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Formation of