5,6].
tion
(i)
in
observed
Et,Zn
with
Upon oxidation
However , zinc
CL (4.7.1D8 time
the [38].
EtCal
as C6H5HgBr, oxygen.
abruptly.
difluoride.
of
eye
No CL was
CL faded
Ca organics
one
naked
the
of
factors: OAC peroxides;
the
oxygen,
starting and
subsequently
27 growing
oxidation
by the
02 dissolving
establishing itself ion
the
in
the
due
rate
from
the
quenching
increase
solution
to
(open
the
increase
air
flow;
effect
of
of
the
(iii)
02.
CL intensity
cell)
in
02 concentration,
deactivation
That
with
-
removing
deactivating
factor
bubbling
through
air
caused and
reveals the
react-
(Fig.8).
Fig.8 Deactivating effect of oxygen on CL in autoxidation of diethoxyethylaluminium in toluene, 300 K, [561. (1) [OAC]= 1M; (a) with air bubbling off and Ar inlet; (b) with air bubbling on and Ar off (open ceil); (2,3) [OAC]= 0.1, 0.025, 0.02, 0.015M with 0.006M starting oxygen (closed ccl 1).
200
lot ,” ._ 0 r al 240 CI o *5 160
80
60
120
The
induction
out
any
its
In by the
to
the
the
of
oxidation kinetic
of
OAC autoxidation
the
Since
the
reaction only
kinetics
of
the are
consumption
described
was
(C2~50)2~LC2~5 is
abruptly
first + o2 lowered
proved [56].
in
consumption
is
the
slow
of
a CL emitter). determined
the
oxidation by the
The
successive
peroxide
occurs
in
of
this
due
OAC,
the
accumulation
involvement
was shown also
(C2H50)2A100C(CH3)3
the
O2 has
CL is
stage
(with-
R Al and two intermediates 3 this OAC series decreases
particularly
peroxides.
of
the
each
cell of
a quencher
peroxide
by the
of
those
and inter-
by observing
with
CL
(i-C4H9)3A1,
reaction,
the
CL
curve.
involvement
of
free
inhibition
of
the
The absorption
immediately
CL in
CL excitation
by a sloping
Upon OMC autoxidation, emission
of
of
a closed
alkyl), at
initial
Therefore,
in
stable
(02
arising
i.e.
in
the
(R -
determined
organoaluminium
the
after
type
intensity
is
oxidation
solution
R3Al
emission
rate.
curve
consumption of
the
bonds,
The
[55].
because CL only
the
Al-C
mediates in
in
OAC of
al 1 three
lowered of
exhibits value
of
RAI (OR)2
300
CL occurs
contribution
of
R2AIOR,
of
critical
total
240
phase)
oxidation
oxidation
shape
period
gaseous
reached
180
after
of the
oxygen
galvinoxyl
radicals
in
causing
chemiluminescent ceases
and
addition.
the
reaction CL intensity
After
a short
29
+h3 YHO Ii
0 h)*
(RC<
1>AIR Initiation diate
involves
was established decrease
in
the
the
initiation
[59,69]
,
main
and
the
(14)
3.2.
is
of
Thermolysis
FL spectra
formed
in
their
view
of
that
of
alkyl
disproportionation a side
reported
that
high
radicals
[59], ground
data
of
thermolysis
Thus, as
are
of
the
studies
main
in
ini tiat-
region
ketones) (12,13)[6,551.
alkoxides
as
is
quenched
Earlier, to
Vasil’ev
the
hydrocarbons
dispro[55a].
peroxides.
with
the
relatively
that
peroxide
stable
(CH3) 3 158,591. “dark” the
thermolysis
following
and excited
of
scheme
was
[6g]
suggested
for
the
and on CL products
states. Scheme
(CH ) COH +
(C2H50
the
compounds
owing
of
the
and
a cabonyl
CL emitter
organoaluminium
mechanism
(or
OAC (15).
excited
oxidation
OAC possessing
radicals
formation
(CH;C:O) ?. P, -
* ?: P2 -
(C H OAIO)x :H:CHO P2 + h3
O2
(C,H50)2AlC2H5,
R Al is 3 incorporating
The
of (3),
on CL inhibition
peroxide
were
the
removal
for
aldehydes
with
abrupt the
intramolecular (4)
(4)
peroxide
for
each
rate.
reaction
in
the
by trialkylaluminium
ketones
RO;
and
the
oxidation
hydrolysis in
to
CL exhibited
chemical
(1)
excited of
reaction
into
groups
the
compounds to
by the
by an
CL maximum
attributed
their
on the
for
as
OAC.
interme-
duting
introduced
following
alkoxy
occurs
and
radicals
as well
of
processes
by the
and
their
(1)
organoaluminium
types
Accounting
from
the
all
oxygen of
was
solution
in
and
(C2~50)2A100C
From data and
in
[65]
decomposing
radicals;
strong
CL was observed peroxide
inhibitor
peroxides
were
the
colleagues
portionation
traps
an
with
OAC.
both
formation
spin
d-carbon
emission
the
mainly
his
and
process
by oxygen
The
of
the
related
CL emitters
products;
results
the
these
through
latter
OAC with
when
occur
no free for
for the
generated The
give
With
not
the
absorption
assigned group
at
of
reactions
oxygen
(4).
method
[56].
atom
to
of
peroxides
does
decomposition
ing
(15)
diethoxyethylaluminium
solution
a hydrogen
RH + >AlOR
CL intensity
chemiluminescent from
(14)
interaction
by the the
quenching
the
organoaluminium
(13)
(CL)
10
+ CH CHO +
+ h3 (>510
(Z30 nm)
i9m)
(1) (2)
30 scheme
TO shows
Intramolecular as the
and
and
to
in
of
its
light
/\
[601.
the
.
The
The
CL was
latter,
[58]
that
excited
aldehyde
later
on,
to in
ethyl
CL similar
to
later
the
stages
of
accumulated
reaction
of
water
bright
Reactions
With
less
(C,H~O)~A~OOC~H~
stable added
intermediate,
to
the
was which
all,
OAC with
due
is
to
the
OAC violently
Li[AlH4]
the
identified
resulted
to
+
the
third
amount
high
of
Al-C of
(C2H50)2A100C2H5 of
while
with
water
bond of
selectivity
peroxides,
water,
c,ti500~
introduction
reacting
CL in
autoxidation
water.
CL was observed
as well
to
f48].
dioxetane,molybdenum
another
or
from
the
adamantanone
neither
in
excited
state
its
the
ground
of
is
of
red
spectral
intermediate
in
the
(no
longer
An unidentified curves
(i-C4H9)2AlH
peroxy
CL was
in
known CL [TO]
state
(CL
oxygen
Usually,
new type
as
singlet-excited
found
(c2h50)2
an organoaluminium
other
OAC peroxides
(i-C4H9)3Al,
in
arise
interest
with
powdered
with
differs of
kinetic
by stable
complex,
originally
adamantylideneadamantan-l,Z-dioxetane(AAD)
(C2H5)3A1,
was
nm).
and
peroxides.
of
entirely
mainly
of
of
can
special
a few
dioxetans,
ion
First
through
as another
brutto-stage
(C,H50)2~T~~i
described
exactly
than
organic
~20 -
Of
involves
Upon contact
react
acts
water
(C H ) Al oxidation with 02 when 253 suffers oxidation and a sufficient
[60].
solution
3.3.
c
above
triethylaluminium
less
deactiv-
passes
illustrated
with light
is
(2)
hydroperoxide.
(C,H~~)~A~OOC,H~
in
by
be observed
aldehyde,
(A=510
time
The (C H 0) AlC2H5 reacted with 02. 25 2 be the hydrolysis of that OAC autoxidation
is
P2 which
first
solution
at
CL pathway
luminescence
and,
acetaldehyde
unexcited
second
the
CL can
gives
with
product
for for
products.
group
together
(1)
nm.
responsible
(C,H50)2AlOOC(CH3)3
unidentified alkoxy
state
P , and an excited
CL emitter
With
for
peroxide
compound
Upon OMC hydrolysis, peroxide
the
(max)=430
intermediate
unidentified
stand
excited
al umi nooxane
emit
unstable
P2 which
oxidation
CL emitter
alcohol, ated
p,
FL at
410
and
for
CL revealed
solution
after
metal
complexes
region
their
react
to
maxima
reaction with
not
absence
was assumed
the
and CH2C12
during
does
as shown by the
in
That
the than
result of
is
CL
reaction) 410 from
emission
nm). the at
CL emitter,
formed
nor The
in
its
CL is
emission 1270
of
nm.
since
no FL corresponding
the to
CL
[63]. OAC in
the
OAC as
[63].
thermolysis
be the and
such
upon AAD thermolysis.
nm after
wavelength
region
toluene
exhibited
CL emitter
discovered with
the
absence
of
oxygen
to
be
31 emit
no
light
that
complex
[71], to
by a molybdenum which
(ca:
but
give
CL.
peroxy
dioxetane.
CL was
(CH3)3COOH
and
the
about
result
[551,
three
of
is
higher
for
161.
brighter
for
luminescence
the
In
peroxy
and
[6]
the
displayed
enables
intensity
of
by those
OAC
(i-C4Hg)3Al with
in
reaction
(C2H5)3Al,
peroxide,
which
by the
compounds
group
) AlH can be oxidized
CL displayed
reaction
benzoyl
yield
by arylcarbonyl-containing
i.e.
to
(C2H5)3Al
peroxide
times
a bound-to-metal
comparable
registered
benzoyl
of
(C H ) Al and (i-C H 253 492 in toluene to emit light
Thus,
complex
with
is
existence
1D8photon/S*mo’e)
with
flash
the
is
supposed
as opposed
to
the
CL
evidently CL emitters
their
alkyl
analogues.
3.4.
Reactions
of
CL in
reaction
reported
the
in
OAC with
[72]
xenon
of
and was
tomass-spectrometry
methods
the
of
The
principal
bonds
to
consequent of
the
these
solutions by the
activity
H>R>OR>C I
of
the
one
active
the
free-radical
elucidate their
involves
degree,
at
in
via
reacts
the
an OAC aluminium
main mild
chroma-
of
excited
emission
states.
OAC active products;
fluorination
with
C2H50-Al
reaction
atom
NMR, and
the
as the
XeF2
was originally
mechanism and
attacking
prepared
ethoxytaluenes
FL,
the
ground
XeF2
be efficiently
To a less
the
with
of
than
bonds
products
decreases
as
[73].
in
the
series
was
K,
1)
[77].
found
The and
when
an NMR probe.
multiplet
polarization
fluoride,
and
butane
of [77,
the
XeF2,
(2~0.2),
derive
kinetic
parameters
model in
;
to
781.
lower
During
methylene
more
latter
lo-15
protons
and was
galvinoxyl
1 iberation
set,
[48].
shown
chemically
the
ethylated
to
the
be of overall
induced
dynamic
discovered leads
(Fig.10)
(C2H50)2AlC2H5
of
(2.9+0.2).‘0-’
possessing
and
was originally of
gas
and
derived
kca’/mole
galvinoxyl,
as by the
of
constants
(C2H50)2AlC2H5,
detail of
introduction
solutions
rate
~a=6.5*0.2
compound
effect
the
the
(6.7+0.2).10-’ and
as well
(C’DNP)
CL decay
was
with
inhibiting
(Table
XeF2
were
investigated
effect
usually
to
respectively, of
by the
products
in
CL decay 233
reaction
bond,
effect
method
(C2H50)2AlC2H5
of and
the
convenient
XeF2.
curve 262,
with
directly
most
of
type
OMC reactions
mixed
to both
toluene
by CL,
OAC derivatives
of
polarization
CIDNP
reaction
by XeF2.
of
Al-C
composition
abrupt
in
presence
reaction
The mechanism
The
that
OAC can
out
from the linear M-ls-1 at 293,
nucleus
species
substituents
OAC reactions For
[5,6,72-801
the
CH2C12 and
[73].
CL turned of
in
investigated
fluorine-substituted
1y,
confirmed The
mode of
give
XeF2
extensively
and
composition
difluoride.
OAC with
and
a more
[761. XeF2
PMR spectrum toluenes,
to
for
were
showed ethyl
32
s
10
I
I
+P
800 --
\
t ,min W,ml
‘\
-3 2
-1
Inhibited CL (1) and gas liberation (2) with the addition of galvinoxyl upon autoxidation of 0.02M diethoxyethylaluminium 0.01 M xenon difluoride in toluene, 201 K [94]; _ points galvinoxyl additions; V(m1) - total amount of gases.
Fig.10
For
(C2H50)2A1C2H5
region radical
with
its
(XeF’)*
oxidized
(Fig.11)
400 Fig.11
by XeF2,
maximum at
450
the
CL spectrum
nm and was assigned
is to
in
the
t. : 350-550 emission
of
0.000 2M by of
nm the
[79].
5oo
A ,nm
CL spectra recorded in the reaction of diethoxyethyialuminium with xenon difluoride (I-3) [79] and CL spectra for XeF* emission generated with laser illumination (248 nm) of Xe+Fs mixture in liquid krypton 182,831. (1) in toluene; (2) in methylene chloride; without solvent; (4) dashed line is for the emission component X) of XeF” recorded in the background of Kr,F* emission.
33 Table
Compositions
1.
and yields
of
l.l4~lO-‘M(C2H50)2AlC2H5
with
Yield,
0.90
1.94
0.10
45.0
97.0
0.97
5.0
products
excited
of
states
reaction
with
be described
the
in
0.22
products following
reaction
toluene
0.20
65.5"
100%. Traces method, traces
its
in
the
of
300 K.
at
%
23.5” as
in
XeF2
XeF,,
0.15
97.0
that
can
of
r a c e s
T ‘ he total sum of products was taken detected by chromatomass-spectrometry traces of n-C4H,G by GLC. The mechanism
5.7.10-*M
mole/mole
t
formed
0.025
0.08
of F-toluenes were of C2H5F by CIDNP,
formed
in
their
ground
-s
>Al-F
XeF’
f
XeF2
-
+ XeF’
+ >AI-C2H5
. [>Al-C2H5.XeF2]
[>Al+-C2H5*XeFi]
(1)
25
>Al-F
(2)
+ Xe + C2H5
CH
H3 + Xe _
+ C6H5CH3 eH
2 ‘ ”6
11
-
+ C H -c
F XeF’
-
and
scheme. Scheme
>Al-C2H5
tr
4.02: 7.0"
3 + H’
F
(3) (4)
+ 2 ‘ ”4
(5)
n-C4H1 0
.
g ‘ HsCH2 C2H6 + C6H5CH2 C ‘ 2H5
C6”5CH2CH2C6H5
(6)
+ CH3C6H5 CH3 C2H5 + o- ,m- ,p-C2H5
I,
. L-
g ‘ HgC H2
CH3 (7) CH
3
C6H5Cti3+ o-
(8)
34
CH
‘2”5
SH5
-
+ C2H5
C2H6 + C2H5
3 (9)
C2H5 CH C6H5CH2 + CH3C6H5 -
XeF2
3 -
C H CH 65 H
+ H20
-
C2H5 C6H5CH2-C6H4Ct13
HF + 02 + Xe
-%
+ XeF2
z3@
‘,@“1
HF2;“.“F
C6H5CH;
acH3
(12)
+ 2HF + Xe HF
+
HF2..
.XeF -
C2H5CH3
(10)
(11)
. C6H5CH3 “bH C6H5CH3
+ C2H6
.
C6H5CH2F
+
C6H5CH2 + HF + XeF’
-
C6H5CH2
(13)
C6H5CH
-CL
C6H5CH2-C6H4CH3 (14)
C2H5 + XeF2 C2H5
+
.
in
C2H5
C2H5F +
In’
-
the
presence
of
2C2H502 C6H5CH2
+ O2
reaction
give
cation-
[ST]
in
disappear (2).
The
traces
of
nm)
(15)
(17)
c2H50;
>
(CH3C<‘)” H C6H5CH20;
with
(19)
anion-radicals
starting their
reaction
of
ethane,
(1). the
interactions these
Intermediate ethylene
+ C6H5CH20H
transfer
OAC reduces
during
“-
H)
electron
(18)
+ O2 + C2H50H
//O (C6H5C\
and
(3).
toluenes
(450
oxygen
-
starts
the
h@
(16)
-
2 (C6H5)CH20;
The
-
C2H51n
‘2
l
(XeF’)A
radicals
from
OAC to
A complexed yield
of the
with
toluene
radicals
(4))
and
butane
closest
react (5);
electrophilic
spiroaluminooxane
radicals
with
C2H5
+ O2
XeF’; AI-C
gives (i) (ii)
with
to
structure probably
bond of
the
traces
of
fluoro-
other
to
yield
only
with
they
XeF2
each
toluene
at
OAC
the
35 side
chain
ethyl-
to
(7,8)
give
dibenzyl
(6)
and
and diethyl-toluenes
.
two processes.
The
radical
ethylmethylcyclohexadienyl
C I DNP data,
forms
(8) radical.
The
can
The
radical
suppress
[79]
is
for
pairs
the
of
reaction
at
(17,18),
radicals
result
3.5.
but in
may result
Reactions
of
A visible
bluish
exhibited
and
in
the
OMC. Triplet-excited identified escence
as for
the
the
CL emitters
individual
[Fog.12)
[85].
with
oxidation
only
a long
(both
wavelength
components
length the
the
component stage
of
i.e.
presumably
species [67,6$]. of
arises
of
the
>MO2 are
Earlier,
compounds
exists
such
bands
at
emission
(500-650
nm)
as
reaction
the
oxygen
of
those
up to
increases
in
CL decay
the
in
the
the
responsible The
due
the
released
inhibition
to
the
occurrence
from
the
main
of
process
peroxy
by excited
benzal-
such
B-C
[84,85].
bonds
in
those
cyclooctanone of
CL and
solutions
as
were
phosphorafter
spectra
in
THF
is
CL kinetic
maximum,
with
a monochromator
registered filters);
later,
intensity
a short
so that
it
wave-
prevails
at
(Fig.12).
. That
in
statement
classic
202
was
borohydride, 547
(15);
balance)
(g-BBN)
spectra
CL emitter
the
of
additions
(19,ZO).
and
of
change
glass
emission
styrene
radical
B-H and
the
with
CL is
in
c-complexes.
boralkylhydrides
pinocamphone
Thus,
>BO;
[86-881.
in
Emission
active
of
met
520,
since
C2H5 away
CL.
through
as zirconium 490,
all
agother
radical often
the
emission
and
ditolyls
intermediate
disproportionation
oxygen.
time.
sloping
there
the
by matching
be seen
gently
Therefore
radicals
with
of
component
can
asymmetric
[82,83].
An interesting
reaction
benzyl
are
of
ketones
observed
or
(7)
nature,
of
reaction
such
the
ethyl
g-borabicyclo[3.3.1]-nonane
ketones
latter
the
bond energy
autoxidation
oxidation
give
the
to
by galvinoxyl
brighter
CL follows
to
give
in
according
X transition)
[02]<10-4,
boralkylhydrides
and
CL emitter
B-state
the
a similar
diisopinocampheylborane CL is
the
the
a somewhat
from
(9)
related
diffusion
nm (B--c
at
another
by the
diverts
ring
with
to
formed
[78].
is
excite
450
Oxygen
by reactions
dehyde
to
aromatic
the
ring
also
which,
of
their
and CL suppression
(16).
can
terms
(XeF’)*
sufficient
liberation
in
aromatic
being
radical pair
as calculated
luminescence
gas
the
CIDNP signals
radical
the
diethyltoluenes
reveal
the
Cal/mole
quite
of
of
formed
excited
(ca.79
a radical
rationalized
completely
The energy
further formation
be also
at ethane
C2H5 attacks
d-complexed
(10)
(iii)
(g),
nm were Besides,
THF
recorded B2H6, in
we have
addition
to
is well-reasoned.
schemes
found
(in
for
The
OMC autoxidation
upon gas-phase and the
H3BC0, long
established
ketones),
oxidation
with
B-H
bonds;
wavelength that
the
long
36
400
600
500
h,lJsl
1
0
1
$0 .2
J
c .-
0
301 201 101
% Fig.12
inherent
IU
b
t,mrn
Spectral assignments (T-8) and kinetics (9) of CL upon autoxidation of 9-BBN in THF [85]. (1,2) FL at 298 K and phosphorescence at 77 K of cyclooctanone and the solution after 8-BBN oxidation, A (excitation)=320 nm; (3,4) CL for O.lM 8-BBN in benzene and toluene; (5,8, 9) CL for O.OlM 9-BBN in THF; (a) and (b) with air bubbling on and off, respectively; A3, CD, EF, GH-sections of Curve 9 for spectral measurements 5-8.
wavelength length
4
component
one. in
boralkylhydride
At the
the
of
CL
is
same time,
gas-phase autoxidation
quenched
by oxygen
the
quenching effect of oxygen is al50 ?: by BO; [86,871. The mechanism of
strong
CL exhibited is
described
within
more
the
than
the
following
short
scheme
wave-
1851.
37 Scheme
R\ B-H
+
02
R\
OOH +
Rs R R
OOH +
>
R\
R’
B-H
-
R\
BOH -
80’
+
RLB. HO’ R\
0
BOH +
02
+ O2 -
(4)
(5)
R\
-
(6) +
R’
RO’ 2
(7) ROO\
R\
+
.
R\
R’
RO;
(3)
2 -Ho/BO;
HOHBo’
R’
R\ HO/BoH
HO/
R
-
+
R\
BOR +
RYBoH
+
+ R’
R R
R\
RNBo’
(2)
BOH
2R/ R
R’
R\
(1)
RkBCIOH R’
-
R’ R\
12
BOH + R’ BoH -
R’
(8)
R’
RO. ‘BOH ‘BOH R’
RO’
+
\OH R’
--K
RO; +
ROO, ,BOH ROO
In’
_
(14) L
ROH + O2 + 3(R=O)*
-
(where
(13)
ROOln
I R stands
oxidation
non-excited
(11)
(12)
R'
octanone
+
l -
BOH + O2 -
Upon
(9)
(10)
ROH
-
ROO,
2RO;
+ RO’
;;>OH
H
+
RO; +
+ R’
R’
R
ROO
of
emission state
for g-BBN [89].
the by
O2
R=O
organic H2Cr04,
That
in reaction
ketone with
(CL
fragments we
(15)
CL
observed was
earlier
H2Cr04
[go].
quenching) of CL
boralkylhydrides) in
the
reported
region to
of form
cycloin
its
38 3.6.
Reactions
of
When water CL is
sharply
ered
reaction
the
most
peroxides
introduced
enhanced
The
lytic
organoboron
is
of
and
into then
gently
intermediate
obvious
source
with
water.
THF solutions drops
excited
CL spectrum
addition
was
provides
the
in
to
the
peroxides
states
sloping
with
water:
an
branch
region
simitarity
We believe
of
form
at
same spectral
of
reactions.
presence
water
measured
the
evidence
nescent
further
with
excited
state,
of
the
as
(ca.3
in
the
0
with
alkoxy
which
-0OH
“dry”
is
under
above
the
addition
ketones
the
considhydro-
of (that
of
are
group
and
difluoride.
peroxide
(C5Me5)2YbCl
[92],
Cp2Eu,
After
oxidation
Cp=C5H5. 935
and
more Eu(l
440
nm for
narrow
I I)
Cp2Sm,
of
(C5Me5)*Yb
FL bands
at
980
provides
to
with reacts
//O
in
its
of
hyroperoxides
additional
processes
a solution of
CL
of
boron)
support
simulated 9-BBN
for
via
after
its
yielded
CL in
oxygen,
water,
the
[89] Yb, of
Sm, and
ELI with
lanthanide
by the
ions
Ianthanide
of
organic
peroxides.
lanthanides
organics
Cp3Eu,
by 02,
CL in
reacts
a ketone
reaction
those
derivative
Hydrolysis
and
0
the
which
Besides,
phosphorescence
of
lumi-
for
<:
CL.
from
[91],
an alkoxy
upon autoxidation
both
+ ROOH which
to give
boron with
result
OMC CL emitted
the
That
followed
-B-OH
-OH + >BOH +
cyclopentadienyl
of
to
hydroperoxide
containing
of
discovered
0
cyclooctane
Reactions xenon
deactivated
CL mechanism.
cyclooctanone
A new type
attached
then
known to
water
bH
group
alkoxy
described
oxidation region
is
in is
organoboron
after
autoxidation.
pathway
-BOOR c HOH -
+ >BOR -
CIAC containing
the
for
by 02,
water
+ 02
min)
CL emitters
following
intermediate
a hydroperoxide,
the
Non-excited
into
with
9-BBN
bH
at
oxidized
conditions. The
3.7.
9-BBN
1891.
organoboron
of
of
{LO)
Ln”
such
and Cp9Sm [5,93,95],
broad
FL maxima
and Cp2Eu, nm for
of
the
respectively,
Yb(lfi)
and at
was
as
(C5Me5)2Yb,
where
Me=CH3
starting are
580,
(Ill)
LO
transformed
595,
613,
640
nm
(Fig.13). Scheme
13
:‘:
Cp2Ln(ll)
Cp,Ln(l
+ O2 ---c
L
CP h3
(LC)
+
/)Ln(lll) 0
_g&_
I I_)
quenching of ketones
(1)
39 CPOO, 3: 6Ln(III) 0
-P+
Cp3Ln(l
I I)
+ 02 -
cp*L:(III)
(I I I ) o’->L;(lll)
Cp2Ln
CPOO, &Ln(lll) 0
-
6\
+
-
I
oocp
oocp
+&j
,
oocp
(3)
Cp2Ln(lll)
I
+ hti (LC)
-&+d
I
I
+ hfl (LC)
P + >Ln(lll)
(5)
+hg(SC)
I
1COCP
(4)
II
+ h3
(LC)
(6)
I oocp (where SC -
The in
P stands long
for
a complex
and short
wavelength
processes the
resulting
scheme
ketones
above
effectively
as
quenched lanthanide
for
long wavelength
the
case
with
dienone with
(4)
disappears
other
identified
(KI
a possible simpliest
was
of
oxidation
which
With the
Cp3Ln,
emission
each
The above
of
responsible
except too.
as well
as
either,
possessing
the
its
reaction was
CL spectra
of
a peroxide cannot
rule
being
“red”
the
peroxide of
CP O~L~(I!l)
promoting
for
Cyclopenta-
in
organic
statement
is
yields
is
by a good match
products
oxides
The former
oxidation
of
A lanthanide
H20).
be capable
(1).
Further
dimerization
[93,95]
Cp2Ln autoxidation,
excited
CL.
be represented
CL of
out
the
divalent
Cp2Eu and Cp2Sm. example
the
of
reported The
(PEM) with
(350-450
an unusual
light
of
an argon
latter
matching Sm(OH)
the
long
is
also
in
reaction
by unoxidized
OMC with
of
water
Cp Sm with
3
ca.2.106photon/S*ml
water
CL spectrum
species 3
of
(0.5
atmosphere.
nm) and one
as its
CL displayed
emission
luminescence
an aliquot
Cp2Sm in THF in
CL.
stage
exhibit
the
by lanthanide to
of
[95].
with
Eu and Sm LO can
LC and
respectively).
deactivation
CL emitter the
of
are
ketones
during
CL-test
emission
THF [94,95].
short
FL of
among those
The first
ed
“red”
reaction;
lanthanides
water
, excited
oxides;
CL,
fast
component
participants
as the
Eu and Sm LO to group
“red”
and metal
of
LO (1).
peroxide,
rapidly
reactive
first
starting
organic
LE(III)
the
oxoderivatives
by the
excited
polymers
autoxidation
At
its
of
components
from [95].
and Li(III)
mixture
ml)
to
the
The CL spectrum
wavelength of
added
(-5
components,
Cp3Sm autoxidation.
excited
in
the
hydrolysis
min) 2.10m3M
consisted the
bands
Therefore, of
in
was registersolution of
of
two
of
the Si(lI
Cp Sm to 3
emit
I)
40
Fig.13
Spectral assignments upon autoxidation of cyclopentadienyls of ytterbium [92], europium and samarium [PS]. (1) and (2) - FL registered before and after oxidation of OLYb(l I), 295 K; (3) before and after oxidation of OLEu(l I), and (4) - FL registered 77 K; (5)- FL for OLSm(l t I), 77 K; (6)- CL for OLYb(L I ,I 11); (7) and (8)CL for OLEu(II I) and Eu(lf); (9) and (IO)CL for OLSm(lll) and Sm(ll); (6-10) - [OL]=O.OOlM, THF, 295 K.
THF solutions
of
Cp2SmC1 [5]
upon oxidation
by a toluene
three
No spectral
3.8.
minutes. Reactions This
year,
of
boron
CL and
along
with
solution
of
measurements hydride
FL were
complexes found
for
other XeF2. were of the
Eu and That
Sm LO exhibited
CL fades
rapidly
CL within
made. lanthanides complexes
with of
type
oxygen. NaLn(BH4)4-nDME,
41 where
Ln -
compounds, of
T%(III)
Sm(ltl),
observed
in
Pr(lll)
FL is of
THF before
(n=4),
extremely
the
state
and after
and Tb(lll)(n=3)
bright,
of
which
aggregation
oxidatian
with
[96].
is
caused
(either
With
Tb
by the
crystal
emission
line
or
02)(Fig.14).
Spectral assignments upon autoxidation of lanthanide boron hydride complexes in YHF 2961. (1) and (2) FL for crystals and solution of Tb before and after oxidation (3); (4) and (5) FL for crystals and O.OBSM solution of Eu before and after oxidation (61, 77 K; (7) and (8) FL of crystals and solution of Sm after oxidation, 77 K; (9) FL recorded after oxidation of Pr complexes, 77 K; (10,11,12) CL for Tb, Eu, SW, respectively, 298 K.
Starting but
the
irrespective
dissolved
Fig.14
Eu(lll),
solutions
on oxidation
and PF(II Before blue
I).
the
which
(max-465,
blue
FL vanishes,
blue
FL of of
give
nescence by L?~(l!l)
the
those in
the
unequivocal it
emitters. ions
in
are FL is
region
decreases
spectra
its
very
Eu>Tb>Sm to
evidence
reactions
is
of
recently of
for
intense
red
FL is
of
the
&(liI)
ELI comp’lex.
band
in
the
very
weak.
the
red
FL of
EE(llf).
similar
to
the
FL of
Eu(lIf
02 yield
reach
CL the
zero
for
ions
L?~fIll)
[98a]
that
inorganics.
[97].
intensity
Pr complexes.
the
deepAfter
into
lanthanide
lanthanide
300 K and 77 K,
emission
obtained
The
with
reported
the
as an
77 K).
oxidized
to
results
transforming
ELI complex
was
the
no FL at
owing
revealed
300 K,
complexes series
exhibit
registered
interest
wi th 02,
the
THF solutions
FL is
02,
Of special
spectral
Thus,
Sm and Pr complexes
with
oxidation
oxidation,
of
as the
of The CL
tumi-
CL was emitted
42 3.9.
Reactions
of
cyclopentadienyls
of
uranium
(IV)
with
oxygen
and
xenon
difluoride. Upon oxidation for
Cp4U and
orders
of
of
uranium
magnitude
with
XeF2
suggested
for autoxidation 4+ XmCpnU for short (X=
as
organics
(UO)
[48] and for
Cp3U(n-C4H9)
than
of
with
02.
uranocenes
Cp or
Cl;
by 02 and
Cp3UCI
[98].
The
XeF2,
CL is
fol lowing
Cp4U,
Cp,UCI,
Cp= C5H5;
m +‘n
CL was
found
brighter
by two
CL mechanism
and
CpUCl,
is
designated
= 4). Scheme
4+ XmCPnU
+30
. ‘02]
ixmcpnu4+
-
2
/H-S
14
__L
I
(1)
Is*
I
[xmcpnu5+ . 0; ] +
-
(2)
HS-solvent
_ +
xmcPn_2uo;+ + C5H6
I
(3)
X_Cp_lJ*+OOH II,
II
(HP)
L--- +:
$_
0
xmcpn_2bo;+ -
0
CL
(5)
C5H6 + ‘2 LI According
to
state
of
state
with
to
U(V)
extracted
from with of
emission
(4).
above
decomposition HP gives
is
in
with
complete.
since The
by the
radicals
follow
the
influences
appear
of
of
at
absence
stage
those
(2),
result (5)
of the
from
“dark”
[Sg].
the
or
is
C5H6
is
emission
of
uranyl
Uranyl not
is
shown
of
CL
in
of
at
also at
the
uranocenes of
effectively
autoxidation addition
with
upon autoxidation
oxidation
are
decom-
deactivated
oxidation
[99]
their
because
processes
which
triplet
oxidized
atom
Simultaneously,
which
maximum.
the
the is
uranocene
products
bonds,
until
which
singlet
FL characteristic
CL spectral Cp-U
the
into
a hydrogen
(HP).
group
UO [99],
uranium(lV)
Next,
a solvent,
uranyl
intermediates the
that
hydroperoxide
the
mechanism of
from
of
transformed
uranyl-containing
ketones
hence
is
(1,2).
registered
reaction
free-radical neither
of
autoxidation
result
presence
oxidation CL is
excited
by C5H6 molecules, Though
of
region
further
i .e. of
by the
the
the formed
an excited
formation [98]
is
(D),
the
scheme,
catalyzed
donors
The
“dark” complex
with
ion
the
77 K (Fig.15)
for
intermediate
transfer
the
demonstrated
excited
obtained
an
a superoxide
position
was
data in
electron
and
formed
the
oxygen
the
C5H6 quenched
CL spectrum. and
CL do not
galvinoxyl
(to
10m3M)
43
400 Fig.15
A ,nm
Spectral assignments upon autoxidation of uranium(lV) dienyls [98]. (l-4) FL registered after oxidation of (4) FL for hydrolyzed oxidation Cp3UC1 (Z), CpUCl (3); Cp4U in 5M HCl; (2) CL for all uranocenes, saturated in THF, oxygen bubbling.
4.
CHEMILUMINESCENCE
4.1.
Reactions
PERIODIC
immediately rapidly
of
silicon
at
(C2H5)3SiCH2=CH2 peroxides
The
luminescence
CL of
OF FOURTH GROUP METALS OF THE
of
up to
for
that
weakening
argon
containing
toluene
6O”C,
is
of
of
originates A strong
of
the
reagents
only
traces
of
of
No CL is
the
the
is
displayed
CL is Q2.
air
of
in of
CL decay
effect
with
inertness
reactions
magnitude
the
exhibited
of
when
Thus,
difluoride.
solutions
quenching
CL.
xenon
by XeF2,
shown by a gentle two order
and
(C2H5)3SiCH2=CH2
because
because
turns
HSiCl 3.
of
and
4.3*106photon/s-mole
j*106photon/s-mole
solution
oxygen
two minutes.
mainly as
with
(C2H5)6Si2
within
Weak CL of
con
organics
contact
20-85% even
(C2H5)6Si2 O,[S].
of
after
to
OF ORGANOMETALLICS
cyclopentaCp4U (l), product solutions
TABLE
Upon oxidation
of
600
500
after
the
five-times
that
O2 is
brighter
of
of organosilimaximum
XeF2.
through one
fade
OMC towards
reaction
kinetic
with
bubbled
of
to
O2 and
intermediate
brighter is
the
CL arises
Very
a toluene the with
[S].
weak
reasons bubbling
44 4.2.
Reaction xenon
ions
germanium,
and
titanium,
tin
organics
with
oxygen
and
difluoride.
Upon oxidation
by O2 and
of
(C2H50)3TiC6H5
such
(3.0.107), the
of
OMC as
(C2H5)2GeH2
phton/s-mole
-
values
XeF2,
CL was -
recorded
2.6.108(7.2*108), are
given
[5,6]
8.3*108(6.8*10g), (CH3)6Sn2
for
the
for
toluene
(C2H5)6Ge2-
solut-
1 .0*107
2.5.106(2.8.108);
maximum CL intensities
with
O2
(XeF2). In in
the
match
course
of
region
of
400-500
with
stable and
the
the
but
tin
autoxidation nm with
CL spectrum
unidentified
organics,
its
CL can
broad
measured
product be
(C2H50)2TiC6H5 maximum at
by the
of
flow
at
THF,
450
method.
autoxidation
recorded
in
emits
higher
FL is
displayed
nm giving
a good
This the
implies
CL.
temperatures
With
that
a
germanium
(60°C)
only.
CHEMI LUMI NESCENCE OF ORGANOMETALLi CS OF FI FTH GROUP METALS
5.
OF THE PERIODIC 5.1.
Reactions
of
Reactionsof fading
(ca.
(C2H5)3Bi CL of
CL of
) Bi with
OF THE 6.1.
XeF2
and
With
the
and
oxygen
and
xenon
difluoride.
with O2 in toluene give rapidly 7 photon/ssmole intensities,
2.5.10
of
air
cyclopentadienyls
through
as a reaction to
the
phosphorescence
to
(>6DO
weak
fade
in
the
GROUP
reaction
of
METALS
intermediate.
ketones
as
were
to
are
displayed
difluride.
solutions rise
a minute
(Imax=
[loll.
Cr(lll)
wavelength
transformed
xenon
toluene
by emitting
which
CL was
that
they
within
short
ketones
since
and
THF or
caused
The
by excited
Cp-rings,
oxygen
CL was observed
rapidly
was
hm)
with
-1.5*10V3M
C5H5CrF,
and
emission
of
1.5.10-2
or
compohent
chromocene
exhibited
OF ORGANOMETALLICS OF SlXTH
chromium
bubbled
CL red
is
TABLE.
(C H ) Cr, [C5H5Cr04], 65 5 2 6.10 -8-10~ photon/s.mole)
assigned
with
(C2H5)2BiF
l_0.108
of
involved
(C2&_)2BiF
[48].
PERIODIC
Reactions
The
and
3.4*108photon/s.mole
CHEMILUMINESCENCE
6.
Bi
[5,48].
Brighter (C H 253
TABLE.
(C2H&
2 min)
respectively
of
of
which
CL (425-575
products in
of
the
further
nm) was
oxidation
region
into
is
of
C,0H,004
[1021. In ion
of
formation similar
agreement
with
the
results
(C H ) Cr [102] 552 of unexcited
and
those
to
that
which
on the for
and excited was
given
CL and products
for
mechanism
the
FL of can
CL with
of
the
“dark”
chromocenes
be accommodated uranocenes.
autoxidat-
[loll,
the
by a scheme
45 Scheme cp2cr2+
donor
+ 02 _
H’ -
ICp2Cr 2+.
Cp,Cr3+00H-
-
‘02]
-
C H 56
h’)
[Cp2Cr3+.0$
+ $3;
15
__c
(1)
(2)
l--
(>600 nm) + [CpCr3+014
h3
(3)
(BT)
3+
[Wr
Ol,,4
C5H6 + O2 -
hJ
Excited as
is
generated
oxidation
from
Since
the
the
oxidation,
by the
transformation
CL was
6.2.
displayed
of
observed
believed toluene
is
that
CO among
743
cm-’
6.3.
since
in
the the
give
Reaction
of
CL reaction proceed
with
and
the
its
(4)
CL is
by
intensive
for
W(CO),
with
of
W(CO),
concomitant
the
with
the
excited
as well latter
ketone
region
oxygen
within
also
[loll.
difluoride. weak
.
CL
FL is
and a carbon
room temperature
in
bands carbonyl
for
the
Mo(CO)6 That
respectively. The
appearance
of
nm)
and xenon
molybdenum
liberation.
(those
substitution
(~600
the
Mo(C06). at
the
lmax=l.5.107
toluene;
a minute
photon/s*mole,
gas
CL was
THF or
of C6H5CH3Mo(C0)3,
rapidly of
of
in
with
observed
and
xenon
gas
(2)
(BT),
emitted of
intensity
(60’~)
with
reaction
with
also
spectral
n-bond
3.6.107
products
evidence
is
the
fading
and
after
(HP)
tetramer
formation
derivatives
1.105
solution
blue
concentration
registered
by XeF2,
gaseous
the
a toluene
weak
no CL is
hydroperoxide
the
wavelength
through
O2 attacks
in
by XeF2,
reagent
shorter
Mo(CO),
Upon oxidation
bond)
(C5H5)2Cr
bubbled
C H CH Mo(C0) at 65 3 3 process is accompanied
and
nm)
CpOOCrO.
(9.1 06photon/s.mole),
ring,
(>6BO
Cp2Cr.
assume
peroxide
the
and
MO-F
of
CL component
should
1.6.10-3~ in
Reactions When air
is
of
decomposing
bonds
wavelength
of
with
Cp-Cr
oxidation
one
Upon oxidation
by the
of
dosed
short
tetramer
photon/s.mole
h$
nm) +
Cr(lIi)
by further
-
cat.
(425-575
resulting
“3+ [CpOOCr 01 ,,4
+ O2 -
of
presence bands
being
of
at
727
inherent
CO groups
Xe and to
the
by fluorine.
difluoride.
XeF2
liberation,
was originally precipitation,
described
in
11031
and multiple
to
colour
46 The
change5. ground
and
reaction
excited
products
states
W(CO)4F2,
as shown
Xe,
by the
CO,
CO2,
following
WF2 are
scheme
formed
in
their
[103-1061. Scheme
W(CO)6
f
xEf*
-[W(C0)6*XeF2]
W(C0) -r:
+ CL,
W(CO)5F
-
complex
[W(CO)5F]“.
‘Y,
CL 3, (12)
w(co)6 CL,
with
start
tration ing
to
effect
and
XeF2.
and
gas
was
were
(8)
(10)
3
CL5,
The
first
+ CL
(12)
5
a maximum at
time
magnitude of
traces
the is
[106]. of
An
derivatives
was
emitter
give
rise
of
to
the
brightest
lower
than
CL,
in
induction are
a certain can
long
the
waveseparate-
luminescence among those main
reaction
induction
period
(appearance
on the
reagent
period
exists to
at
earlier
dependent
difficult
be
emission
conducted
of
reaction
The
the
intermediate
intensity
reversibly
which
to
XeF2(1),
give
(5). of
nm. The
medium).
CL emitter
By experiments [105]
the
its
to
(3).
carbonyl
and 533
lit
decomposes
deactivation
unidentified.
reaction
electrophi
states
primary
W(CO)5
established
of
stage
to
cat.-
to
excited
the
with
liberation)
water
(11)
fluorination;
assigned
though
temperature of
complex
(9)
carbonyl
their
attacking
have
two orders
of
red
(13) of
the
in
remained
(9-12)
was
in
FL exhibited
[107]
CL4,
(6) (7)
F-derivatives
tungsten
W(CO)5F XeF’
CL component
reactions
CL2’ CL5
with
in
length
------
WOF4 + CL
stages
from
CL spectrum
The
described
+ CO
WF6 + CO
toluene
formed
molecules
the
(5)
C + CO2 (traces)
transfer
generated
+ Xe(XeF’)
+ CL, (540nm)
HF + Xe + 02 + CL4
. . . - successive
electron
nm in
Ha0
-
WH HF6
cat. tOC
intermediate
540
cells)
+ toluene
(where
W(CO)5F
WO3 + 6HF + CL2
+ H20
co + co
. . ,-
(WF * toluene) 6
WF6 + SiO(glass
of
:(3)
(4)
-
W(CO)4F2
-
-
WF6 + 3H20
also
__c
+ XeF’ (XeF2)
WF6 + toluene
portion
nm)
F + Xe + CO
5
[W(CO+F]‘:
+ XeF’ (XeF2)
W (CO) 4F2
After
(540
+ XeF’
---II
XeF2
(1) (2)
W(CO)5F
W(C0)
XeF2
-
+ CO
F + XeF’
IW(Co55F]-~.‘h -
W(CO)6
. XeFi]
[W(CO)t
-
16
due
remove
to
from
the
of of
conceninhibi
toluene.
t-
47
WQ, on the other At ly
higher
recorded
effect
is
is
hand,
followed
caused
swept
end
argon and
point
falling
7.
phase
by the
of
the
drops
from
refluxing
and
the
Reactions
of
benzoyl
in
product WF6 which
reaction
a
in
catalyst
was called
(Ar
reaction
makes
solvent
The CL flashes
This
is
the
are
the
drop
thus
“drop-flashed”
usual-
[lob].
WF6 circulating
medium in
flashes
is
the is
atmosphere
condensed
formed
at
the
by the
CL [lob].
SYSTEM.
and
organics
brightness to
with
(photon/s.mole)
the
02 and
oxygen,
CL with
xenon
in
(6.0.10~)
in
the
manganese
dependent
presence
XeF2
decreases
C6H5MnCl
of
be appreciably
to MN and
OMC with
02)
light
CL which
OF ORGANOMETALLICS OF SEVENTH GROUP METALS
[5,6]
attached
(with
maximum of
reiterated
dissolved
unit.
manganese
The existence
ligand
kinetic
difluoride,
and
peroxide.
described
manganese
of
system; the
effect
initiator.
the
volatile
the
subsequently
OF THE PERIODIC
ly
highly
flow
is
as an
(55’C),
of
CHEMILUMINESCENCE
7.1.
acting
by a number
by the
solution-gaseous
oxygenless)
is
temperatures
of
organics
on both
an Mn-Mn bond.
toluene
and CH2CI2,
following
were
the In
the
original-
nature
of
reactions
the
of
CL brightness
series:
> [(C6H5)3Mn]Li
(2.0-10’)
> (C5H5)2Mn
(5.107)
> Mn2(CO),0 (0); (with
XeF2)
Mn2 (CO)
1o does not
Cp2Mn is XeF2
(C5H5)2Mn
at
half the
and the
CL not
bony1
introduced
or
CH2C12
to
the
1s to occur the
specific
quenching
effect
1 i berated
toluene
solution
of
Mn2(CO),0
reacts
with
the
1 iberation
bands
at
quite
the
Such
of
CL in
reaction in
about
reaction rate
seven
of
(60% of hours,
the while
with
calculated that
nm.
gas In
reverse, of
[103]. rise
(Xe,
this when
XeF2
a phenomenon
Mn-Mn bond
Mn2(CO)10
of
345
solution
C H Mn(C0) does not quench but gives 5 5 3 to XeF2 reacting with the substituted
owing
low
of
(0).
a minute.
but,
quenched.
> Mn2(CO),0
a 1.5*10-2M
than
chemiluminescent
CL is
The absence
with
fai into
background
of
whilst less
Mn-CO absorption
the
addition
to the
02, in
(2.2.107)
band as shown by the of
only
> C5H5Mn(C0)3
with by 02
metal-carbon
however,
flash
react
oxidized
disappearance
is
(4.108)
in
carbonyl
amount was
of
car-
toluene
the
a luminescence C5H5-Mn
XeF2 was ascribed
process
the
was ascribed
Indeed, to
CO) case,
gas
bond. in
[481
COcXe was
seven-times
faster
C5H5Mn(C0)3). By analogy
we assigned
the
with red
the
reaction
CL exhibited
of in
C6H5MgBr with the
reacti.on
benzoyl
peroxide
C H MnCI+BP
65
to
the
(BF)[47], emission
>
48 by
[6,48].
(Ph3C’ )j’;
reaction either
Now, to accent
for
the
results
Ph CNa+O 2 [lO,ll], we wou’id rather 3 substituted derivatives of Ph C’, or
advocate
intermediates,
triphenylmethide,
Imax =3.4*106photon/s~ml
CL of DE+THF)
or
oxidized
by 02
to
was
originate
the
compfex
3
reaction
obtained
of
which
also
as a rapidly
CL in
alternative
Ph C- with 3 capable of
is
recorded
with
with
fading
red
PhMgCl light
of other CL[19].
(8.lO-*M
flash
in
(0.5
min)
[SSI. 7.2.
Electrochemiluminescence ECL originates
current)
electrolysis
throline for
or
the
of
of
by matching
the
wide
at
of
light
upon cyclic
of
3
ECL and
of
3
containing
[108].
FL spectra
AC(alternating
fat-ClRe(C0)
,I&-phenanthroline)
electroconductivity
580
fat-ClRe(CO),L. flashes
a CH CN solution
4,7-diphenyl-1
sake
maxima
(ECL)
as separate
The
the
(L=
O.lM
CL emitter
initial
L
(n-Bu4N)C104
was
complex
l,lO-phenan-
identified
solution
with
their
nm (Fig.16). Fig.16 FL(l) and ECL (2) spectra for rhenium carbonyl comp!ex in acetonitrile containing O.lM tetrabutyl-
*>-3 I_ P c2 +J c *_
jT!oJ
yZxZK:fZLYZ20
nm
-:I d 0 ,nm The
light
reaction
of
differently
charged
ion-rad’icals
generated
at
a Pt-
electrode. Scheme [fat-ClRe(C03t]+ -
[fat-ClRe
7.3.
Reaction
of
reaction
of
Volger
into
which
matched was
al.
the
linearly
CL emitter
for
CL excitation
1 Re (CO) 3L] ‘*-
with , (CO)~Re-Re(CO)~(phen) found
that
FL of
the
dependent was
with
upon addition
formed was
by Schuster
in
and water
the
during
described et
al.
to
primary on
for
nm)
hydroperoxide
of
and
Re(phen)(C0)3Cl, tetralin
bright
rhenium
complex
[IO91
aromatic
the
was
red
[TO9J.
of
The CL inten-
reaction. similar
trans-
spectrum
indicating
hydrocarbons,
slowly
rapidly
CL the
concentration
bimolecular
by a scheme
(580
chlorine.
boiling give
complex
the
[IlO]
h?
tetralinyl
hydroperoxide
al-tetralone
the
suggested
Cfat-C
-
Re(phen)(CO),Cl
tetralinyl
formed
sity
[fat-ClRe(E0)3L]’
(C03L] ’ +
et
decomposing
+
17
that
The mechanism to
that i.e.
CIEEL.
49
H Re(phen)(CO)$l
H
+
[Re(phen)(C03Cll+
H20 + [Re(phen)(CO)3C1]+[
1 )
0 I
O-OH
a3
[
Ii '---c
18
Scheme
O-OH
1 ’ /
I--
I--
co +
[Re(phen)(C0)3Cl]B
-
h3
(580
nm)
I> 03
Similar the same
CL was
responsible oxidation suggested
reported
peroxide
for
[log].
[k(bipy)3]*+
The emission
for the bright
CL which
catalyzing
of the above was
observed
the decomposition rhenium
complex
to originate
of
(CO) Re-Re(C0) (phen) by chlorine in DMF 5 3 by Vogler et al. in [ill] is as fo'IlowS.
[ill].
of
was
in the The scheme Scheme
(CO)5Re_Re(C0)3(phen)
a.
CHEMILLIMINESCENCE OF THE
PERIODIC
8.1.
Reactions
with
O2 and XeF2
CL
Table
+ Cl2 -
2. CL
OF ORGANOMETALLICS
Rh organics
[5,481
(Table
Intensities
and XeF2
OF EIGHTH
with
in reactions
oxygen
hg(580
METALS
of some
and xenon
difluoride.
OMC of Fe, Ni, and
Rh
(I) in Oxidation
(300 K)
in Tvluene
of Fe, Ni, and Rh OMC
by 02
(330 K)
[5,48].
I, photon/s-mole XeF,
1
(C5H5)*Fe
0.0
0.0
2
Fe(C0)5
0.0
1 .a406
3
Fe2(CO)g
0.0
1.0.105
4
[P(C6H5)312Ni
2.a.lo7
4.6.10'
9.2.105
2.4407
1.7*106
4.a.107
SitCH,), 6
(acac)Rh(CO)2
4
nm)
2).
OMC
no.
GROUP
-
TABLE.
of Fe, Ni,
is exhibited
+ [Re(C0)3(phen)CI]*
Re(C0)5CI
19
Si (CH3)3
Si (CH,),
50 Iron
carbonyls
solid
(entries
precipitate.
oxidized
by both
brighter
with
be assumed
bright
CL with
activity
of
5)
Electrolysis the
of
spectrum
of
the
(Fig.171
[1131.
of
ECL is
the
of
I
540
is
attack to
almost passive
of that
Ni-Cp
of
of
a Pt
to
yield
(entry
an order
on the
Xe, 4)
of
Ni-C
magnitude
1,
bond.
4 shows
platinum
(II)
CO and
is
XeF2[112
entry
complex
with from
FL spectrum
two -1.5
for
the
the
Less
h gher
Pt-C
complex. bond yields
to +0.85
the
eV.
The
same complex
(Wd2
I
I
620
660
spectra (exci
for O.OOOlM plarinum tation)= nm [ 1131.
580
to
bond.
changed
the
XeF2 bonds
towards
XeF2
ortho-metalated
a Pt-electrode similar
CL with
and Si-C is
bond
Pt
I
Ni-
CL which
the
a solution
potential
weak
its
compared
bond than
Electrochemiluminescence
ECL as
only
CH2-Si
from
(entry
Ni-Ph
emit
the
result
XeF2
the
to
Since to
reveal OMC with
reagents
XeF2.
CL can
8.2.
2,3)
Complex
A,nm Fig.17
The
FL (1) and complex in
ECL(2) DMF,
ECL excitation
ear I ier
for
scheme
the
ECL of
[113]
the
differs
very
little
organometallic
from
that
suggested
compl ex.
rhenium
Scheme 20 Pt(Thpyj2
+ e- -
Pt (Thpy);
Pt(Thpy12
-
Pt (Thpy);
Pt (Thpy);
+ Pt (Thpy);
In
the
presence
of
the
potential
actions
of
anion
e- -
of
-
10e5M K2S208,
changes Pt(Thpy);
from and
pt(Thpy):!
+
ECL was observed
-1.8 S20i--
to
0 eV. ion
with
This the
[Pt(ThpyJ21’
within
-
hd(58Onm)
a different
was caused subsequent
by the
range inter-
formation
of
51 SO,
species
which
take
latter
in
as
strong
an electron its
Pt(Thpy);
from
+ SO,
literature
reagents
with
Grignard
Indeed,
02-saturated
butyl
the
CL spectrum
while of
the
time,
upon
the
was
rhodamine
or
organic as all
fragment
other
etc.)
with
does
PhMgBr with
are
met.
band with
9-BBN
of
With
02,
the
of
the
420
with
9-BBN
a short the is
act
of of
with
increase
pyrene at
DPA.
(1.5-fold
10 -‘M
to
show only
of
DPA suggests
by direct
component
with
of
a long that
triplet-triplet
The
a
due CL is
the
wavelength
to
the
at
versa,
FL of
singlet
much of
DPA,
addition
state p(T,)
iS
+ A(S,)
of a new
DBA [48]. [85],
incorporates
reaction
of
series:
naphthalin
and
activated
CL
(unidentified)
with
and more
nm).
level,
the
incorporates
(max-560
that
hydrides
states
less
in
and
except
for
DPA than than
The peculiar
-
not
P(S,)
it
l&fold
no FL of
excited
an
emitter)
shows
the
of
one
the as
of
energy
in
spectrum
wavelength
singlet
the
CL spectrum to
that than
transfer nature
FL of
decreases
CL spectrum
transfer
in
the
penta-
course,
boronalkyl the
vice
10 -3M
is of
agents
amplified
component
activator’s energy
long
it
same as
The
CL.
the
(suitable
and and
[85,89];
increase pyrene);
the
the [55]
activating
the
rubrene,
the
CL intensity
for
two components:
wavelength
reactions
is
alkyls
At effect
rather
(C H ) Mg, the 372 CL spectrum
of
additions
[46].
energy
provided,
by DBA (Fig.18)
coefficient
observable We consider
and
the
quenching
10-3,
in
DPA [9],
indicating
of
the
band
of
with
any
by
to
second
reaction
CL activator
nm which
nm)
rather
added
derivatives of
(otherwise
oxidation
addition
as quenchers
shows
any
[47].
intensity
the
unchanged
chemical
metal
desired
are
activators,
of
to
the
(580
FL spectrum
absence
CL activation
aluminium
the
about the
introduction
rise
DBA>rubrene>anthracene>pyrene>DPA benzophenone
SO,
the
CL exhibited
(DPA)
remain
the
peroxide
the
activated
DBA.
with
give
oxygen
maximum at
effectively
FL of
in
of
9,10-substituted
course
hv
additions
bring
to
The
that for
of
to
luminescent
the
luminescence
Upon oxidation CL is
not
Thus, the
its
its
those
not
factor
requirements
DBA enhances
generate
-
activation
luminescent
stated
benzoyl
and
a determining
to
+ SO;-+
UPON CL OF OMC. LOW-TEMPERATURE CL.
on the
reported
transfer.
cene,
CL of
and
energy
the
anion
[Pt(Thpy)2]*
band matching
was
in
of
+
reported
that
generated
a result
the
was
publications
CL emitters
CL emitter
Pt(Thpy)2
9,10-diphenylanthracene
PhMgBr,
, anthracene both
-
complex
ADDITIONS
by various
same CL spectrum
chrysene
same
02
ether
SO;-
data
2.5.1t4M
of
another
--
existing
discrepant.
+ S20;-
state
THE EFFECT OF LUMINESCENT The
the
away
excited
Pt(Thpy);
9.
oxidizers
DPA
effect Only
+ k(s,),
52
5
lo
15
20
[A].io3,M
+0.2 i
-
\
1
0.1
% 38C CI .: 0) 34C CI t: .& 3oc cc 8c 4c 0
&
lg[Al Fig.18.
(1) dependence of CL intensity on DBA concentration (A) in autoxidation of 0.0068M 9-BBN in THF [89]; (2) linear representation of (1); (3) and (4) dependence of CL intensity on lg[A] for DBA and pyrene, respectively, in oxidation of 0.002 diethoxyethylaluminium by O.OOlM xenon difluoride in toluene [ES].
but also
via
the
formation
k+,) which
are
further
p(T,) and due
to
The above the
different
low
-
P(S,)
transformed of
+ %(T,) the
i(T,)
molecules
in
the
activator
-
+ W(Tl) scheme
for
effective
+ A(T,)
by the
reaction
with
triplet-state
ketone
at
A -
[P.A]“----w
triplet-triplet
P(S,)
annihilation
__c
[AA]“‘-
CL activation formation
+ B(S,)
at
high
i(S,)
its
excited
of
A
+ A(S,)
rationalizes of
concentration
the states
absence X(T,)
of in
DPA FL in comparison
terms with
activators. Upon autoxidation
too.
triplet-excited
?c
+ A(S,)
low concentration
of
of
)
i(S,
However,
of
DBA additions
Cp2Hg result
[53] in
and Cp2Cr only
[loll,
a slightly
the
ketones
amplified
are
excited
CL (2.5-fold
53 increase
at
distorted high
10-*M
due
to
DBA).
The
effect
of
DBA concentration.
low effective Cp-ring
The
energy
the
same type
Usually, observable found
the
the
of
DPA to
amplify
CL can
be identified
-10w3M.
curve
the
It
is
indicative
the
where
the
emitter
the
activator
activator it
makes
is
FL is
activators
in
are
that
there the
chemical
excited
in
[Sg]
10’3M
was
proved
for
of
The
the
ketones
We have
formed
XeF2
and
(Fig.18).
solutions of
1y
recent DBA,
with
[A]=
concentration dependence
(Fig.18).
is
That
a matter the
of
the
curve
the The
some difficulty
states CL.
p-terphenyl, nm).
of
same spectral
singlet
activated
FL (max=345
following
low DBA
CL activation.
emission
nm. With
its
of
by the
increasing
occupies
to
by the
products
a new type
concentration
DBA FL
appreciably
with
steadily
of
band at
anthracene,
reagent
CL spectrum
390
of
is
[ 1141.
found
usual
contribution
as
was
(C2H50)2A1C,H5
nature
displayed.
region
accounted the
1 O”M
CL (XeF’)*
maximum at the
CL is
that
wavelength
ketones.as
pyrene,
in
activator
an activated
a sufficient
observed
eye
from
nonactivated
as a sharp
occurs
ing
of
of
naked
the
short
derivatives ca.
p-terphenyl,
reaction
the
with
of
of
excited
anthracene
lo-‘M
the
CL matches
the
assignment
with
different
of
of
concentration
even
The measurement
activated
of C H with O2 in THF, where 56 autoxidation of Hg and Cr OMC.
the
interesting is
CL intensity
since
reaction in
with
of
shape
in
CL in
is
which
the
latter
as
activator
addition
dependence
from
CL activation
at
of
reabsorption
low amplification
The
CL observed
of
spectrum
transfer
transformations.
activated were
lo+
of the
region
of
With
an
pyrene,
spectral
singlet
broaden-
states
of
scheme. Scheme
A + XeF*(XeF’) >AI-R(R’) The
starting
its
cation
A+ + XeFi(XeF-)
-
>Al+-R’(R+)
+ A’ XeF2
A+(l).
by a molecule
of
or
the
The the
reaction
starting
(1) -
+ ii
intermediate
singlet-excited
A*
OAC or
21
CL
XeF’
is
oxidizes
generated
by another
upon
(2) the
the
intermediate
activator
to
reduction
-
alkyl
of
A+
radical
R’ (2). Upon autoxidation Ru(bipy)3C12*6H20 cation there
of
occurs
Ru(bip~)~Cl, the
CL,
complex established
OAC [62]
to
the
added the
maximum of
a redox *6H20
concomitamt
of
reaction
1 iberation
in
of
the
in
the
activated
the
the
water
toluene
gaseous
boralkyl gives
is
of
[Ru(bipy)3C1*(OMC)n], by a match
solution
which of
(insoluble
and
latter
of
hydrides rise
red
to
[115],
an appreciable
spectral
region
crystallization
and THF) hydrogen
with
and
emitting CL spectrum
the
of
to
amplifi(6ooi.15 the
nm);
solid
OMC involved,
formation the
crystalline
of
activated FL of
a soluble CL.
the
with
It
was
complex.
salt
54 Two mechanisms
were
and
[62].
“physical”
intensity
as
considered by the
the
Later
the
for
on
acceptor
that
differently
CL of
suggested
of
CL activation
in
[116],
energy
CL activation shaped
in
from
the
was
excited
had a chemical
kinetic
OAC autoxidations
Ru(bipy)3C12
dependences
shown
ketones,
nature.
for
so
That
activated
-
to
“chemical”
have it
the
can
lowest
be
was confirmed
and
nonactivated
OAC [62]. We are
rather
inclined
electron-exchanged
to
advocate
luminescence
the
(CIEEL)
mechanism
according
of
to
the
chemically below
initiated
scheme. Scheme
>M-R + 02 Ru (I
>MOOR
22
(1)
I ) + >MOOR v
I ).>MOOR]
[Ru(l
------r-[Ru(l
I I)*>MOOR’]
-
(2)
9:
I I)*(R-0)-l
-[Ru(I
(where
M -
-
boron
The organometallic (OMC),].
After
Ru(lll) from
(2), which
state
of
electron the
the was
a linear
with
catalytic
e.g.
for
CH2C12) with
[118].
(3)
intermediate
peroxide
for
ketone
the
of
ruthenium R=OL
to
of
CL intensity
[Ru(bipy)3C12’
radical-anion its
emission
feature
activated
complex
and oxidation
the
be reduced
peculiar
to
[63]
a bright
generation by the
peroxides
to
of
the
of
CIEEL,
divalent
excited
activated
CL.
i.e.
on OMC and
by the
Ru(ll)
+ XeF’
Ru(l I I)+ presence
That
existence
ruthenium
of
XeF2
following
[72],
luminescence
complex
the
in
of
chemical data
CIEEL metal
mechanism complexes
>AIR of
the
in
crystalloluminescence
[48],
the
crystallization
of
activation
of
luminescent
the
complex
for
a few
With
the
flashed
[$u(bipy)3C12(0AC)n]
[Ru(bipy)3C12(0AC)n] other
CL reactions
latter, like
the
activation
a burning emitting
in of
CL at
toluene
OAC, was
flame
so
[48]. 610
nm is
scheme. Scheme
The
to
solutions.
solution
and
In
follow
excitation
and
reported
also
a good activator
red
to
and
[ 1091
be possible
t10m3M out
observed
(C03)
OMC reaction
dioxetane
demonstrated
of
According
from
turned
that The
the
Re”(phen)
be assumed
complexes
effective
of
an
form to
CL was originally
A homogeneous (or
the to
responsible by the
decomposition media
Ru”(bipy)3CI
metal
CL
[48].
amplified
OMC CL can
forms
an electron
being
dependence
homogeneous of
accepts latter
to
decomposes
established
concentrations The
>MOOR (1)
transfer
complex
-
.Ru( I I)]
aluminium)
peroxide
Ru(lll)
(3),
mechanism
[R-O’ or
-
Ru(l I I)
___c
Qll)
strongly
oxidized
+ XeF-
(1) CL
radical
23
(2) XeF’
as an
intermediate
species
55 in
the
reaction
trivalent of
of
state
Ru(lII)
(1).
450
region
the
emitter
of
decrease the
visible
due
recently CL of
activated
in
the
slowly
at
The
of
the
the
dependence
of
Ru(ll)
by the
to
its
reduction
[Ru(bipy)3C12.(OAC)n]
Ru(bipy)9C12
of
in
the
453 nm
from
to observe K)
formed
of
surface
of it
nature:
melting
point
POSSIBLE Nowadays, research
ruthenium
of
the
[74].
of
at
500
at
500 nm.
reactions Thus,
(C2H5)3Al
anf
the
nm
with
emission
solutions
red
to
the
of
OMC
with
a
XeF2
in
luminescence
the
of
can
of
CL) to
the
as well
CH2 Cl 2, crystals.
The
is caused CH2ClZ
rate
due to
higher
high
by the (176
data
point [117]
100 K (the
with the
reagent
at
mixing
second
radical
Radicals
C H’ 25
tecnique solutions
The CL maximum at transition,
on the
maximum at of
so the
reagent
phase
activity
mobility
level
first
technique).
recom-
growing
occur.
exothermal
temperature
of
the
liguid
of
temperature
temperature,
CL decays
of
The
activity
increasing
77 K (the
chemical
growing
of
causes
The curve
maxima.
on the
transformations
under
[74].
temperature
With
as from
77 K (the
reaction
starting
temperature
chemical
nm)
reported
shows several
medium).
lower
was
CL (max=61B
reported
region
as other
freshly
190 K is
initial
i.e.
of
more
reagents
near
K).
USES OF APPLICATION liquid-phase
of redox
CL intensity
152 K; at
grinding
development.
was the
ligand
triethylaluminium
C2H5 increases,
frozen
of
sources
to
a concomitant
organic
.(C2~5)3.Alnl,
with
that
from in
increased
with
unique
solutions
involving
mechanical
crystallization
frozen
&J(lll)
and a new FL arises
chelated
the
low-temperature
low-temperature
the
in CH2ClZ
Et~(TTA)~phen
activated
possible
in an amorphous
reduced
subsequently
160 K marks
the
I)
the
lo-‘M
magnitude.
!
follows
up to is
of of
Eu(ll of
[Ru(bipy)3C12
of
EPR signals
CL intensity
FL of
95 K was attributed
processes
concentration
frozen
the
addition
OMC illustrated
95 K
C2H5 radicals
rate
result
at
which
of
binationof
of
of
excited
complex
The CL is
product
dependence
CL at
C2H5 radicals,
the
complex
for
temperature of
of
complex
be responsible
nm).
be one of
CL of
even
to
emergence
of
to
the
low temperatures
excited
of
10.
of
absorption
[89]
reaction
mixture
be registered
the
oxidation
CL is
O2 by two orders
CL (max=613
The
very
heated
presence
trivial
the
activated
presence
to strong
intensity
solution.
occurring
(200
the
observed
Low-temperature
of
in
9-BBN with
g-BBN was established
the
of
about
(& =14000). We have
the
brings
The emitter
CL exhibited
nm is
amplify
in
XeF2
by OAC (2).
Dark-blue at
OAC with
CL with The overaIl
OF OMC CHEMILUMINESCENCE OMC is results
growing
out
obtained
of
IN SOLUTION. its
so far
early provide
stages reliable
56 predictions
of
The
A.
ability
in
of
H ) 493 10 -8M
AI
or
analysis
air.
The
CL
intensity
The
above
approach
industrial
stage
the of
the
small
control
A few
11.
CONCLUSIONS. REACTIONS
time,
which
to
peculiar
reactions
of
as
02,
Hz0
thermal active
or
can
of
application
be
to
of
the
and,
of
the
their
an
OMC with
of
the
process)
at
alkoxides by
alkoxides
of
IR absorption
bigger
oxidation
employed
at
of
as
opposed bands
present
Continuous
for
to
control
reported
the
by
a much
their
OMC CL were
most
OMC concentration, control
to 10%)
solution,
bubbled
industrial
process. CL.
aliquot
of
are
of
upon
quanti-
The
OAC (ALFOL
OF LIQUID-PHASE
observed the
an
important
generate
various and
of
in
a
can
in
our
CHEMILUMINESCENT
elucidation
of
OMC.
with
of
the
for
the
of
common in
Indeed,
as
sholJn
of
different
peroxides of
active
represented
by
molecular
of
At the
solution,
in
this
the
same
potentials which
review,
chemical
of
is
CL arises nature
dioxetanes,
intermediates. and
reactions
regularities
in
including
generations
chemical
solution.
estimation
states
species
different
be
variety
products
basis
OMC with
CL can
great
electron-excited
electrochemical
stages
the
use
an
advantage
(below
of
the
the
in
oxygen.
to
from
which
or
even
for
activated
continuously
Czo )
OMC transformation
feature
in
XeF *,
intensity
complicates
provides
OMC reactions another
of
to
ruthenium
designed
analytical
course
Cg
the
CL with (C2H513
CL exhibited
bonds
that
the
has
the
to
OF OMC.
excitation it
in
species
products, stage
be
OMC with
[48]
to
method
CLASSIFICATION
emission
OMC, the
in
with
uses
by
alcohols
in
the
of
proportional
fatty
from
final
can
intensities
solvent
amplify either
of
of
(metal-hydride) high
applied
This
important
other
[481.
with
usually
(ranging
impemented
book
Light
is be
to is
owing
[48].
consists
the
of
change
that be
the
intensity
and
O2
trialkylaluminium
[48]. CL
OAC
starting
also
with
into
can
of
oxygen in
mixtures to
to
possible
complexes
intensity
CL exhibited
production
oxidation
the
the
technique
syringed
aerobic
metal
instruments
non-activated
is
becomes
R Al, where R3Al 3 enables the estimation
metal-carbon
owing
ions
to
solution
of
possible
solution
change
added
luminescence.
metal
fluorescent
that
estimations is
convenient
C.
of
H ) AIH, 492 by measuring
of
that
express-CL-testing
sometimes,
for
(i-C
solutions
contact
tative
bright
Ru(bipy)3C12
Small-sized
which
for
estimation
some
Thus,
direct B.
applications
quantitative
OMC. (i-C
some
free-radical
such upon
The
photoprocesses
involving while
electron
that
is
The mechanisms their
emitter
generation
of
n+ >M
-
All
transfer.
condition
of
often the
natures
in
species
accordance
with
OMC are
generate with
the
highly
OMC can
following
states.
be classified
general
j:;;;,b:,;
24
RR*)
(R.)+c
C
(R-Ox)“’
d
-I%
for
(R-Ox)”
Rjli(and/or
b
by
schemes Scheme
j$-;
R + Ox-d
exothermic,
excited
[“8].
a
>M”+ ---c
of to
known CL reactions
excited
R + Ox-d
CL reactions
insufficient
+ >M”+’
(Ox’)*
* (where
The
M- metal; J- excited
R -
pattern
of
first
represented vary
(I of
(I
Cp3Eu,
or
e.g. in
be attributed second
ed only
to
types
one
of
XeF2,
an organic
radical
much more widespread; types
OMC organic
for
molecule;
with (I
their
the
the
The of
can in
(C5Me5)2Yb
oxid-
[92]
oxidized
and metal
CL pattern
is
an OMC organic
(I b).
The
>LnOOCp and
fragment
emitters
the
emitters those
of
which
The emission
fragments.
fragments,
example,
CpnUXm,
are
oxidation
for
c)[98].
peroxides
which
CL dis-
Cp3Ln
194.951
as well.
alkali
being
of
metal
oxidation
metals as
Ph CNa with 02[10,11]. 3 r (Ox’)“(lI d), which
(XeF’)*
of
Cp2Sm [93-951,
of
organic
of
rate
emitters
cyclopentadienyls
reactions
of
of
oxidant
exhibited,
[92];
pattern
adducts
The
emitter
products
OMC organic
‘ar
of
first
fragment
-
the
CL is
Cp2Eu,
the
ketones
of
reaction
organic
163.
a)
lanthanide
the
are
a rule
ions. b).
is
includes
excitation in
OAC with
of
reactions
oxidant
(I
excited
based
CL pattern
by different
of
(I
fragment
by the
Cp-ring
The
The
metal
by O2 as
hydrolysis
in
Ox-d
redox-reactions
unchanged
an oxidant
can
201.
fragment;
CL emitter).
CL incluedes
remain
characterized
occurs
of
Cp3Sm [93-95],(Cp5Me5)2YbCl
to
ligand, played
OMC organic
state
metallocenes
attached also
(CL)
by electron-excited
a,c)
ation b)
h3
emitter are
electron
radical
(R’)*
The
same
was found [79].
represented
being
of
and
excited
are
represented
molecular
R*
acceptors (‘I
b)
is
with
only
in
Reactions by the ketones
(II
a)
[‘7,‘8,
was registerthe
emission
reaction
of
(‘I
following oxidized and
C)
n-olecu-
aldehydes
as
58 We have
recently
observed
naphthalene,
diphenylanthracene,
in
of
oxidation
Ce(lV), has
sodium
Ru(llI).
been
by singlet-excited and
rubrene,
adducts
Besides,
with
existence
of
of
the
said the
XeF2,
anthracene
hydrocarbons emission
of
molecules which by XeF2
hydrocarbon
are
of
generated
[llg], eximers
recorded.
Despite
the one
CL reactions, beautiful
CL emitted
light
should
reactions.
look
only
rare
forward
instances to
future
illustrating observations
each of
new
type
of
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11
Review
CHEMILUMINESCENCE Bulgakov
R.G.
institute of USSR Acad.Sci.
OF ORGANOMETALLICS
, Kazakov
V.P.,
IN SOLUTION
and Tolstikov
Chemistry, .Bashkirian Ural Department,
G.A.
Research Centre, Ufa, SU-450054
(Received January 3rd, 1990) CONTENTS 0. 1.
2.
3.
4.
5.
6.
*
The
introduction Chemiluminescence of Organo~tal~i~s of First Group Metals of the Periodic Table. 1.1 Reactions of lithium and sodium alkyls, cyclopentadienyls, and aryl s wi th oxygen, xenon difluoride, and organic peroxides. 1.2 Reactions of polycyclic hydrocarbon adducts of alkali metals and their ketyls with electron acceptors and oxygen. 1.3 Reactions of alkali metal solutions with chloronorbornene derivatives in liquid ammonia. Chemiluminescence of Organometallics of Second Group Metals of the Periodic Table . 2.1 Reactions of Grignard reagents with haloidpicrines. 2.2 Reactions of Grignard compounds with oxygen. The effect of Imagnetic field. Electrochemi luminescence. 2.3 Reactions of Grignard reagents with organic peroxides, benzene triozonide, and carbon tetrachloride. 2.4 Reactions of (CH3CH~CH*)~Mg and (CSHs)zMg with oxygen. 2.5 Reactions of Ca organics with oxygen. Oxidation of (CZH5f2Zn by oxygen and xenon difluoride. Chemi luminescence of Organometal 1 its of Thi rd Group Metals of the Periodic Table. 3.1 Reactions of organoaluminium compounds (OAC) with oxygen. 3.2 Thermolysis and hydrolysis of organoaluminium peroxides. 3.3 Reactions of OAC with dioxetan, molybdenum peroxy complex, and organic peroxides. 3.4 Reactions of OAC with xenon difluoride. 3.5 Reactions of boralkylhydrides with oxygen. 3.6 Reactions of organoboron peroxides with water. 3.7 Reactions of cyclopentadienyls of Yb, Sm, EU with and xenon difluoride. oxygen, water, 3.8 Reactions of boron hydride complexes of lanthanides with oxygen. 3.9 Reactions of cyclopentadienyls of uranium (IV) with oxygen and xenon difluoride. Chemi 1 umi nescence of Organometal I i cs of Fourth Group Metals of the Periodic Table. 4.1 Reactions of silicon organics with oxygen and xenon difluoride. 4.2 Reactions of germanium, titanium and tin organics with oxygen xenon difluoride. Chemiluminescence of Organometallics of Fifth Group Metals of the Periodic Table. 5.1 Reactions of (C2H5j3Bi and (C2H5)2BiF with oxygen and xenon difluoride. Chemiluminescence of Organometallics of Sixth Group Metals of the Periodic Table.
author
to whom correspondence
OOZZ-328X/90/$18.90
should
be addressed.
01990 Elsevier Sequoia S.A.
12 13 13 16 21 22 22 22 24 25 26 26 26 29 30 31 36 38 38 40 42 43 43 44 44 44 44
12
6.1
Reactions of chromium cyclopentadienyls with oxygen and xenon difluoride. of Mo(C0)6 and its derivatives with oxygen 6.2 Reactions and xenon difluoride. of W(CO)6 with xenon difluoride. 6.3 Reactions Chemiluminescence of 0;ganometallics of Seventh Group Metals of the Periodic Table. 7.1 Reactions of manganese organics with oxygen, xenon difluoride, and benzoyl peroxide. 7.2 Electrochemiluminescence (ECL) of fat-ClRe(C0)3L. 7.3 Reactions of Re(phen) (CO)3C! with tetralinyl hydroperoxide of (CO)5Re-Re(CO)3(phen) wr th chlorine. Chemiluminescence of Organometallics of Eighth Group Metals of the Periodic Table. 8.1 Reactions of Fe, Ni, Rh organics with oxygen and xenon difluoride. 8.2 Electrochemiluminescence of ortho-metallated platinum (II) complex. The Effect of Luminescent Additions upon CL OMC. Low-Temperature CL. Possible Uses of Application of OMC Chemiluminescence in Solution. Conclusions. Classification of Liquid-Phase Chemi luminescent Reactions of OMC.
7.
a.
9. 10. 11.
44 45 46 47 47 48 48 49 49 50 51 55 56
INTRODUCTION Among numerous with
chemical
most
unusual
energy and
luminescence in
1306,
reactions transformed
the
chemistry
This
review
studies
into
CL of
OMC in
the
information
pub1 ications,
Grignard
Since
with
that
are
reactions
with
research
excited coworkers the
on CL of few in
[2],
analyzed
amount
[3].
both of
liquid
its reported
inclusive.
of
metal
reported
in
[5,6],
formation
ions
luminous
the of
abi 1 ity
of
[4]
was
phases.
have
luminescent
and
reactions
review
free
isolat-
metals
gaseous
and
early
rather
alkali
previous
“child-
In
by
of
and
[l]
all
new CL reactions
states
subsequent
two
Our
exhibiting
through
cover
adducts
the
by Wedekind
represented
of
and onyl in
in
1988
to
OMC was
reactions
to
those
considered
OMC reactions
was going
1906
(OMC),
are
discovered
account
from
proceeding a fair
exhibiting
was
organometallics
very
radiation
chemical (CL)
of
described
publication,
those
first
solution
compounds
luminous
first
OMC are
reactions
As we and our redox
the
thus,
amd platinum
concerned
vered,
is
[2,3];
reagents
rhenium
into
chemiluminescence
hood”.
ed examples
organometallic
The
interesting.
called
when
of
been
dico-
radicals. of
OMC to
excited
enter
states
13 can
be regarded
formation should
a new common feature
and deactivation be considered
inherent
processes
to
gain
of
to
OMC.
Therefore,
electron-excited
up-to-date
insight
the
reaction
into
chemical
products
transformat-
ions. 1.
CHEMILIMINESCENCE OF THE PERIODIC
1.1
Reactions aryls
Gilman
alkyls
320-600
eye
result
of
butyl
that
been
or
in
by excited Cp-ring.
luminescence
intermediate
radical partially
both
more
emitter
is
(Ph3C’)*
tion
bands
the
CL and
and e.p.r.
(Fig.1)
tives
between
the
radical
CL and
exhibiting
for
reaction
the
the
scheme
Ph3CyNa+
or
FL at
basis
of “dark is
spectra
as by the
of
longer
CL and
but
of the
of
was
Ph3C’
of
02
is
as a
the
(Fig.21
the
notable
excited 02
and toluene
110,
solutions
have
been
by Gomberg by reac-
of
those
absorp-
by a match
prepared
described
a partially
the
was found
it
identified
solution
[5]
Ph3CNa with
by disappearance
for
in oxidized
with
by
[12,13]
(Fig.3).
Ph3CNa solu-
Ph C’ can be rationalyzed either 3 formation of radical substituted
in
terms
deriva-
wavelength. FL studies
chemistry”
of
[lO,ll] the
reaction
suggested.
+ O2 ____c
molecule
signals
FL spectrum
FL spectrum
FL spectra
complexation
On the [14,15]
(FL)
as well
161,
was synthesized
followed
intensely with
a new type
(THF)
and e.p.r.
CL
by oxidating
in
reaction
The CL emitter
signals.
fluorescence method
The difference and
from
solid
by an
formed
CL of
tetrahydrofuran
of that
CL visible
and CpNa with
CL reported
an organic
formed
oxidized
Ph CC1 with zing 3 Further oxidation by O2 is
tion
to
not
BuLi
recently,
as opposed
fact
effect-
lithium
band was obtained
Recently,
and ketones
Ph C’ which 3 dust.
of
Gomberg’s
of
the
CL absorption
[9].
PhLi for
oxidation
(a wide
due to
of
techniques
stated
CL spectrum
peroxides.
solution
with
just
reactions
Still
Ph CNa absorption bands 3 recorded matching those of
tion
reported
aldehydes
of
of
the
ether
synthetic
was also
[PhLi]=10m3M
observed
111.
In
with
OMC autoxidation;
the
CL with
publications
detect
cyclopentadienyls, and organic
optimal
was unsuccessful
even
emission
radical with
to
nm region)
has
of
Both
alkyls,
difluoride,
observe
Luminescence
solution
naked
to
designing
An attempt
colored
and sodium xenon
happened
their
and aryls.
occurred.
out
lithium
oxygen,
al.
in
GROUP METALS
TABLE.
, PhNa, and PhK [8].
PhLi
in
et
[7]
ed by 02
of
with
OF ORGANOMETALLICS OF FIRST
and of
the
Ph3CNa +
data O2’
reported the
following Scheme
Ph3C’
+ O;(Na202]
in
1 (1)
*
14
8-
.O
6
I.8 4I. 6 / I.4 21.2 0_
I 320
Fig.1
Absorption
(l-3).
(I)
400
360
spectra
by partial
of
440
triphenylmethyl
480
prepared
A ,nm
by different
techniques
02 oxidation
of 0.03M solution of triphenylmethylso-4 -3 dium in THF [ll]; (2,Z’) by d-radiation of 10 and 5.10 M solutions, respectively, of triphenylrnethylchloride [12]; (3,3’) with 0.0002M and O.OOZM solutions, respectively, of the radical synthesized by Gomberg’s reaction in THF, 300 K [ll]; (4) 0.0005M triphenylmethyl cation in 98.3% furic acid, 300 K [II). Ph3C’ Ph3COi
+ 02
+ Ph3CNa
Ph3CO;
-
+ Ph3:’
-
ph3c
.:
Reactions
(6)
and
(8)
are
Ph3COOCPh
(4)
3
+
2
(5)
(Ph3C’)+
inferred
(6)
Ph3C+ +;,
(7)
(Ph3C’)
(8)
+ Ph3C’
Ph C + h3 (523 3 Ph3C’ + Na”
3 Ph3CiNa+
emitter
(3)
Ph3C02
+ Ph3Cf; +(P;3:]
(2)
Ph3COONa + Ph3C’
Ph3C02. :+o
ph3c’ + O2_ Ph3CO; * Ph3C: Ph3C;
Ph3CO;
as the
most
sul-
nm)
(9) (10)
obvious
source
of
the
excited
(Ph3C’)4. Weak CL observable
reactions
of
solvents
by FL,
BuLi
only
with
PMR,
IR,
with
benzoyl,
a photomultiplier lauryl,
UV spectral
and
methods
tert-butyl [l6].
(PEM) was
investigated
peroxides The energy
in
in organic released
in
15
Fig.2
EPR spectra
phenylmethyl different THF.
(1)
of
prepared techniques
with
triby in
partially
O2 oxidized
triphenylme-
thylsodium;
(2)
by Gom-
berg’sreaction.
Fig.3 Spectra of CL(l),fL(2-6),and excited FL(7,8) for the triphenylmethyl radical. (1)0.2MtriphehylmethyIsodiumwith O2 in THF,300 K [11];(2)0.002M species synthesized by Gomberg’s method,300 K [11];(3) as in (2),77 K; (4)reported measurements [12];(5) partially oxidized triphenylmethylsodium, 300 K [11];(5’,5”)with further oxidized triphetiylmethylsodium;(6) 0.0005M solution of triphenylmethyl cation in sulfuric acid [11];(7) A (excitation)= 350 nm; (8) reported data [12].
16
the
first
reaction
step
Ph-i-0-0-C-Ph
accepted
by
BuLi
-
from
which
butyl
vinyl
Ph-i-Bu
ketone
BuOLi
+
,
+ BuLi--cPh-$-OLi II 0
0 in
but
+
the
the
second
0
reaction
primarily
is
Bu-0-Cn-Ph
0 step
excited
Ph-ti-o-Bu 0
product
+
0
formed
energy
in
butyl
the
third
phenyl
mainly
with
the
FL
spectrum
for
The
second
emitter
1.2.
with
with
electron
cyclic electron the
acceptors
The
the
electron
nic
and
[17,18]. of
first acceptor
was
reaction
results
for
diphenyl
anthracene)
latter the
with
the
-
as
FL
to
be
emitter
of
alkali
spectra
of
a CL emitter did
not
close
to
(Amax=
the nm).
metals
and
bright
CL
elimination
the
to
their
a
all
these as
to
DPACI’ intermediate electron ion
to
If
(DPA
+
DPAC12
_
DPA
+
cl-
___c
DPA
+
DPA”
DPACl +
orga-
stands reacts
from lead
the thus
to
Scheme
DPA’
the
acceptors,
(2).
+
allow
of
reactions.
electron
That
chlorine
to
moieties
OMC anion-radical
act
an
poly-
inorganic
enough
organic the
accepts
of
bright
reactions
with
and
radical 2).
and
metals
organic
from
chlorine
(Scheme
of
were
as
common
+
DPACI’
class
with
intermediate (1)
be
was
alkali
new
transfer
OMC anion-radical
Cl
where
in
of
adducts
containing
unstable
a
species
electron
complex
unidentified.
reaction
CL and
shown
concomitant
CL
DPA’ DPACl
in
another
excited
of
it BuLi
are
oxygen.
of
upon
CL emitting
compounds
the!
with
number
The
the
stage
inorganic
further
a
The to
but and
adducts
discovered
hydrocarbons
identification
adducts.
for
aromatic
products
nm region)
ketones
remained
and
final
recognized
400-600
acetonitrile
nm)
acceptors
transfer
and
in
phenyl
540
originally
al.
was
bands
of
The
Ph-CBu2-OLi .
-
hydrocarbon
electron et
BuLi
alkyl
at
polycyclic
identified.
alcohoiate
solution
(emission
not
+
(wide
for
heptane
of
Chandross
1 i thium
spectrum
spectrum
a
Reactions ketyls
CL
was
I! Ph-C-Bu
with
the
FL
transferred
step
ketone
because
agree
was
*
2
(1)
Cl-
(2)
Ph
is
- J< The
transfer
electron logous the
of enters
CL
same
scheme oxidant.
an
electron
the
lowest
was
assumed
CL arises
from
DPA’
antibonding for only
the upon
into level oxidation
DPACI’ of
can the
yield
radical
of
sodium
OMC oxidation
with
DPACl
if
the
DPACI’.
An
ana-
naphthalenide an
aromatic
with peroxide.
17
lA, 1
Fig.4
2
(I)
for
the
0.03M
CL
DPA and
peroxide 1181;
(2)
adduct
of
the
and
O.OlM
DPA;
of
nescence chanism
the
impelled CL for
of
DPA-
+
(4)
The
above
+
nature
of
the
the
authors
of
the
reaction
(C6H5C02)2
scheme is
benzoate
radical
the
higher
radical
is
(2).
they
bonding
orbital
The
absence
with
react
CL spectra
Thus,
of
in
(5) phosphorescence
N-phenylcarbazole,
C6H5C02
-
DPA”
in
that
80 K, nm [IS].
of of
sodium
to and
form
Scheme
(3)
transfer
radicals excited
potassium
to
into
with
explained than might molecules
adducts
of
the
to
by that of
ion
transfer the
aliphatic
that
peroxide
benzoate
by electron
OMC anion-radical
is
me-
(2)
latter
excited
much higher
alkylcarboxy DPA’
is
lumi-
(1)
electron the
of
different
peroxide.
CL upon oxidation
is
a somewhat
C6H5CO;
of
radicals
presence
+ C6H5CO;
+
another
or
(C6H5C02);
the
CL emitter
absence
advance
benzoyl
-
radical
with
to
DPA +
to arylcarboxylate
radical. could
The
on the
[17,18]
by decomposition
an arylcarboxylate
xylate
peroxide
-
unusual
followed
(3).
as opposed of
’
C6H5C02
acceptor
BP0 in FL of
A ,nm
(C6H5C02), DPA;
CL
N-phenyl-
h (excitation)=300
The effect
(3)
N-phenylcarbazole
dioxane;
420
benzoyl
dioxane
0.04M
[18];
of
potassium
0.05M
carbazole dioxane
in
FL of
of
adduct
0.04M
(BPO)
spectrum
of
spectrum
potassium
and from
benzoate peroxides
the
stability
an alkylcarbo-
decarboxylate
before
DPA*. N-phenylcarbazole
with
3
18 the
exception
component were
of
at
N-phenylcarbazole
410
and
considered
to
[18].
preferred emitter;
upon The
the
positively
that
of
charged of
powdered
mixture
for
the
the
glass
FL spectra
of
aromatic
1 ,2_benzanthracene, bands
and
tively.
The
cient
to
enough viously 3Ar
thermal even
generated
blue
that
an argon
bright are
given
CL was
in
form
be seen in
reaction
while
Fig.5.
The
(ArO-)”
which
the
is
the
to
through
Ar’
-
to
picene,
pyrene,
phosphorescence
in
anions,
all
+ Na
where The
radical
At-’
which
(2). orbital [22]
Ar=
The to
+ Na+C,OHB
z C,OHB
cases
CL emitters,
observed
___c
-%
-
while
CL emitter
is
being
most
3Ar7: + WB
ob-
and
CH3CN solution
of
daylight.
of
di-9-anthranoyl
O2
in
CL and
emission
ArCO;
ArO;
--+-
the
peroxide
diglyme
solution
FL spectral
by anthrone following
+ Arc02
ArOOOOAr
Na+ + C,OHB f
formed with
CL emitter that
insuffi-
a
assignments
in
its
anthra-
scheme. 4
(ArO-1;:
+ Na+ + C,0H8
------c -
2ArO’
(1)
+ O2
(2)
CL
(3)
@&
Arc02 react
respec-
L
CO2 + At-’
+
a
be similar
pyrene
+ WB+ --c
At-’
OMC with
Scheme
0 II Ar-CO-OC-Ar Arc02
anion,
An ethereal
flow
0
II
CL
cation:
and
a homogeneous
in
[20].
let
found
the
[21].
as
al.
Besides,
NaC ,BHB wj th
from
excited
the
their
as chrysene,
of
presence
of
+ WB* was
bright
identified
CL arises
were
Ar-
in too
being of
carbazole
blue
chrysene
steps:
of
in
visually
et was
such
states
also
latter
reactions
Therefore,
not
of
tetracene. for
reaction
consecutive
upon
atmosphere,
yellow
nolate
found
(At-)
singlet
perceived
in
CL spectra
molecules.
CL can
being
No CL was
lower
triplet through 1 Ar f Ar.
+ 3Ar:c A bright
the
the
possibilities
[19].
Wurster’s
recorded
in
the
emission
by Weller
perylene,
were
effect
generate
WB+ClO&
in
emission
excite
to
the
wavelength
interpretation
anion-radicals
hydrocarbons
anthracene,
eximer
by the
and crystalline
(CH3),NC6H4N(CH3)hC10~(WB+C10~); the
CL,
that
hydrocarbons
aromatic
show a long phosphorescence
wavelength
rejected
was demonstrated of
nm and
decomposition
polycyclic
adducts of
long
CL was caused
ions
365
Eximer
Chandross
on,
phenylcarbazole
excitation
solution
FL at
nm (Fig.4).
account
Later
he assumed
formed
430
of
in
oxygen is
then
the to
first
stage
give
peroxyl
generated
9-oxyanthracene
no CL when oxygen
(3). reacted
(1)
is
decarboxylated
and oxyl
by electron
radicals transfer
As reported with
Na+C,BHi.
in
of from
[2a], This
to
the is
radicals
anthracene anti-bonding authors
surprising,
of
19
300
500
400
A.nm.
400
300
500
A\,
1
\. \ \‘
f
00
-Na+
1
s .f
-jI 0
i(
._ I
J
1
-
0
,C
1
-
300
-----
to
solid
the
lower that
sodium
CL observed and
its
sotvent.
peroxide
sodium is
is added
two orders
We have
poured
on autoxidation
spectrum
metallic
a CL which
A ,nm
A,nm
FL spectra of aromatic hydrocarbons in THF, 300 K 123,241; CL spectra registered upon autoxidation of sodium adducts of aromatic hydrocarbons in THF, 300 K [23,24]; FL spectra (77 K) and electrochemiluminescence (ECL) spectra for aromatic hydrocarbon eximers (ECL only for phenanthrene and anthracene, 300 K 1241).
-*-*-
Thus,
1
LO
0
Fig.6
1
attributed
ihto of
reproducible to of
THF gives sodium only
OMC, but with
argon-saturated magnitude
that
CL to
to
(with
02
of
is
intensity
fi Iters.
when air
ionization
CL which
its
glass
TtiF
brighter the
rise
is
is much
it
traces)
appears also
bubbled
sodium
close
with
yields
through ether
the
20
Fig.5 (1) CL spectrum for 0.0004M di-9-anthranoyl peroxide and O.OlM sodium naphthalenide with oxygen in dimethoxyethane (DME) [21]; (2) FL spectrum for the above solution (3) FL spectrum after reaction: for 0.0004M anthrone in KOBu(t) solution in DME [21]; (4) CL spectrum for O,DlM sodium naphthalenide and oxygen in THF [23,24].
480
since
CL was easily
dicals the
of
many aromatic
ketyl
which
in
states
autoxidation
is widely of
of
aromatic
the
CL spectra
agree
generated
either
Fig.6).
Both
vibrational
that
Na’Ar’ ArO’
In can
the
as
well
with
blue
02
adducts
[23,24].
solution
of
of
anion-ra-
Further, sodium
benzophe-
experimentally, unambiguously
with
are
the
not
indicates
CL emitters,
known emission
electrochemically emissions
[24a] reveal
This
their
provides
of
or
that but
those
singlet-
maximum bands
hydrocarbons’
upon photoirradiation wide
a basis
band maxima for
the
without
ass~pt~on
the
’ (ArAr)*. similar
in
to
The alternative anthrone
in
its
suggestion anthranolate
has form
+ Na’Ar’
autoxidation
(ArO-)* of
in
sodium
reaction
be and
(ArO-)“,
which Scheme 5
At-’ -!-% -
can
been made that
Scheme 5.
+ 02 -
be observed
the
sodium
‘(ArAr)+c which emission of aromatic eximers 1 ArJ: + Ar --c T(ArAr)J: or ion-ion annihilation and as
from
a species
excited
reacted of
FL spectra
structures.
exe i ted by impact + as Ar + Ar- -
is
when the
hydrocarbons
CL and eximer
CL results
CL is
used
CL and
eximers
detailed
visually
hydrocarbons
in
A comparison excited
Jt ,nm
identified
CL is observed
none
560
of
ArOO’
-
--c
ArOOOOAr ---_*
+ 02
(1)
CL
(2)
anion-radicals different
2ArO’
of other
hydrocarbons, components
of
light the
emission
system.
the
21 to
form
oxygen:
the
related
Na’
+ S -
aromatic er
with
02
alkali
in
ammonia.
An interesting
Na,
and
K in
CL.
XeF2
metal
type
derivatives
following
CL through The
gives
its
further
oxidation
a visible
of
reaction
wit h
sodi urn adducts
CL which
is
still
of
much bri ght-
[5]. of
norbornene
gives
02
with
Reactions liquid
which
(Na+S-)
hydrocarbons
than
1.3.
adduct
of
visible
(THF
liquid
solutions
ammonia
with
green
solutions) [25].
CL was
with
The
chloronorbornene
reported
derivatives
for
various
electron-donating
CL mechanism
chloro-
solutions
suggested
here
of
Li,
the
scheme.
x
_
x
x
Cl
94
Scheme
6
I
L&l
(Na+-NH:)
B
i:l
Cl
c,
Cl
c\
x
A
Cl
\
B
Cl
A
(1) x
x
/
Cl
$6
Cl Cl1
Cl
+
I
H
where
h3
6
\
M -
A
2
metal;
X,
A,
subst i tuents
B -
such
H,
as Cl,
OMe,
OBu and OAc,
C02Et. The
first
molecule
to
The
basic
[lg]
is
rather to
give
the
that
its
to
ground
The
vinyl
geometric
between
an organic state
anion
which the
above
CL was assigned
2z
(2.2-2.5
alternative
involj Jf3s electron
here
an anion-radical
difference that
luminescence 2rl
stage
radical adiabatic
(pyramidalization
to
That 2.4
releases
is
vinyl
route
of
the
2n olefinic
-
given in
radical
for
its upon
corresponding transformation
i.e.
nonadiabatic,
transition
that
radical
eV energy
The main
eV).
a chloride
and
vinyl
the
to
eliminates scheme
the
molecule.
transfer
radiationless 2E
carbon
(2)
is
atom)
acceptor anion. by Chandross 2n -state transition to of
green the
(1). favoured
by both
and electronic
OH,
22 (substituent)
factors.
The
substituent.
CL reveals
6-H
in
involved In
addition
ed CL with
2.
the
its
to
2.1.
The
almost
well
of
history
of
iodides
from
authors
exhibiting
caused
the
vacua
Birch
required
X-OMe,
A-OH,
transformations
started
the
report
the
yield-
published
brightest
CL.
and
a photoelectron
[44].
The mechanism
In
Later
on,
as of
lumines-
is
iodopicrine.The
CL
multiplier
was different
from
the
nd reaction”
remains
of
‘Wedeki
the
[34-361,
CL intensity
with
by the
honour
compounds
contrary,
than
cited [27-471
[28].
Grignard
On the
bromopicrine
book
made
Unfortunately,
reagents
reactions”.
some other
observations
inadequately
Grignard
‘Wedekind
with
the
[l ,261.
were
CL with
recently
from
chloropicrine
pioneer
called
using
by oxygen
that
observed
chlropicrine
in
substituents
the
haloidpicrines.
PhMgBr with
concerninc
of
CL was were
with
recorded
of
works
that
with
OMC chemiluminescence
research
reactions
higher
of
[25].
reagents
abstracts
discoverer,
with
presence
OF ORGANOMETALLICS OF SECOND GROUP METALS OF THE
reactions
as by the
cent
brightness
chloroderivatives,
too
Grignard of
for
all
authors
by the
TABLE.
Reactions
by Wedekind
displayed
substrate.
norbornene
CHEMILUMINESCENCE
is
highest
initial
bromoanalogues
PERIODIC
latter
that
unstudied.
2.2.
Reactions field.
of
Wedekind,
reagents
a Grianard that
reagent
was
was
Extremely
bright
H MgBr with 6 4 luciferin, and
of
this
in
[35]
reaction” bright It reported mount acyclic attached
both
somewhat
can in
and, enough
to
do.
first
That
in
a printed
that
For
both
an unsaturated
the the
a 0.5
nature
carbon
pyrometric
paper
CL is
atom.
the
the
reaction in
of
oxidation of
p-BrC6H4MgBr,
the
name “Moeller-Evans
emitted
greenish-blue
[35].
organic emission
brighter
The
Later,
board.
than
of
the
with
the
experiment,
measurements
oxidation
favour
the
in
brighter
1 flask,
of
black
by Spatch CL was
the
his
of
[47].
CL regularities
radicals types,
In
CL was given
for
lsocyciic
magnetic
[28,29].
by the
as observed
works
of
CL upon contact
a sloping
blue
In
This
from
effect
observed
observed dark
reading
The
to Wedekind
[36].
[36].
air onto
was confirmed
be concluded early
with
poured
reactions
oxygen.
(ECL).
ascribed
[3l].
fainter
importance. ones
slowly
CL was
02
light
with
originally
PhMgl)
wrongly
p-CIC
brightness
Heczko
(PhMgBr,
discovery
CL was
compounds
Electrochemiluminescence
Following Grignard
Grignard
Grignard
reagents
fragment
is
of
more
when magnesium
substitution
of
one
of
light
parathan
is hydrogen
23 in
the
of
luminescence.
ness
benzene
ring
brighter
any other
in of
the
the
series
substi
luminescence.
intensity
reduces
species
the
[37]
as
bacteria.
and organomagnesium a substituent
those of
in
the
pub1 ished
oxidation
different
Grignard
species
papers
[9,461,
CL and
FL spectra,
to
since
[g]:
the
form
it
starting into
of
CL,
the
radicals (X)
brightnature
exhibit
in ArMgX,
CL and most
Grignard
the
photographs
the
the
CL
the
In some early
The
initial
448 and 518
and Hercules reacts
bands nm for
(blue)
the
wrong
of
in
recent
similarly
following
in
reaction
which
in
course
[36,39,43]
positioned
p-terphenyl
CL
as
the
C6H5Mg!3r and p-ClC6H4MgBr,
suggested with
natural
wavelength
as well
assignments
are
with
during
FL emitterswereconsidered
intense
only
CL wavelength
works
to grow
03
CL with
longer
wavelength
ring,
was found
with
of
were
showed
shorter
benzene
[36].
reagents
recordings
chlorides
showed
in
FL intensity
the
C6H5MgBr
intensity
same chemical
weight
experimental
iodides
the
a radical
the the
the
substituent
reaction
first
reagents.
e.g.
Bardsley
pestively,
the
luminescence
m->o->pthe
later,
of
the
the
position
series
in
affects
With
higher
Organomagnesium
(green)CL,
increases
1391,
increases
Cl>CH3>Br>l.
of
gave
[37].
With
also
change
Previous
species.
such
position
OMC with
series
CL spectra
hs exposure)
synthesized
radical
p->o->m-
tuent,
With
in
Photographic (3-12
atom or
The substitution
decreasing
and position
for
is
the
resmechanism
produced
to
trans-
anion. 1
C6H5MgBr + C6H5-C6H4-C6H5 which pheny
is
1,
then which
identification An attempt of
and
native
to
suggested
made to
inhibitors
molecular
by 03 or
oxidized
was believed
chose
upon
schemes
to
these
biphenyls
to
for
and
be the
to
rule
CL excitation,
p-ter-
Kearns
questioned
emitters
by observing
appeared the
MgBr
singlet-excited
Bolton
possibilities
brightness
mechanism
generate
CL emitter.
brominated
luminescence
were
peroxide
be the
between
and free-radical
C6H5 + [C6H5-C6H4-C6H5]
-
out
[46]. the
both
effect the
and two alter-
suggested. Scheme 7 Ph02MgX -
PhHgX + 02
-
Ph’
+ MgX2
-
PhMgX + X’
+ PhMgX
-
XPhMgX’ R
-
XPh02MgX
-
XPh-Ph*
X’
XPhMgX + 03 XPh02MgX + PhMgX XPh-Ph* XPh02MgX + PhMgX
Ph’
+ Mg02X
R’ + XPhMgX
+ 2MgOX
-
XPh-Ph
-
XPhMgX + PhOMgX
+ h$
24
Scheme 8 PhMgX + 02 Ph02MgX + PhMgX
PhO2MgX
-
2PhOMgX i
X-Ph-Ph:: Both ion is
schemes source,
assume but
reactions
there
is
X-Ph-Ph
of
Ph-Ph-X”
+ MgO + MgOX
peroxide
to
+ h$
organomagnesium
no experimental
evidence
as to
be the
stage
at
excitat-
which
light
emitted. The effect
of
magnetic
field
02 was originally
found
gauss
to a solution
was applied
was visible to occur
in
authors
clearly:
there
the
most
intense
that
field
assumed
responsible
for
the
Electrochemi Dafford
[40]
nescence seen lysis
Those
with
trolysis
of to
providing
impurities
six
of that
1401,
under
Grignard
for
by 02.
most of
near
labile
reagents
by
strong field of 1500
oxidized
field,
with
of
the
One effect
the
pole
paramagnetic
contours
from
that
of
the
of
emission
which
is
the
of
emission
pieces.
The
species
were
the
confirmed
by the
after
anodic
of
organic
peroxides,
Grignard [4l].
luminescence Upon elec-
a period the
with
of
reaction
of
[44].
This
upon electrolysis occur
be
electro-
reported
ECL to
ECL can
lumi-
could
[44,45].
electrolysis
by
The
during
reaction
was also
of
reported
emission
opinion
released
“pure”
was
C6H5MgBr.
Pt electrodes
the
disappeared
assignment
on whether
of
during
later
conditions
reagents
solution
an opposite
the
oxygen
doubt
Grignard
The nature
ECL were
in vacua, for
of
the
while
milder
support
casts
the
an ether
be different
containing
observation
being
tendency
of
(ECL)
metres.
observations (PEM)
conducted
time,
regions
of
when a
effect.
oxygen
visual
registered
[40]
C6H5MgBr
interactions
much bright
was assumed
reagents
oxidation
al.
was a distinct
luminescence
a distance
et
of
upon electrolysis
wasso
at
upon the
by Dufford
Grignard
reagents. 2.3.
Reactions nide,
of
and carbon
A somewhat Grignard
less
reagents
with
reagents
with
benzene
triozo-
tetrachloride. bright
CL was visually
benzoyl,
ethyl,
identified
in
reactions
and diacetyl
peroxides
C6H5MgBr,
p-ClC6H4MgBr,
of
than
with
f38.l.
oxygen
Bright p-CHjC6H4MgBr ether
Grignard
or
aliphatic
red
CL in
with
the
benzoyl
reactions peroxide
THF was discovered Grignard
A good match
and studied
compounds between
of
and tert-butyl
nor
the
by Bol ton and Kearns
diphenylmagnesium
CL and
the
FL spectra
and
peroxybenzoate
exhibited obtained
[47].
in diethyl Neither
similar for
CL [47]. the
solut-
25
2
h 0
500 Fig.7
ion
Ph3C’
emitter
is
data
4 ,nm
FL at [49-511.
region
SG2,
with
CO,
Ng2,
violently
benzene
CO2,
mentioned in
the
Reactions
less
than
Grignard
oxidation,
ketone
duction
that
proved
formed
determine
the of
of
is
440 further
the
to
of
radicals
galvinoxyl
of
free as an
the
inhibitor,
those the
while
a few
the
is
mixed
Bright
[44].
red
However,
vacuum
[44].
with
starting
O2 is
(C5H5)2Mg
impurities);
long
follow-
wavelength
a stable possibly
An attempt processes, of
reagents
high
The
Thus,
rate
H20,N,0,
(C5H5)2Mg
with
into
OMC Cp-ring. in
and
nm. this
red
oxygen.
[6,52].
and
CL emitter,
role
560
peroxemission
as
1361.
Ccl4
under
with
connected
transformed
by oxidation
removed
reagents
CL maximum at
be the
PhMgBr with
(n-C3H7)2Mg
nm (propably
eye
the
wavelength
species
the
77 K)
benzoyl
longer
CL
with
by the
Grignard
to
(CG2Mg of
the
different
CL visible
and
(300,
CL was observed,
was
for
in
the
-
institute
agreement
be excited
[32,33,35].
reaction
that
maximum matching
with
O2 which
oxidation
its
is
of
the
ing
product
the
in
can
as
in our
by PhMgBr with
it
no visual
for
FL at
(Ph3C’);b
in good
radiate
much heat
(CH3CH,CH2L2Mg
displays
e.g.
reagents
resulted for
radical
[lO,ll]
CL exhibited
which
Na2g2_,
absence
of
CL found
bright
solution
red
nature,
liberate
triotonide
no CL arose
The
The
nm (Fig.7)
Grignard
to
CL was also
2.4.
523
different
of
the
the
Ph C’ derivatives 3 [SO].
Upon contact
reacted
identified
Ph C’ solution prepared 3 no FL in the red spectral region
revealed
of
substituted
H,g,,
However,
distinct
probably
spectral
by Gomberg
(Fig.7).
same method
showed
Ii terature
of
prepared
[47]
by the
ide
700
(I) CL spectrum measured with boundary filters for phenylmagnesium bromide peroxide with BP0 in diethyl ether [47]; (2,3) FL spectrum for triphenylmethyl prepared in reaction of triphenylmethylchloride with zinc dust, 300 K, A(excitation)=447 nm; (2) [47]; (3) [lO,ll]. of
and
600
but
FL with
autoxidation an excited
was made to after
O2 absorption
the by
intro(C5H5)2Mg
26 was
not
2.5.
decreased
Reactions oxygen
the
of and
PhCal with
and
is
xenon
nescence
comparable
observed
for
solution.
The
to
of
of
Hg-
(C2$.)2Zn
by
(C,H5)2Hg. , OMC which exhibited
by 02,
that
of
of
“nonmagnesium”
intensity
PhCal
PhMgI.
displays CL was
CL seen
yellow not
lumi-
visually
[38]. in
oxidation [45],
C6H5ZnBr,
and mercury
oxidized
by 0,
1 .O~lOy
CL much
(1=1.4.106
low
and
and
Zn-organic
C6H5Znl,
OMC are XeF,
photonTS.ml,
(ca.lml
of
broad
maxima
appears
of
02
of
less
the
CL maxima products
per
glass
at
470,
after
in
compounds
p-BrC6H4ZnBr
capable
of
toluene
by
CL in
rather
rapidly
such
[43]
exhibiting
reveals
rezpectively),
the
PERIODIC 3.1.
530,
bright
fading
w th
CL was
and
coordination
the
majority
in
a darkened
registered
with
the
slow
K).
be
The
in
the
starting
then
the
emission
of
of
5*10-‘M
55°C)
of
CL spectrum
nm. The in
in at
rate
region
The on
was measured
400-600
of
T HF solu-
[53]
autoxidat
OMC gives
region
ketones
with
nm with no FL;
the
formed
OF THIRD
with
compound of
those
room.
-
diffusion point
the and
For is
due
cyclic
short
its
it
wavelength
as oxidation
GROUP METALS OF THE
number
of
to
and carbon
atoms
as well
Ru(bpy)3C12.
display
feature
ranging
from
and
consumption
falling
rate
of of
of
of
the
the
solved
to
at
iso-
with
Ii thium
M solutions, visually
formation
three
main
intermediate
OAC oxidation the
two
CL identified
OAC (C,-C8),
OAC.
trialkyl-
norbornene,
as OAC complexes -1 In 10 -1
by a combination
of
OAC [54-631:
bluish-green
oxidized
consumption
oxygen.
derivatives,
derivatives, ruthenium
with
acyclic
of
rapidly
rapid
(OAC)
a characteristic
halide-substituted
conditioned
abruptly
considered
both
compounds
accumulation -
compounds
is for
cyclohexene
CL maxima
reaction
bubbling
OF ORGANOMETALLICS
hydride-
and
kinetic
the
organoaluminium
compounds
, their
kinetic
and
(C5H5)2Hg
air
TABLE.
luminescence”
camphene,
298
of
hour
Cp-ring.
of
twenty
at
to
of
Reactions
aluminium
0.5
and 580
“Chemical Indeed,
Ih
oxidation,
CHEMI LUMINESCENCE
3.
autoxidation
connected
filters
characteristic of
in after
CL is
absorbed
boundary
only
bright
photon/S.ml
brightness
a set
(ii)
Oxidation
Autoxidation
first
p-CH3C6H4HgBr
atd
oxygen.
[5,6].
tion
(i)
in
observed
Et,Zn
with
Upon oxidation
However , zinc
CL (4.7.1D8 time
the [38].
EtCal
as C6H5HgBr, oxygen.
abruptly.
difluoride.
of
eye
No CL was
CL faded
Ca organics
one
naked
the
of
factors: OAC peroxides;
the
oxygen,
starting and
subsequently
27 growing
oxidation
by the
02 dissolving
establishing itself ion
the
in
the
due
rate
from
the
quenching
increase
solution
to
(open
the
increase
air
flow;
effect
of
of
the
(iii)
02.
CL intensity
cell)
in
02 concentration,
deactivation
That
with
-
removing
deactivating
factor
bubbling
through
air
caused and
reveals the
react-
(Fig.8).
Fig.8 Deactivating effect of oxygen on CL in autoxidation of diethoxyethylaluminium in toluene, 300 K, [561. (1) [OAC]= 1M; (a) with air bubbling off and Ar inlet; (b) with air bubbling on and Ar off (open ceil); (2,3) [OAC]= 0.1, 0.025, 0.02, 0.015M with 0.006M starting oxygen (closed ccl 1).
200
lot ,” ._ 0 r al 240 CI o *5 160
80
60
120
The
induction
out
any
its
In by the
to
the
the
of
oxidation kinetic
of
OAC autoxidation
the
Since
the
reaction only
kinetics
of
the are
consumption
described
was
(C2~50)2~LC2~5 is
abruptly
first + o2 lowered
proved [56].
in
consumption
is
the
slow
of
a CL emitter). determined
the
oxidation by the
The
successive
peroxide
occurs
in
of
this
due
OAC,
the
accumulation
involvement
was shown also
(C2H50)2A100C(CH3)3
the
O2 has
CL is
stage
(with-
R Al and two intermediates 3 this OAC series decreases
particularly
peroxides.
of
the
each
cell of
a quencher
peroxide
by the
of
those
and inter-
by observing
with
CL
(i-C4H9)3A1,
reaction,
the
CL
curve.
involvement
of
free
inhibition
of
the
The absorption
immediately
CL in
CL excitation
by a sloping
Upon OMC autoxidation, emission
of
of
a closed
alkyl), at
initial
Therefore,
in
stable
(02
arising
i.e.
in
the
(R -
determined
organoaluminium
the
after
type
intensity
is
oxidation
solution
R3Al
emission
rate.
curve
consumption of
the
bonds,
The
[55].
because CL only
the
Al-C
mediates in
in
OAC of
al 1 three
lowered of
exhibits value
of
RAI (OR)2
300
CL occurs
contribution
of
R2AIOR,
of
critical
total
240
phase)
oxidation
oxidation
shape
period
gaseous
reached
180
after
of the
oxygen
galvinoxyl
radicals
in
causing
chemiluminescent ceases
and
addition.
the
reaction CL intensity
After
a short
29
+h3 YHO Ii
0 h)*
(RC<
1>AIR Initiation diate
involves
was established decrease
in
the
the
initiation
[59,69]
,
main
and
the
(14)
3.2.
is
of
Thermolysis
FL spectra
formed
in
their
view
of
that
of
alkyl
disproportionation a side
reported
that
high
radicals
[59], ground
data
of
thermolysis
Thus, as
are
of
the
studies
main
in
ini tiat-
region
ketones) (12,13)[6,551.
alkoxides
as
is
quenched
Earlier, to
Vasil’ev
the
hydrocarbons
dispro[55a].
peroxides.
with
the
relatively
that
peroxide
stable
(CH3) 3 158,591. “dark” the
thermolysis
following
and excited
of
scheme
was
[6g]
suggested
for
the
and on CL products
states. Scheme
(CH ) COH +
(C2H50
the
compounds
owing
of
the
and
a cabonyl
CL emitter
organoaluminium
mechanism
(or
OAC (15).
excited
oxidation
OAC possessing
radicals
formation
(CH;C:O) ?. P, -
* ?: P2 -
(C H OAIO)x :H:CHO P2 + h3
O2
(C,H50)2AlC2H5,
R Al is 3 incorporating
The
of (3),
on CL inhibition
peroxide
were
the
removal
for
aldehydes
with
abrupt the
intramolecular (4)
(4)
peroxide
for
each
rate.
reaction
in
the
by trialkylaluminium
ketones
RO;
and
the
oxidation
hydrolysis in
to
CL exhibited
chemical
(1)
excited of
reaction
into
groups
the
compounds to
by the
by an
CL maximum
attributed
their
on the
for
as
OAC.
interme-
duting
introduced
following
alkoxy
occurs
and
radicals
as well
of
processes
by the
and
their
(1)
organoaluminium
types
Accounting
from
the
all
oxygen of
was
solution
in
and
(C2~50)2A100C
From data and
in
[65]
decomposing
radicals;
strong
CL was observed peroxide
inhibitor
peroxides
were
the
colleagues
portionation
traps
an
with
OAC.
both
formation
spin
d-carbon
emission
the
mainly
his
and
process
by oxygen
The
of
the
related
CL emitters
products;
results
the
these
through
latter
OAC with
when
occur
no free for
for the
generated The
give
With
not
the
absorption
assigned group
at
of
reactions
oxygen
(4).
method
[56].
atom
to
of
peroxides
does
decomposition
ing
(15)
diethoxyethylaluminium
solution
a hydrogen
RH + >AlOR
CL intensity
chemiluminescent from
(14)
interaction
by the the
quenching
the
organoaluminium
(13)
(CL)
10
+ CH CHO +
+ h3 (>510
(Z30 nm)
i9m)
(1) (2)
30 scheme
TO shows
Intramolecular as the
and
and
to
in
of
its
light
/\
[601.
the
.
The
The
CL was
latter,
[58]
that
excited
aldehyde
later
on,
to in
ethyl
CL similar
to
later
the
stages
of
accumulated
reaction
of
water
bright
Reactions
With
less
(C,H~O)~A~OOC~H~
stable added
intermediate,
to
the
was which
all,
OAC with
due
is
to
the
OAC violently
Li[AlH4]
the
identified
resulted
to
+
the
third
amount
high
of
Al-C of
(C2H50)2A100C2H5 of
while
with
water
bond of
selectivity
peroxides,
water,
c,ti500~
introduction
reacting
CL in
autoxidation
water.
CL was observed
as well
to
f48].
dioxetane,molybdenum
another
or
from
the
adamantanone
neither
in
excited
state
its
the
ground
of
is
of
red
spectral
intermediate
in
the
(no
longer
An unidentified curves
(i-C4H9)2AlH
peroxy
CL was
in
known CL [TO]
state
(CL
oxygen
Usually,
new type
as
singlet-excited
found
(c2h50)2
an organoaluminium
other
OAC peroxides
(i-C4H9)3Al,
in
arise
interest
with
powdered
with
differs of
kinetic
by stable
complex,
originally
adamantylideneadamantan-l,Z-dioxetane(AAD)
(C2H5)3A1,
was
nm).
and
peroxides.
of
entirely
mainly
of
of
can
special
a few
dioxetans,
ion
First
through
as another
brutto-stage
(C,H50)2~T~~i
described
exactly
than
organic
~20 -
Of
involves
Upon contact
react
acts
water
(C H ) Al oxidation with 02 when 253 suffers oxidation and a sufficient
[60].
solution
3.3.
c
above
triethylaluminium
less
deactiv-
passes
illustrated
with light
is
(2)
hydroperoxide.
(C,H~~)~A~OOC,H~
in
by
be observed
aldehyde,
(A=510
time
The (C H 0) AlC2H5 reacted with 02. 25 2 be the hydrolysis of that OAC autoxidation
is
P2 which
first
solution
at
CL pathway
luminescence
and,
acetaldehyde
unexcited
second
the
CL can
gives
with
product
for for
products.
group
together
(1)
nm.
responsible
(C,H50)2AlOOC(CH3)3
unidentified alkoxy
state
P , and an excited
CL emitter
With
for
peroxide
compound
Upon OMC hydrolysis, peroxide
the
(max)=430
intermediate
unidentified
stand
excited
al umi nooxane
emit
unstable
P2 which
oxidation
CL emitter
alcohol, ated
p,
FL at
410
and
for
CL revealed
solution
after
metal
complexes
region
their
react
to
maxima
reaction with
not
absence
was assumed
the
and CH2C12
during
does
as shown by the
in
That
the than
result of
is
CL
reaction) 410 from
emission
nm). the at
CL emitter,
formed
nor The
in
its
CL is
emission 1270
of
nm.
since
no FL corresponding
the to
CL
[63]. OAC in
the
OAC as
[63].
thermolysis
be the and
such
upon AAD thermolysis.
nm after
wavelength
region
toluene
exhibited
CL emitter
discovered with
the
absence
of
oxygen
to
be
31 emit
no
light
that
complex
[71], to
by a molybdenum which
(ca:
but
give
CL.
peroxy
dioxetane.
CL was
(CH3)3COOH
and
the
about
result
[551,
three
of
is
higher
for
161.
brighter
for
luminescence
the
In
peroxy
and
[6]
the
displayed
enables
intensity
of
by those
OAC
(i-C4Hg)3Al with
in
reaction
(C2H5)3Al,
peroxide,
which
by the
compounds
group
) AlH can be oxidized
CL displayed
reaction
benzoyl
yield
by arylcarbonyl-containing
i.e.
to
(C2H5)3Al
peroxide
times
a bound-to-metal
comparable
registered
benzoyl
of
(C H ) Al and (i-C H 253 492 in toluene to emit light
Thus,
complex
with
is
existence
1D8photon/S*mo’e)
with
flash
the
is
supposed
as opposed
to
the
CL
evidently CL emitters
their
alkyl
analogues.
3.4.
Reactions
of
CL in
reaction
reported
the
in
OAC with
[72]
xenon
of
and was
tomass-spectrometry
methods
the
of
The
principal
bonds
to
consequent of
the
these
solutions by the
activity
H>R>OR>C I
of
the
one
active
the
free-radical
elucidate their
involves
degree,
at
in
via
reacts
the
an OAC aluminium
main mild
chroma-
of
excited
emission
states.
OAC active products;
fluorination
with
C2H50-Al
reaction
atom
NMR, and
the
as the
XeF2
was originally
mechanism and
attacking
prepared
ethoxytaluenes
FL,
the
ground
XeF2
be efficiently
To a less
the
with
of
than
bonds
products
decreases
as
[73].
in
the
series
was
K,
1)
[77].
found
The and
when
an NMR probe.
multiplet
polarization
fluoride,
and
butane
of [77,
the
XeF2,
(2~0.2),
derive
kinetic
parameters
model in
;
to
781.
lower
During
methylene
more
latter
lo-15
protons
and was
galvinoxyl
1 iberation
set,
[48].
shown
chemically
the
ethylated
to
the
be of overall
induced
dynamic
discovered leads
(Fig.10)
(C2H50)2AlC2H5
of
(2.9+0.2).‘0-’
possessing
and
was originally of
gas
and
derived
kca’/mole
galvinoxyl,
as by the
of
constants
(C2H50)2AlC2H5,
detail of
introduction
solutions
rate
~a=6.5*0.2
compound
effect
the
the
(6.7+0.2).10-’ and
as well
(C’DNP)
CL decay
was
with
inhibiting
(Table
XeF2
were
investigated
effect
usually
to
respectively, of
by the
products
in
CL decay 233
reaction
bond,
effect
method
(C2H50)2AlC2H5
of and
the
convenient
XeF2.
curve 262,
with
directly
most
of
type
OMC reactions
mixed
to both
toluene
by CL,
OAC derivatives
of
polarization
CIDNP
reaction
by XeF2.
of
Al-C
composition
abrupt
in
presence
reaction
The mechanism
The
that
OAC can
out
from the linear M-ls-1 at 293,
nucleus
species
substituents
OAC reactions For
[5,6,72-801
the
CH2C12 and
[73].
CL turned of
in
investigated
fluorine-substituted
1y,
confirmed The
mode of
give
XeF2
extensively
and
composition
difluoride.
OAC with
and
a more
[761. XeF2
PMR spectrum toluenes,
to
for
were
showed ethyl
32
s
10
I
I
+P
800 --
\
t ,min W,ml
‘\
-3 2
-1
Inhibited CL (1) and gas liberation (2) with the addition of galvinoxyl upon autoxidation of 0.02M diethoxyethylaluminium 0.01 M xenon difluoride in toluene, 201 K [94]; _ points galvinoxyl additions; V(m1) - total amount of gases.
Fig.10
For
(C2H50)2A1C2H5
region radical
with
its
(XeF’)*
oxidized
(Fig.11)
400 Fig.11
by XeF2,
maximum at
450
the
CL spectrum
nm and was assigned
is to
in
the
t. : 350-550 emission
of
0.000 2M by of
nm the
[79].
5oo
A ,nm
CL spectra recorded in the reaction of diethoxyethyialuminium with xenon difluoride (I-3) [79] and CL spectra for XeF* emission generated with laser illumination (248 nm) of Xe+Fs mixture in liquid krypton 182,831. (1) in toluene; (2) in methylene chloride; without solvent; (4) dashed line is for the emission component X) of XeF” recorded in the background of Kr,F* emission.
33 Table
Compositions
1.
and yields
of
l.l4~lO-‘M(C2H50)2AlC2H5
with
Yield,
0.90
1.94
0.10
45.0
97.0
0.97
5.0
products
excited
of
states
reaction
with
be described
the
in
0.22
products following
reaction
toluene
0.20
65.5"
100%. Traces method, traces
its
in
the
of
300 K.
at
%
23.5” as
in
XeF2
XeF,,
0.15
97.0
that
can
of
r a c e s
T ‘ he total sum of products was taken detected by chromatomass-spectrometry traces of n-C4H,G by GLC. The mechanism
5.7.10-*M
mole/mole
t
formed
0.025
0.08
of F-toluenes were of C2H5F by CIDNP,
formed
in
their
ground
-s
>Al-F
XeF’
f
XeF2
-
+ XeF’
+ >AI-C2H5
. [>Al-C2H5.XeF2]
[>Al+-C2H5*XeFi]
(1)
25
>Al-F
(2)
+ Xe + C2H5
CH
H3 + Xe _
+ C6H5CH3 eH
2 ‘ ”6
11
-
+ C H -c
F XeF’
-
and
scheme. Scheme
>Al-C2H5
tr
4.02: 7.0"
3 + H’
F
(3) (4)
+ 2 ‘ ”4
(5)
n-C4H1 0
.
g ‘ HsCH2 C2H6 + C6H5CH2 C ‘ 2H5
C6”5CH2CH2C6H5
(6)
+ CH3C6H5 CH3 C2H5 + o- ,m- ,p-C2H5
I,
. L-
g ‘ HgC H2
CH3 (7) CH
3
C6H5Cti3+ o-
(8)
34
CH
‘2”5
SH5
-
+ C2H5
C2H6 + C2H5
3 (9)
C2H5 CH C6H5CH2 + CH3C6H5 -
XeF2
3 -
C H CH 65 H
+ H20
-
C2H5 C6H5CH2-C6H4Ct13
HF + 02 + Xe
-%
+ XeF2
z3@
‘,@“1
HF2;“.“F
C6H5CH;
acH3
(12)
+ 2HF + Xe HF
+
HF2..
.XeF -
C2H5CH3
(10)
(11)
. C6H5CH3 “bH C6H5CH3
+ C2H6
.
C6H5CH2F
+
C6H5CH2 + HF + XeF’
-
C6H5CH2
(13)
C6H5CH
-CL
C6H5CH2-C6H4CH3 (14)
C2H5 + XeF2 C2H5
+
.
in
C2H5
C2H5F +
In’
-
the
presence
of
2C2H502 C6H5CH2
+ O2
reaction
give
cation-
[ST]
in
disappear (2).
The
traces
of
nm)
(15)
(17)
c2H50;
>
(CH3C<‘)” H C6H5CH20;
with
(19)
anion-radicals
starting their
reaction
of
ethane,
(1). the
interactions these
Intermediate ethylene
+ C6H5CH20H
transfer
OAC reduces
during
“-
H)
electron
(18)
+ O2 + C2H50H
//O (C6H5C\
and
(3).
toluenes
(450
oxygen
-
starts
the
h@
(16)
-
2 (C6H5)CH20;
The
-
C2H51n
‘2
l
(XeF’)A
radicals
from
OAC to
A complexed yield
of the
with
toluene
radicals
(4))
and
butane
closest
react (5);
electrophilic
spiroaluminooxane
radicals
with
C2H5
+ O2
XeF’; AI-C
gives (i) (ii)
with
to
structure probably
bond of
the
traces
of
fluoro-
other
to
yield
only
with
they
XeF2
each
toluene
at
OAC
the
35 side
chain
ethyl-
to
(7,8)
give
dibenzyl
(6)
and
and diethyl-toluenes
.
two processes.
The
radical
ethylmethylcyclohexadienyl
C I DNP data,
forms
(8) radical.
The
can
The
radical
suppress
[79]
is
for
pairs
the
of
reaction
at
(17,18),
radicals
result
3.5.
but in
may result
Reactions
of
A visible
bluish
exhibited
and
in
the
OMC. Triplet-excited identified escence
as for
the
the
CL emitters
individual
[Fog.12)
[85].
with
oxidation
only
a long
(both
wavelength
components
length the
the
component stage
of
i.e.
presumably
species [67,6$]. of
arises
of
the
>MO2 are
Earlier,
compounds
exists
such
bands
at
emission
(500-650
nm)
as
reaction
the
oxygen
of
those
up to
increases
in
CL decay
the
in
the
the
responsible The
due
the
released
inhibition
to
the
occurrence
from
the
main
of
process
peroxy
by excited
benzal-
such
B-C
[84,85].
bonds
in
those
cyclooctanone of
CL and
solutions
as
were
phosphorafter
spectra
in
THF
is
CL kinetic
maximum,
with
a monochromator
registered filters);
later,
intensity
a short
so that
it
wave-
prevails
at
(Fig.12).
. That
in
statement
classic
202
was
borohydride, 547
(15);
balance)
(g-BBN)
spectra
CL emitter
the
of
additions
(19,ZO).
and
of
change
glass
emission
styrene
radical
B-H and
the
with
CL is
in
c-complexes.
boralkylhydrides
pinocamphone
Thus,
>BO;
[86-881.
in
Emission
active
of
met
520,
since
C2H5 away
CL.
through
as zirconium 490,
all
agother
radical often
the
emission
and
ditolyls
intermediate
disproportionation
oxygen.
time.
sloping
there
the
by matching
be seen
gently
Therefore
radicals
with
of
component
can
asymmetric
[82,83].
An interesting
reaction
benzyl
are
of
ketones
observed
or
(7)
nature,
of
reaction
such
the
ethyl
g-borabicyclo[3.3.1]-nonane
ketones
latter
the
bond energy
autoxidation
oxidation
give
the
to
by galvinoxyl
brighter
CL follows
to
give
in
according
X transition)
[02]<10-4,
boralkylhydrides
and
CL emitter
B-state
the
a similar
diisopinocampheylborane CL is
the
the
a somewhat
from
(9)
related
diffusion
nm (B--c
at
another
by the
diverts
ring
with
to
formed
[78].
is
excite
450
Oxygen
by reactions
dehyde
to
aromatic
the
ring
also
which,
of
their
and CL suppression
(16).
can
terms
(XeF’)*
sufficient
liberation
in
aromatic
being
radical pair
as calculated
luminescence
gas
the
CIDNP signals
radical
the
diethyltoluenes
reveal
the
Cal/mole
quite
of
of
formed
excited
(ca.79
a radical
rationalized
completely
The energy
further formation
be also
at ethane
C2H5 attacks
d-complexed
(10)
(iii)
(g),
nm were Besides,
THF
recorded B2H6, in
we have
addition
to
is well-reasoned.
schemes
found
(in
for
The
OMC autoxidation
upon gas-phase and the
H3BC0, long
established
ketones),
oxidation
with
B-H
bonds;
wavelength that
the
long
36
400
600
500
h,lJsl
1
0
1
$0 .2
J
c .-
0
301 201 101
% Fig.12
inherent
IU
b
t,mrn
Spectral assignments (T-8) and kinetics (9) of CL upon autoxidation of 9-BBN in THF [85]. (1,2) FL at 298 K and phosphorescence at 77 K of cyclooctanone and the solution after 8-BBN oxidation, A (excitation)=320 nm; (3,4) CL for O.lM 8-BBN in benzene and toluene; (5,8, 9) CL for O.OlM 9-BBN in THF; (a) and (b) with air bubbling on and off, respectively; A3, CD, EF, GH-sections of Curve 9 for spectral measurements 5-8.
wavelength length
4
component
one. in
boralkylhydride
At the
the
of
CL
is
same time,
gas-phase autoxidation
quenched
by oxygen
the
quenching effect of oxygen is al50 ?: by BO; [86,871. The mechanism of
strong
CL exhibited is
described
within
more
the
than
the
following
short
scheme
wave-
1851.
37 Scheme
R\ B-H
+
02
R\
OOH +
Rs R R
OOH +
>
R\
R’
B-H
-
R\
BOH -
80’
+
RLB. HO’ R\
0
BOH +
02
+ O2 -
(4)
(5)
R\
-
(6) +
R’
RO’ 2
(7) ROO\
R\
+
.
R\
R’
RO;
(3)
2 -Ho/BO;
HOHBo’
R’
R\ HO/BoH
HO/
R
-
+
R\
BOR +
RYBoH
+
+ R’
R R
R\
RNBo’
(2)
BOH
2R/ R
R’
R\
(1)
RkBCIOH R’
-
R’ R\
12
BOH + R’ BoH -
R’
(8)
R’
RO. ‘BOH ‘BOH R’
RO’
+
\OH R’
--K
RO; +
ROO, ,BOH ROO
In’
_
(14) L
ROH + O2 + 3(R=O)*
-
(where
(13)
ROOln
I R stands
oxidation
non-excited
(11)
(12)
R'
octanone
+
l -
BOH + O2 -
Upon
(9)
(10)
ROH
-
ROO,
2RO;
+ RO’
;;>OH
H
+
RO; +
+ R’
R’
R
ROO
of
emission state
for g-BBN [89].
the by
O2
R=O
organic H2Cr04,
That
in reaction
ketone with
(CL
fragments we
(15)
CL
observed was
earlier
H2Cr04
[go].
quenching) of CL
boralkylhydrides) in
the
reported
region to
of form
cycloin
its
38 3.6.
Reactions
of
When water CL is
sharply
ered
reaction
the
most
peroxides
introduced
enhanced
The
lytic
organoboron
is
of
and
into then
gently
intermediate
obvious
source
with
water.
THF solutions drops
excited
CL spectrum
addition
was
provides
the
in
to
the
peroxides
states
sloping
with
water:
an
branch
region
simitarity
We believe
of
form
at
same spectral
of
reactions.
presence
water
measured
the
evidence
nescent
further
with
excited
state,
of
the
as
(ca.3
in
the
0
with
alkoxy
which
-0OH
“dry”
is
under
above
the
addition
ketones
the
considhydro-
of (that
of
are
group
and
difluoride.
peroxide
(C5Me5)2YbCl
[92],
Cp2Eu,
After
oxidation
Cp=C5H5. 935
and
more Eu(l
440
nm for
narrow
I I)
Cp2Sm,
of
(C5Me5)*Yb
FL bands
at
980
provides
to
with reacts
//O
in
its
of
hyroperoxides
additional
processes
a solution of
CL
of
boron)
support
simulated 9-BBN
for
via
after
its
yielded
CL in
oxygen,
water,
the
[89] Yb, of
Sm, and
ELI with
lanthanide
by the
ions
Ianthanide
of
organic
peroxides.
lanthanides
organics
Cp3Eu,
by 02,
CL in
reacts
a ketone
reaction
those
derivative
Hydrolysis
and
0
the
which
Besides,
phosphorescence
of
lumi-
for
<:
CL.
from
[91],
an alkoxy
upon autoxidation
both
+ ROOH which
to give
boron with
result
OMC CL emitted
the
That
followed
-B-OH
-OH + >BOH +
cyclopentadienyl
of
to
hydroperoxide
containing
of
discovered
0
cyclooctane
Reactions xenon
deactivated
CL mechanism.
cyclooctanone
A new type
attached
then
known to
water
bH
group
alkoxy
described
oxidation region
is
in is
organoboron
after
autoxidation.
pathway
-BOOR c HOH -
+ >BOR -
CIAC containing
the
for
by 02,
water
+ 02
min)
CL emitters
following
intermediate
a hydroperoxide,
the
Non-excited
into
with
9-BBN
bH
at
oxidized
conditions. The
3.7.
9-BBN
1891.
organoboron
of
of
{LO)
Ln”
such
and Cp9Sm [5,93,95],
broad
FL maxima
and Cp2Eu, nm for
of
the
respectively,
Yb(lfi)
and at
was
as
(C5Me5)2Yb,
where
Me=CH3
starting are
580,
(Ill)
LO
transformed
595,
613,
640
nm
(Fig.13). Scheme
13
:‘:
Cp2Ln(ll)
Cp,Ln(l
+ O2 ---c
L
CP h3
(LC)
+
/)Ln(lll) 0
_g&_
I I_)
quenching of ketones
(1)
39 CPOO, 3: 6Ln(III) 0
-P+
Cp3Ln(l
I I)
+ 02 -
cp*L:(III)
(I I I ) o’->L;(lll)
Cp2Ln
CPOO, &Ln(lll) 0
-
6\
+
-
I
oocp
oocp
+&j
,
oocp
(3)
Cp2Ln(lll)
I
+ hti (LC)
-&+d
I
I
+ hfl (LC)
P + >Ln(lll)
(5)
+hg(SC)
I
1COCP
(4)
II
+ h3
(LC)
(6)
I oocp (where SC -
The in
P stands long
for
a complex
and short
wavelength
processes the
resulting
scheme
ketones
above
effectively
as
quenched lanthanide
for
long wavelength
the
case
with
dienone with
(4)
disappears
other
identified
(KI
a possible simpliest
was
of
oxidation
which
With the
Cp3Ln,
emission
each
The above
of
responsible
except too.
as well
as
either,
possessing
the
its
reaction was
CL spectra
of
a peroxide cannot
rule
being
“red”
the
peroxide of
CP O~L~(I!l)
promoting
for
Cyclopenta-
in
organic
statement
is
yields
is
by a good match
products
oxides
The former
oxidation
of
A lanthanide
H20).
be capable
(1).
Further
dimerization
[93,95]
Cp2Ln autoxidation,
excited
CL.
be represented
CL of
out
the
divalent
Cp2Eu and Cp2Sm. example
the
of
reported The
(PEM) with
(350-450
an unusual
light
of
an argon
latter
matching Sm(OH)
the
long
is
also
in
reaction
by unoxidized
OMC with
of
water
Cp Sm with
3
ca.2.106photon/S*ml
water
CL spectrum
species 3
of
(0.5
atmosphere.
nm) and one
as its
CL displayed
emission
luminescence
an aliquot
Cp2Sm in THF in
CL.
stage
exhibit
the
by lanthanide to
of
[95].
with
Eu and Sm LO can
LC and
respectively).
deactivation
CL emitter the
of
are
ketones
during
CL-test
emission
THF [94,95].
short
FL of
among those
The first
ed
“red”
reaction;
lanthanides
water
, excited
oxides;
CL,
fast
component
participants
as the
Eu and Sm LO to group
“red”
and metal
of
LO (1).
peroxide,
rapidly
reactive
first
starting
organic
LE(III)
the
oxoderivatives
by the
excited
polymers
autoxidation
At
its
of
components
from [95].
and Li(III)
mixture
ml)
to
the
The CL spectrum
wavelength of
added
(-5
components,
Cp3Sm autoxidation.
excited
in
the
hydrolysis
min) 2.10m3M
consisted the
bands
Therefore, of
in
was registersolution of
of
two
of
the Si(lI
Cp Sm to 3
emit
I)
40
Fig.13
Spectral assignments upon autoxidation of cyclopentadienyls of ytterbium [92], europium and samarium [PS]. (1) and (2) - FL registered before and after oxidation of OLYb(l I), 295 K; (3) before and after oxidation of OLEu(l I), and (4) - FL registered 77 K; (5)- FL for OLSm(l t I), 77 K; (6)- CL for OLYb(L I ,I 11); (7) and (8)CL for OLEu(II I) and Eu(lf); (9) and (IO)CL for OLSm(lll) and Sm(ll); (6-10) - [OL]=O.OOlM, THF, 295 K.
THF solutions
of
Cp2SmC1 [5]
upon oxidation
by a toluene
three
No spectral
3.8.
minutes. Reactions This
year,
of
boron
CL and
along
with
solution
of
measurements hydride
FL were
complexes found
for
other XeF2. were of the
Eu and That
Sm LO exhibited
CL fades
rapidly
CL within
made. lanthanides complexes
with of
type
oxygen. NaLn(BH4)4-nDME,
41 where
Ln -
compounds, of
T%(III)
Sm(ltl),
observed
in
Pr(lll)
FL is of
THF before
(n=4),
extremely
the
state
and after
and Tb(lll)(n=3)
bright,
of
which
aggregation
oxidatian
with
[96].
is
caused
(either
With
Tb
by the
crystal
emission
line
or
02)(Fig.14).
Spectral assignments upon autoxidation of lanthanide boron hydride complexes in YHF 2961. (1) and (2) FL for crystals and solution of Tb before and after oxidation (3); (4) and (5) FL for crystals and O.OBSM solution of Eu before and after oxidation (61, 77 K; (7) and (8) FL of crystals and solution of Sm after oxidation, 77 K; (9) FL recorded after oxidation of Pr complexes, 77 K; (10,11,12) CL for Tb, Eu, SW, respectively, 298 K.
Starting but
the
irrespective
dissolved
Fig.14
Eu(lll),
solutions
on oxidation
and PF(II Before blue
I).
the
which
(max-465,
blue
FL vanishes,
blue
FL of of
give
nescence by L?~(l!l)
the
those in
the
unequivocal it
emitters. ions
in
are FL is
region
decreases
spectra
its
very
Eu>Tb>Sm to
evidence
reactions
is
of
recently of
for
intense
red
FL is
of
the
&(liI)
ELI comp’lex.
band
in
the
very
weak.
the
red
FL of
EE(llf).
similar
to
the
FL of
Eu(lIf
02 yield
reach
CL the
zero
for
ions
L?~fIll)
[98a]
that
inorganics.
[97].
intensity
Pr complexes.
the
deepAfter
into
lanthanide
lanthanide
300 K and 77 K,
emission
obtained
The
with
reported
the
as an
77 K).
oxidized
to
results
transforming
ELI complex
was
the
no FL at
owing
revealed
300 K,
complexes series
exhibit
registered
interest
wi th 02,
the
THF solutions
FL is
02,
Of special
spectral
Thus,
Sm and Pr complexes
with
oxidation
oxidation,
of
as the
of The CL
tumi-
CL was emitted
42 3.9.
Reactions
of
cyclopentadienyls
of
uranium
(IV)
with
oxygen
and
xenon
difluoride. Upon oxidation for
Cp4U and
orders
of
of
uranium
magnitude
with
XeF2
suggested
for autoxidation 4+ XmCpnU for short (X=
as
organics
(UO)
[48] and for
Cp3U(n-C4H9)
than
of
with
02.
uranocenes
Cp or
Cl;
by 02 and
Cp3UCI
[98].
The
XeF2,
CL is
fol lowing
Cp4U,
Cp,UCI,
Cp= C5H5;
m +‘n
CL was
found
brighter
by two
CL mechanism
and
CpUCl,
is
designated
= 4). Scheme
4+ XmCPnU
+30
. ‘02]
ixmcpnu4+
-
2
/H-S
14
__L
I
(1)
Is*
I
[xmcpnu5+ . 0; ] +
-
(2)
HS-solvent
_ +
xmcPn_2uo;+ + C5H6
I
(3)
X_Cp_lJ*+OOH II,
II
(HP)
L--- +:
$_
0
xmcpn_2bo;+ -
0
CL
(5)
C5H6 + ‘2 LI According
to
state
of
state
with
to
U(V)
extracted
from with of
emission
(4).
above
decomposition HP gives
is
in
with
complete.
since The
by the
radicals
follow
the
influences
appear
of
of
at
absence
stage
those
(2),
result (5)
of the
from
“dark”
[Sg].
the
or
is
C5H6
is
emission
of
uranyl
Uranyl not
is
shown
of
CL
in
of
at
also at
the
uranocenes of
effectively
autoxidation addition
with
upon autoxidation
oxidation
are
decom-
deactivated
oxidation
[99]
their
because
processes
which
triplet
oxidized
atom
Simultaneously,
which
maximum.
the
the is
uranocene
products
bonds,
until
which
singlet
FL characteristic
CL spectral Cp-U
the
into
a hydrogen
(HP).
group
UO [99],
uranium(lV)
Next,
a solvent,
uranyl
intermediates the
that
hydroperoxide
the
mechanism of
from
of
transformed
uranyl-containing
ketones
hence
is
(1,2).
registered
reaction
free-radical neither
of
autoxidation
result
presence
oxidation CL is
excited
by C5H6 molecules, Though
of
region
further
i .e. of
by the
the
the formed
an excited
formation [98]
is
(D),
the
scheme,
catalyzed
donors
The
“dark” complex
with
ion
the
77 K (Fig.15)
for
intermediate
transfer
the
demonstrated
excited
obtained
an
a superoxide
position
was
data in
electron
and
formed
the
oxygen
the
C5H6 quenched
CL spectrum. and
CL do not
galvinoxyl
(to
10m3M)
43
400 Fig.15
A ,nm
Spectral assignments upon autoxidation of uranium(lV) dienyls [98]. (l-4) FL registered after oxidation of (4) FL for hydrolyzed oxidation Cp3UC1 (Z), CpUCl (3); Cp4U in 5M HCl; (2) CL for all uranocenes, saturated in THF, oxygen bubbling.
4.
CHEMILUMINESCENCE
4.1.
Reactions
PERIODIC
immediately rapidly
of
silicon
at
(C2H5)3SiCH2=CH2 peroxides
The
luminescence
CL of
OF FOURTH GROUP METALS OF THE
of
up to
for
that
weakening
argon
containing
toluene
6O”C,
is
of
of
originates A strong
of
the
reagents
only
traces
of
of
No CL is
the
the
is
displayed
CL is Q2.
air
of
in of
CL decay
effect
with
inertness
reactions
magnitude
the
exhibited
of
when
Thus,
difluoride.
solutions
quenching
CL.
xenon
by XeF2,
shown by a gentle two order
and
(C2H5)3SiCH2=CH2
because
because
turns
HSiCl 3.
of
and
4.3*106photon/s-mole
j*106photon/s-mole
solution
oxygen
two minutes.
mainly as
with
(C2H5)6Si2
within
Weak CL of
con
organics
contact
20-85% even
(C2H5)6Si2 O,[S].
of
after
to
OF ORGANOMETALLICS
cyclopentaCp4U (l), product solutions
TABLE
Upon oxidation
of
600
500
after
the
five-times
that
O2 is
brighter
of
of organosilimaximum
XeF2.
through one
fade
OMC towards
reaction
kinetic
with
bubbled
of
to
O2 and
intermediate
brighter is
the
CL arises
Very
a toluene the with
[S].
weak
reasons bubbling
44 4.2.
Reaction xenon
ions
germanium,
and
titanium,
tin
organics
with
oxygen
and
difluoride.
Upon oxidation
by O2 and
of
(C2H50)3TiC6H5
such
(3.0.107), the
of
OMC as
(C2H5)2GeH2
phton/s-mole
-
values
XeF2,
CL was -
recorded
2.6.108(7.2*108), are
given
[5,6]
8.3*108(6.8*10g), (CH3)6Sn2
for
the
for
toluene
(C2H5)6Ge2-
solut-
1 .0*107
2.5.106(2.8.108);
maximum CL intensities
with
O2
(XeF2). In in
the
match
course
of
region
of
400-500
with
stable and
the
the
but
tin
autoxidation nm with
CL spectrum
unidentified
organics,
its
CL can
broad
measured
product be
(C2H50)2TiC6H5 maximum at
by the
of
flow
at
THF,
450
method.
autoxidation
recorded
in
emits
higher
FL is
displayed
nm giving
a good
This the
implies
CL.
temperatures
With
that
a
germanium
(60°C)
only.
CHEMI LUMI NESCENCE OF ORGANOMETALLi CS OF FI FTH GROUP METALS
5.
OF THE PERIODIC 5.1.
Reactions
of
Reactionsof fading
(ca.
(C2H5)3Bi CL of
CL of
) Bi with
OF THE 6.1.
XeF2
and
With
the
and
oxygen
and
xenon
difluoride.
with O2 in toluene give rapidly 7 photon/ssmole intensities,
2.5.10
of
air
cyclopentadienyls
through
as a reaction to
the
phosphorescence
to
(>6DO
weak
fade
in
the
GROUP
reaction
of
METALS
intermediate.
ketones
as
were
to
are
displayed
difluride.
solutions rise
a minute
(Imax=
[loll.
Cr(lll)
wavelength
transformed
xenon
toluene
by emitting
which
CL was
that
they
within
short
ketones
since
and
THF or
caused
The
by excited
Cp-rings,
oxygen
CL was observed
rapidly
was
hm)
with
-1.5*10V3M
C5H5CrF,
and
emission
of
1.5.10-2
or
compohent
chromocene
exhibited
OF ORGANOMETALLICS OF SlXTH
chromium
bubbled
CL red
is
TABLE.
(C H ) Cr, [C5H5Cr04], 65 5 2 6.10 -8-10~ photon/s.mole)
assigned
with
(C2H5)2BiF
l_0.108
of
involved
(C2&_)2BiF
[48].
PERIODIC
Reactions
The
and
3.4*108photon/s.mole
CHEMILUMINESCENCE
6.
Bi
[5,48].
Brighter (C H 253
TABLE.
(C2H&
2 min)
respectively
of
of
which
CL (425-575
products in
of
the
further
nm) was
oxidation
region
into
is
of
C,0H,004
[1021. In ion
of
formation similar
agreement
with
the
results
(C H ) Cr [102] 552 of unexcited
and
those
to
that
which
on the for
and excited was
given
CL and products
for
mechanism
the
FL of can
CL with
of
the
“dark”
chromocenes
be accommodated uranocenes.
autoxidat-
[loll,
the
by a scheme
45 Scheme cp2cr2+
donor
+ 02 _
H’ -
ICp2Cr 2+.
Cp,Cr3+00H-
-
‘02]
-
C H 56
h’)
[Cp2Cr3+.0$
+ $3;
15
__c
(1)
(2)
l--
(>600 nm) + [CpCr3+014
h3
(3)
(BT)
3+
[Wr
Ol,,4
C5H6 + O2 -
hJ
Excited as
is
generated
oxidation
from
Since
the
the
oxidation,
by the
transformation
CL was
6.2.
displayed
of
observed
believed toluene
is
that
CO among
743
cm-’
6.3.
since
in
the the
give
Reaction
of
CL reaction proceed
with
and
the
its
(4)
CL is
by
intensive
for
W(CO),
with
of
W(CO),
concomitant
the
with
the
excited
as well latter
ketone
region
oxygen
within
also
[loll.
difluoride. weak
.
CL
FL is
and a carbon
room temperature
in
bands carbonyl
for
the
Mo(CO)6 That
respectively. The
appearance
of
nm)
and xenon
molybdenum
liberation.
(those
substitution
(~600
the
Mo(C06). at
the
lmax=l.5.107
toluene;
a minute
photon/s*mole,
gas
CL was
THF or
of C6H5CH3Mo(C0)3,
rapidly of
of
in
with
observed
and
xenon
gas
(2)
(BT),
emitted of
intensity
(60’~)
with
reaction
with
also
spectral
n-bond
3.6.107
products
evidence
is
the
fading
and
after
(HP)
tetramer
formation
derivatives
1.105
solution
blue
concentration
registered
by XeF2,
gaseous
the
a toluene
weak
no CL is
hydroperoxide
the
wavelength
through
O2 attacks
in
by XeF2,
reagent
shorter
Mo(CO),
Upon oxidation
bond)
(C5H5)2Cr
bubbled
C H CH Mo(C0) at 65 3 3 process is accompanied
and
nm)
CpOOCrO.
(9.1 06photon/s.mole),
ring,
(>6BO
Cp2Cr.
assume
peroxide
the
and
MO-F
of
CL component
should
1.6.10-3~ in
Reactions When air
is
of
decomposing
bonds
wavelength
of
with
Cp-Cr
oxidation
one
Upon oxidation
by the
of
dosed
short
tetramer
photon/s.mole
h$
nm) +
Cr(lIi)
by further
-
cat.
(425-575
resulting
“3+ [CpOOCr 01 ,,4
+ O2 -
of
presence bands
being
of
at
727
inherent
CO groups
Xe and to
the
by fluorine.
difluoride.
XeF2
liberation,
was originally precipitation,
described
in
11031
and multiple
to
colour
46 The
change5. ground
and
reaction
excited
products
states
W(CO)4F2,
as shown
Xe,
by the
CO,
CO2,
following
WF2 are
scheme
formed
in
their
[103-1061. Scheme
W(CO)6
f
xEf*
-[W(C0)6*XeF2]
W(C0) -r:
+ CL,
W(CO)5F
-
complex
[W(CO)5F]“.
‘Y,
CL 3, (12)
w(co)6 CL,
with
start
tration ing
to
effect
and
XeF2.
and
gas
was
were
(8)
(10)
3
CL5,
The
first
+ CL
(12)
5
a maximum at
time
magnitude of
traces
the is
[106]. of
An
derivatives
was
emitter
give
rise
of
to
the
brightest
lower
than
CL,
in
induction are
a certain can
long
the
waveseparate-
luminescence among those main
reaction
induction
period
(appearance
on the
reagent
period
exists to
at
earlier
dependent
difficult
be
emission
conducted
of
reaction
The
the
intermediate
intensity
reversibly
which
to
XeF2(1),
give
(5). of
nm. The
medium).
CL emitter
By experiments [105]
the
its
to
(3).
carbonyl
and 533
lit
decomposes
deactivation
unidentified.
reaction
electrophi
states
primary
W(CO)5
established
of
stage
to
cat.-
to
excited
the
with
liberation)
water
(11)
fluorination;
assigned
though
temperature of
complex
(9)
carbonyl
their
attacking
have
two orders
of
red
(13) of
the
in
remained
(9-12)
was
in
FL exhibited
[107]
CL4,
(6) (7)
F-derivatives
tungsten
W(CO)5F XeF’
CL component
reactions
CL2’ CL5
with
in
length
------
WOF4 + CL
stages
from
CL spectrum
The
described
+ CO
WF6 + CO
toluene
formed
molecules
the
(5)
C + CO2 (traces)
transfer
generated
+ Xe(XeF’)
+ CL, (540nm)
HF + Xe + 02 + CL4
. . . - successive
electron
nm in
Ha0
-
WH HF6
cat. tOC
intermediate
540
cells)
+ toluene
(where
W(CO)5F
WO3 + 6HF + CL2
+ H20
co + co
. . ,-
(WF * toluene) 6
WF6 + SiO(glass
of
:(3)
(4)
-
W(CO)4F2
-
-
WF6 + 3H20
also
__c
+ XeF’ (XeF2)
WF6 + toluene
portion
nm)
F + Xe + CO
5
[W(CO+F]‘:
+ XeF’ (XeF2)
W (CO) 4F2
After
(540
+ XeF’
---II
XeF2
(1) (2)
W(CO)5F
W(C0)
XeF2
-
+ CO
F + XeF’
IW(Co55F]-~.‘h -
W(CO)6
. XeFi]
[W(CO)t
-
16
due
remove
to
from
the
of of
conceninhibi
toluene.
t-
47
WQ, on the other At ly
higher
recorded
effect
is
is
hand,
followed
caused
swept
end
argon and
point
falling
7.
phase
by the
of
the
drops
from
refluxing
and
the
Reactions
of
benzoyl
in
product WF6 which
reaction
a
in
catalyst
was called
(Ar
reaction
makes
solvent
The CL flashes
This
is
the
are
the
drop
thus
“drop-flashed”
usual-
[lob].
WF6 circulating
medium in
flashes
is
the is
atmosphere
condensed
formed
at
the
by the
CL [lob].
SYSTEM.
and
organics
brightness to
with
(photon/s.mole)
the
02 and
oxygen,
CL with
xenon
in
(6.0.10~)
in
the
manganese
dependent
presence
XeF2
decreases
C6H5MnCl
of
be appreciably
to MN and
OMC with
02)
light
CL which
OF ORGANOMETALLICS OF SEVENTH GROUP METALS
[5,6]
attached
(with
maximum of
reiterated
dissolved
unit.
manganese
The existence
ligand
kinetic
difluoride,
and
peroxide.
described
manganese
of
system; the
effect
initiator.
the
volatile
the
subsequently
OF THE PERIODIC
ly
highly
flow
is
as an
(55’C),
of
CHEMILUMINESCENCE
7.1.
acting
by a number
by the
solution-gaseous
oxygenless)
is
temperatures
of
organics
on both
an Mn-Mn bond.
toluene
and CH2CI2,
following
were
the In
the
original-
nature
of
reactions
the
of
CL brightness
series:
> [(C6H5)3Mn]Li
(2.0-10’)
> (C5H5)2Mn
(5.107)
> Mn2(CO),0 (0); (with
XeF2)
Mn2 (CO)
1o does not
Cp2Mn is XeF2
(C5H5)2Mn
at
half the
and the
CL not
bony1
introduced
or
CH2C12
to
the
1s to occur the
specific
quenching
effect
1 i berated
toluene
solution
of
Mn2(CO),0
reacts
with
the
1 iberation
bands
at
quite
the
Such
of
CL in
reaction in
about
reaction rate
seven
of
(60% of hours,
the while
with
calculated that
nm.
gas In
reverse, of
[103]. rise
(Xe,
this when
XeF2
a phenomenon
Mn-Mn bond
Mn2(CO)10
of
345
solution
C H Mn(C0) does not quench but gives 5 5 3 to XeF2 reacting with the substituted
owing
low
of
(0).
a minute.
but,
quenched.
> Mn2(CO),0
a 1.5*10-2M
than
chemiluminescent
CL is
The absence
with
fai into
background
of
whilst less
Mn-CO absorption
the
addition
to the
02, in
(2.2.107)
band as shown by the of
only
> C5H5Mn(C0)3
with by 02
metal-carbon
however,
flash
react
oxidized
disappearance
is
(4.108)
in
carbonyl
amount was
of
car-
toluene
the
a luminescence C5H5-Mn
XeF2 was ascribed
process
the
was ascribed
Indeed, to
CO) case,
gas
bond. in
[481
COcXe was
seven-times
faster
C5H5Mn(C0)3). By analogy
we assigned
the
with red
the
reaction
CL exhibited
of in
C6H5MgBr with the
reacti.on
benzoyl
peroxide
C H MnCI+BP
65
to
the
(BF)[47], emission
>
48 by
[6,48].
(Ph3C’ )j’;
reaction either
Now, to accent
for
the
results
Ph CNa+O 2 [lO,ll], we wou’id rather 3 substituted derivatives of Ph C’, or
advocate
intermediates,
triphenylmethide,
Imax =3.4*106photon/s~ml
CL of DE+THF)
or
oxidized
by 02
to
was
originate
the
compfex
3
reaction
obtained
of
which
also
as a rapidly
CL in
alternative
Ph C- with 3 capable of
is
recorded
with
with
fading
red
PhMgCl light
of other CL[19].
(8.lO-*M
flash
in
(0.5
min)
[SSI. 7.2.
Electrochemiluminescence ECL originates
current)
electrolysis
throline for
or
the
of
of
by matching
the
wide
at
of
light
upon cyclic
of
3
ECL and
of
3
containing
[108].
FL spectra
AC(alternating
fat-ClRe(C0)
,I&-phenanthroline)
electroconductivity
580
fat-ClRe(CO),L. flashes
a CH CN solution
4,7-diphenyl-1
sake
maxima
(ECL)
as separate
The
the
(L=
O.lM
CL emitter
initial
L
(n-Bu4N)C104
was
complex
l,lO-phenan-
identified
solution
with
their
nm (Fig.16). Fig.16 FL(l) and ECL (2) spectra for rhenium carbonyl comp!ex in acetonitrile containing O.lM tetrabutyl-
*>-3 I_ P c2 +J c *_
jT!oJ
yZxZK:fZLYZ20
nm
-:I d 0 ,nm The
light
reaction
of
differently
charged
ion-rad’icals
generated
at
a Pt-
electrode. Scheme [fat-ClRe(C03t]+ -
[fat-ClRe
7.3.
Reaction
of
reaction
of
Volger
into
which
matched was
al.
the
linearly
CL emitter
for
CL excitation
1 Re (CO) 3L] ‘*-
with , (CO)~Re-Re(CO)~(phen) found
that
FL of
the
dependent was
with
upon addition
formed was
by Schuster
in
and water
the
during
described et
al.
to
primary on
for
nm)
hydroperoxide
of
and
Re(phen)(C0)3Cl, tetralin
bright
rhenium
complex
[IO91
aromatic
the
was
red
[TO9J.
of
The CL inten-
reaction. similar
trans-
spectrum
indicating
hydrocarbons,
slowly
rapidly
CL the
concentration
bimolecular
by a scheme
(580
chlorine.
boiling give
complex
the
[IlO]
h?
tetralinyl
hydroperoxide
al-tetralone
the
suggested
Cfat-C
-
Re(phen)(CO),Cl
tetralinyl
formed
sity
[fat-ClRe(E0)3L]’
(C03L] ’ +
et
decomposing
+
17
that
The mechanism to
that i.e.
CIEEL.
49
H Re(phen)(CO)$l
H
+
[Re(phen)(C03Cll+
H20 + [Re(phen)(CO)3C1]+[
1 )
0 I
O-OH
a3
[
Ii '---c
18
Scheme
O-OH
1 ’ /
I--
I--
co +
[Re(phen)(C0)3Cl]B
-
h3
(580
nm)
I> 03
Similar the same
CL was
responsible oxidation suggested
reported
peroxide
for
[log].
[k(bipy)3]*+
The emission
for the bright
CL which
catalyzing
of the above was
observed
the decomposition rhenium
complex
to originate
of
(CO) Re-Re(C0) (phen) by chlorine in DMF 5 3 by Vogler et al. in [ill] is as fo'IlowS.
[ill].
of
was
in the The scheme Scheme
(CO)5Re_Re(C0)3(phen)
a.
CHEMILLIMINESCENCE OF THE
PERIODIC
8.1.
Reactions
with
O2 and XeF2
CL
Table
+ Cl2 -
2. CL
OF ORGANOMETALLICS
Rh organics
[5,481
(Table
Intensities
and XeF2
OF EIGHTH
with
in reactions
oxygen
hg(580
METALS
of some
and xenon
difluoride.
OMC of Fe, Ni, and
Rh
(I) in Oxidation
(300 K)
in Tvluene
of Fe, Ni, and Rh OMC
by 02
(330 K)
[5,48].
I, photon/s-mole XeF,
1
(C5H5)*Fe
0.0
0.0
2
Fe(C0)5
0.0
1 .a406
3
Fe2(CO)g
0.0
1.0.105
4
[P(C6H5)312Ni
2.a.lo7
4.6.10'
9.2.105
2.4407
1.7*106
4.a.107
SitCH,), 6
(acac)Rh(CO)2
4
nm)
2).
OMC
no.
GROUP
-
TABLE.
of Fe, Ni,
is exhibited
+ [Re(C0)3(phen)CI]*
Re(C0)5CI
19
Si (CH3)3
Si (CH,),
50 Iron
carbonyls
solid
(entries
precipitate.
oxidized
by both
brighter
with
be assumed
bright
CL with
activity
of
5)
Electrolysis the
of
spectrum
of
the
(Fig.171
[1131.
of
ECL is
the
of
I
540
is
attack to
almost passive
of that
Ni-Cp
of
of
a Pt
to
yield
(entry
an order
on the
Xe, 4)
of
Ni-C
magnitude
1,
bond.
4 shows
platinum
(II)
CO and
is
XeF2[112
entry
complex
with from
FL spectrum
two -1.5
for
the
the
Less
h gher
Pt-C
complex. bond yields
to +0.85
the
eV.
The
same complex
(Wd2
I
I
620
660
spectra (exci
for O.OOOlM plarinum tation)= nm [ 1131.
580
to
bond.
changed
the
XeF2 bonds
towards
XeF2
ortho-metalated
a Pt-electrode similar
CL with
and Si-C is
bond
Pt
I
Ni-
CL which
the
a solution
potential
weak
its
compared
bond than
Electrochemiluminescence
ECL as
only
CH2-Si
from
(entry
Ni-Ph
emit
the
result
XeF2
the
to
Since to
reveal OMC with
reagents
XeF2.
CL can
8.2.
2,3)
Complex
A,nm Fig.17
The
FL (1) and complex in
ECL(2) DMF,
ECL excitation
ear I ier
for
scheme
the
ECL of
[113]
the
differs
very
little
organometallic
from
that
suggested
compl ex.
rhenium
Scheme 20 Pt(Thpyj2
+ e- -
Pt (Thpy);
Pt(Thpy12
-
Pt (Thpy);
Pt (Thpy);
+ Pt (Thpy);
In
the
presence
of
the
potential
actions
of
anion
e- -
of
-
10e5M K2S208,
changes Pt(Thpy);
from and
pt(Thpy):!
+
ECL was observed
-1.8 S20i--
to
0 eV. ion
with
This the
[Pt(ThpyJ21’
within
-
hd(58Onm)
a different
was caused subsequent
by the
range inter-
formation
of
51 SO,
species
which
take
latter
in
as
strong
an electron its
Pt(Thpy);
from
+ SO,
literature
reagents
with
Grignard
Indeed,
02-saturated
butyl
the
CL spectrum
while of
the
time,
upon
the
was
rhodamine
or
organic as all
fragment
other
etc.)
with
does
PhMgBr with
are
met.
band with
9-BBN
of
With
02,
the
of
the
420
with
9-BBN
a short the is
act
of of
with
increase
pyrene at
DPA.
(1.5-fold
10 -‘M
to
show only
of
DPA suggests
by direct
component
with
of
a long that
triplet-triplet
The
a
due CL is
the
wavelength
to
the
at
versa,
FL of
singlet
much of
DPA,
addition
state p(T,)
iS
+ A(S,)
of a new
DBA [48]. [85],
incorporates
reaction
of
series:
naphthalin
and
activated
CL
(unidentified)
with
and more
nm).
level,
the
incorporates
(max-560
that
hydrides
states
less
in
and
except
for
DPA than than
The peculiar
-
not
P(S,)
it
l&fold
no FL of
excited
an
emitter)
shows
the
of
one
the as
of
energy
in
spectrum
wavelength
singlet
the
CL spectrum to
that than
transfer nature
FL of
decreases
CL spectrum
transfer
in
the
penta-
course,
boronalkyl the
vice
10 -3M
is of
agents
amplified
component
activator’s energy
long
it
same as
The
CL.
the
(suitable
and and
[85,89];
increase pyrene);
the
the [55]
activating
the
rubrene,
the
CL intensity
for
two components:
wavelength
reactions
is
alkyls
At effect
rather
(C H ) Mg, the 372 CL spectrum
of
additions
[46].
energy
provided,
by DBA (Fig.18)
coefficient
observable We consider
and
the
quenching
10-3,
in
DPA [9],
indicating
of
the
band
of
with
any
by
to
second
reaction
CL activator
nm which
nm)
rather
added
derivatives of
(otherwise
oxidation
addition
as quenchers
shows
any
[47].
intensity
the
unchanged
chemical
metal
desired
are
activators,
of
to
the
(580
FL spectrum
absence
CL activation
aluminium
the
about the
introduction
rise
DBA>rubrene>anthracene>pyrene>DPA benzophenone
SO,
the
CL exhibited
(DPA)
remain
the
peroxide
the
activated
DBA.
with
give
oxygen
maximum at
effectively
FL of
in
of
9,10-substituted
course
hv
additions
bring
to
The
that for
of
to
luminescent
the
luminescence
Upon oxidation CL is
not
Thus, the
its
its
those
not
factor
requirements
DBA enhances
generate
-
activation
luminescent
stated
benzoyl
and
a determining
to
+ SO;-+
UPON CL OF OMC. LOW-TEMPERATURE CL.
on the
reported
transfer.
cene,
CL of
and
energy
the
anion
[Pt(Thpy)2]*
band matching
was
in
of
+
reported
that
generated
a result
the
was
publications
CL emitters
CL emitter
Pt(Thpy)2
9,10-diphenylanthracene
PhMgBr,
, anthracene both
-
complex
ADDITIONS
by various
same CL spectrum
chrysene
same
02
ether
SO;-
data
2.5.1t4M
of
another
--
existing
discrepant.
+ S20;-
state
THE EFFECT OF LUMINESCENT The
the
away
excited
Pt(Thpy);
9.
oxidizers
DPA
effect Only
+ k(s,),
52
5
lo
15
20
[A].io3,M
+0.2 i
-
\
1
0.1
% 38C CI .: 0) 34C CI t: .& 3oc cc 8c 4c 0
&
lg[Al Fig.18.
(1) dependence of CL intensity on DBA concentration (A) in autoxidation of 0.0068M 9-BBN in THF [89]; (2) linear representation of (1); (3) and (4) dependence of CL intensity on lg[A] for DBA and pyrene, respectively, in oxidation of 0.002 diethoxyethylaluminium by O.OOlM xenon difluoride in toluene [ES].
but also
via
the
formation
k+,) which
are
further
p(T,) and due
to
The above the
different
low
-
P(S,)
transformed of
+ %(T,) the
i(T,)
molecules
in
the
activator
-
+ W(Tl) scheme
for
effective
+ A(T,)
by the
reaction
with
triplet-state
ketone
at
A -
[P.A]“----w
triplet-triplet
P(S,)
annihilation
__c
[AA]“‘-
CL activation formation
+ B(S,)
at
high
i(S,)
its
excited
of
A
+ A(S,)
rationalizes of
concentration
the states
absence X(T,)
of in
DPA FL in comparison
terms with
activators. Upon autoxidation
too.
triplet-excited
?c
+ A(S,)
low concentration
of
of
)
i(S,
However,
of
DBA additions
Cp2Hg result
[53] in
and Cp2Cr only
[loll,
a slightly
the
ketones
amplified
are
excited
CL (2.5-fold
53 increase
at
distorted high
10-*M
due
to
DBA).
The
effect
of
DBA concentration.
low effective Cp-ring
The
energy
the
same type
Usually, observable found
the
the
of
DPA to
amplify
CL can
be identified
-10w3M.
curve
the
It
is
indicative
the
where
the
emitter
the
activator
activator it
makes
is
FL is
activators
in
are
that
there the
chemical
excited
in
[Sg]
10’3M
was
proved
for
of
The
the
ketones
We have
formed
XeF2
and
(Fig.18).
solutions of
1y
recent DBA,
with
[A]=
concentration dependence
(Fig.18).
is
That
a matter the
of
the
curve
the The
some difficulty
states CL.
p-terphenyl, nm).
of
same spectral
singlet
activated
FL (max=345
following
low DBA
CL activation.
emission
nm. With
its
of
by the
increasing
occupies
to
by the
products
a new type
concentration
DBA FL
appreciably
with
steadily
of
band at
anthracene,
reagent
CL spectrum
390
of
is
[ 1141.
found
usual
contribution
as
was
(C2H50)2A1C,H5
nature
displayed.
region
accounted the
1 O”M
CL (XeF’)*
maximum at the
CL is
that
wavelength
ketones.as
pyrene,
in
activator
an activated
a sufficient
observed
eye
from
nonactivated
as a sharp
occurs
ing
of
of
naked
the
short
derivatives ca.
p-terphenyl,
reaction
the
with
of
of
excited
anthracene
lo-‘M
the
CL matches
the
assignment
with
different
of
of
concentration
even
The measurement
activated
of C H with O2 in THF, where 56 autoxidation of Hg and Cr OMC.
the
interesting is
CL intensity
since
reaction in
with
of
shape
in
CL in
is
which
the
latter
as
activator
addition
dependence
from
CL activation
at
of
reabsorption
low amplification
The
CL observed
of
spectrum
transfer
transformations.
activated were
lo+
of the
region
of
With
an
pyrene,
spectral
singlet
broaden-
states
of
scheme. Scheme
A + XeF*(XeF’) >AI-R(R’) The
starting
its
cation
A+ + XeFi(XeF-)
-
>Al+-R’(R+)
+ A’ XeF2
A+(l).
by a molecule
of
or
the
The the
reaction
starting
(1) -
+ ii
intermediate
singlet-excited
A*
OAC or
21
CL
XeF’
is
oxidizes
generated
by another
upon
(2) the
the
intermediate
activator
to
reduction
-
alkyl
of
A+
radical
R’ (2). Upon autoxidation Ru(bipy)3C12*6H20 cation there
of
occurs
Ru(bip~)~Cl, the
CL,
complex established
OAC [62]
to
the
added the
maximum of
a redox *6H20
concomitamt
of
reaction
1 iberation
in
of
the
in
the
activated
the
the
water
toluene
gaseous
boralkyl gives
is
of
[Ru(bipy)3C1*(OMC)n], by a match
solution
which of
(insoluble
and
latter
of
hydrides rise
red
to
[115],
an appreciable
spectral
region
crystallization
and THF) hydrogen
with
and
emitting CL spectrum
the
of
to
amplifi(6ooi.15 the
nm);
solid
OMC involved,
formation the
crystalline
of
activated FL of
a soluble CL.
the
with
It
was
complex.
salt
54 Two mechanisms
were
and
[62].
“physical”
intensity
as
considered by the
the
Later
the
for
on
acceptor
that
differently
CL of
suggested
of
CL activation
in
[116],
energy
CL activation shaped
in
from
the
was
excited
had a chemical
kinetic
OAC autoxidations
Ru(bipy)3C12
dependences
shown
ketones,
nature.
for
so
That
activated
-
to
“chemical”
have it
the
can
lowest
be
was confirmed
and
nonactivated
OAC [62]. We are
rather
inclined
electron-exchanged
to
advocate
luminescence
the
(CIEEL)
mechanism
according
of
to
the
chemically below
initiated
scheme. Scheme
>M-R + 02 Ru (I
>MOOR
22
(1)
I ) + >MOOR v
I ).>MOOR]
[Ru(l
------r-[Ru(l
I I)*>MOOR’]
-
(2)
9:
I I)*(R-0)-l
-[Ru(I
(where
M -
-
boron
The organometallic (OMC),].
After
Ru(lll) from
(2), which
state
of
electron the
the was
a linear
with
catalytic
e.g.
for
CH2C12) with
[118].
(3)
intermediate
peroxide
for
ketone
the
of
ruthenium R=OL
to
of
CL intensity
[Ru(bipy)3C12’
radical-anion its
emission
feature
activated
complex
and oxidation
the
be reduced
peculiar
to
[63]
a bright
generation by the
peroxides
to
of
the
of
CIEEL,
divalent
excited
activated
CL.
i.e.
on OMC and
by the
Ru(ll)
+ XeF’
Ru(l I I)+ presence
That
existence
ruthenium
of
XeF2
following
[72],
luminescence
complex
the
in
of
chemical data
CIEEL metal
mechanism complexes
>AIR of
the
in
crystalloluminescence
[48],
the
crystallization
of
activation
of
luminescent
the
complex
for
a few
With
the
flashed
[$u(bipy)3C12(0AC)n]
[Ru(bipy)3C12(0AC)n] other
CL reactions
latter, like
the
activation
a burning emitting
in of
CL at
toluene
OAC, was
flame
so
[48]. 610
nm is
scheme. Scheme
The
to
solutions.
solution
and
In
follow
excitation
and
reported
also
a good activator
red
to
and
[ 1091
be possible
t10m3M out
observed
(C03)
OMC reaction
dioxetane
demonstrated
of
According
from
turned
that The
the
Re”(phen)
be assumed
complexes
effective
of
an
form to
CL was originally
A homogeneous (or
the to
responsible by the
decomposition media
Ru”(bipy)3CI
metal
CL
[48].
amplified
OMC CL can
forms
an electron
being
dependence
homogeneous of
accepts latter
to
decomposes
established
concentrations The
>MOOR (1)
transfer
complex
-
.Ru( I I)]
aluminium)
peroxide
Ru(lll)
(3),
mechanism
[R-O’ or
-
Ru(l I I)
___c
Qll)
strongly
oxidized
+ XeF-
(1) CL
radical
23
(2) XeF’
as an
intermediate
species
55 in
the
reaction
trivalent of
of
state
Ru(lII)
(1).
450
region
the
emitter
of
decrease the
visible
due
recently CL of
activated
in
the
slowly
at
The
of
the
the
dependence
of
Ru(ll)
by the
to
its
reduction
[Ru(bipy)3C12.(OAC)n]
Ru(bipy)9C12
of
in
the
453 nm
from
to observe K)
formed
of
surface
of it
nature:
melting
point
POSSIBLE Nowadays, research
ruthenium
of
the
[74].
of
at
500
at
500 nm.
reactions Thus,
(C2H5)3Al
anf
the
nm
with
emission
solutions
red
to
the
of
OMC
with
a
XeF2
in
luminescence
the
of
can
of
CL) to
the
as well
CH2 Cl 2, crystals.
The
is caused CH2ClZ
rate
due to
higher
high
by the (176
data
point [117]
100 K (the
with the
reagent
at
mixing
second
radical
Radicals
C H’ 25
tecnique solutions
The CL maximum at transition,
on the
maximum at of
so the
reagent
phase
activity
mobility
level
first
technique).
recom-
growing
occur.
exothermal
temperature
of
the
liguid
of
temperature
temperature,
CL decays
of
The
activity
increasing
77 K (the
chemical
growing
of
causes
The curve
maxima.
on the
transformations
under
[74].
temperature
With
as from
77 K (the
reaction
starting
temperature
chemical
nm)
reported
shows several
medium).
lower
was
CL (max=61B
reported
region
as other
freshly
190 K is
initial
i.e.
of
more
reagents
near
K).
USES OF APPLICATION liquid-phase
of redox
CL intensity
152 K; at
grinding
development.
was the
ligand
triethylaluminium
C2H5 increases,
frozen
of
sources
to
a concomitant
organic
.(C2~5)3.Alnl,
with
that
from in
increased
with
unique
solutions
involving
mechanical
crystallization
frozen
&J(lll)
and a new FL arises
chelated
the
low-temperature
low-temperature
the
in CH2ClZ
Et~(TTA)~phen
activated
possible
in an amorphous
reduced
subsequently
160 K marks
the
I)
the
lo-‘M
magnitude.
!
follows
up to is
of of
Eu(ll of
[Ru(bipy)3C12
of
EPR signals
CL intensity
FL of
95 K was attributed
processes
concentration
frozen
the
addition
OMC illustrated
95 K
C2H5 radicals
rate
result
at
which
of
binationof
of
of
excited
complex
The CL is
product
dependence
CL at
C2H5 radicals,
the
complex
for
temperature of
of
complex
be responsible
nm).
be one of
CL of
even
to
emergence
of
to
the
low temperatures
excited
of
10.
of
absorption
[89]
reaction
mixture
be registered
the
oxidation
CL is
O2 by two orders
CL (max=613
The
very
heated
presence
trivial
the
activated
presence
to strong
intensity
solution.
occurring
(200
the
observed
Low-temperature
of
in
9-BBN with
g-BBN was established
the
of
about
(& =14000). We have
the
brings
The emitter
CL exhibited
nm is
amplify
in
XeF2
by OAC (2).
Dark-blue at
OAC with
CL with The overaIl
OF OMC CHEMILUMINESCENCE OMC is results
growing
out
obtained
of
IN SOLUTION. its
so far
early provide
stages reliable
56 predictions
of
The
A.
ability
in
of
H ) 493 10 -8M
AI
or
analysis
air.
The
CL
intensity
The
above
approach
industrial
stage
the of
the
small
control
A few
11.
CONCLUSIONS. REACTIONS
time,
which
to
peculiar
reactions
of
as
02,
Hz0
thermal active
or
can
of
application
be
to
of
the
and,
of
the
their
an
OMC with
of
the
process)
at
alkoxides by
alkoxides
of
IR absorption
bigger
oxidation
employed
at
of
as
opposed bands
present
Continuous
for
to
control
reported
the
by
a much
their
OMC CL were
most
OMC concentration, control
to 10%)
solution,
bubbled
industrial
process. CL.
aliquot
of
are
of
upon
quanti-
The
OAC (ALFOL
OF LIQUID-PHASE
observed the
an
important
generate
various and
of
in
a
can
in
our
CHEMILUMINESCENT
elucidation
of
OMC.
with
of
the
for
the
of
common in
Indeed,
as
sholJn
of
different
peroxides of
active
represented
by
molecular
of
At the
solution,
in
this
the
same
potentials which
review,
chemical
of
is
CL arises nature
dioxetanes,
intermediates. and
reactions
regularities
in
including
generations
chemical
solution.
estimation
states
species
different
be
variety
products
basis
OMC with
CL can
great
electron-excited
electrochemical
stages
the
use
an
advantage
(below
of
the
the
in
oxygen.
to
from
which
or
even
for
activated
continuously
Czo )
OMC transformation
feature
in
XeF *,
intensity
complicates
provides
OMC reactions another
of
to
ruthenium
designed
analytical
course
Cg
the
CL with (C2H513
CL exhibited
bonds
that
the
has
the
to
OF OMC.
excitation it
in
species
products, stage
be
OMC with
[48]
to
method
CLASSIFICATION
emission
OMC, the
in
with
uses
by
alcohols
in
the
of
proportional
fatty
from
final
can
intensities
solvent
amplify either
of
of
(metal-hydride) high
applied
This
important
other
[481.
with
usually
(ranging
impemented
book
Light
is be
to is
owing
[48].
consists
the
of
change
that be
the
intensity
and
O2
trialkylaluminium
[48]. CL
OAC
starting
also
with
into
can
of
oxygen in
mixtures to
to
possible
complexes
intensity
CL exhibited
production
oxidation
the
the
technique
syringed
aerobic
metal
instruments
non-activated
is
becomes
R Al, where R3Al 3 enables the estimation
metal-carbon
owing
ions
to
solution
of
possible
solution
change
added
luminescence.
metal
fluorescent
that
estimations is
convenient
C.
of
H ) AIH, 492 by measuring
of
that
express-CL-testing
sometimes,
for
(i-C
solutions
contact
tative
bright
Ru(bipy)3C12
Small-sized
which
for
estimation
some
Thus,
direct B.
applications
quantitative
OMC. (i-C
some
free-radical
such upon
The
photoprocesses
involving while
electron
that
is
The mechanisms their
emitter
generation
of
n+ >M
-
All
transfer.
condition
of
often the
natures
in
species
accordance
with
OMC are
generate with
the
highly
OMC can
following
states.
be classified
general
j:;;;,b:,;
24
RR*)
(R.)+c
C
(R-Ox)“’
d
-I%
for
(R-Ox)”
Rjli(and/or
b
by
schemes Scheme
j$-;
R + Ox-d
exothermic,
excited
[“8].
a
>M”+ ---c
of to
known CL reactions
excited
R + Ox-d
CL reactions
insufficient
+ >M”+’
(Ox’)*
* (where
The
M- metal; J- excited
R -
pattern
of
first
represented vary
(I of
(I
Cp3Eu,
or
e.g. in
be attributed second
ed only
to
types
one
of
XeF2,
an organic
radical
much more widespread; types
OMC organic
for
molecule;
with (I
their
the
the
The of
can in
(C5Me5)2Yb
oxid-
[92]
oxidized
and metal
CL pattern
is
an OMC organic
(I b).
The
>LnOOCp and
fragment
emitters
the
emitters those
of
which
The emission
fragments.
fragments,
example,
CpnUXm,
are
oxidation
for
c)[98].
peroxides
which
CL dis-
Cp3Ln
194.951
as well.
alkali
being
of
metal
oxidation
metals as
Ph CNa with 02[10,11]. 3 r (Ox’)“(lI d), which
(XeF’)*
of
Cp2Sm [93-951,
of
organic
of
rate
emitters
cyclopentadienyls
reactions
of
of
oxidant
exhibited,
[92];
pattern
adducts
The
emitter
products
OMC organic
‘ar
of
first
fragment
-
the
CL is
Cp2Eu,
the
ketones
of
reaction
organic
163.
a)
lanthanide
the
are
a rule
ions. b).
is
includes
excitation in
OAC with
of
reactions
oxidant
(I
excited
based
CL pattern
by different
of
(I
fragment
by the
Cp-ring
The
The
metal
by O2 as
hydrolysis
in
Ox-d
redox-reactions
unchanged
an oxidant
can
201.
fragment;
CL emitter).
CL incluedes
remain
characterized
occurs
of
Cp3Sm [93-95],(Cp5Me5)2YbCl
to
ligand, played
OMC organic
state
metallocenes
attached also
(CL)
by electron-excited
a,c)
ation b)
h3
emitter are
electron
radical
(R’)*
The
same
was found [79].
represented
being
of
and
excited
are
represented
molecular
R*
acceptors (‘I
b)
is
with
only
in
Reactions by the ketones
(II
a)
[‘7,‘8,
was registerthe
emission
reaction
of
(‘I
following oxidized and
C)
n-olecu-
aldehydes
as
58 We have
recently
observed
naphthalene,
diphenylanthracene,
in
of
oxidation
Ce(lV), has
sodium
Ru(llI).
been
by singlet-excited and
rubrene,
adducts
Besides,
with
existence
of
of
the
said the
XeF2,
anthracene
hydrocarbons emission
of
molecules which by XeF2
hydrocarbon
are
of
generated
[llg], eximers
recorded.
Despite
the one
CL reactions, beautiful
CL emitted
light
should
reactions.
look
only
rare
forward
instances to
future
illustrating observations
each of
new
type
of
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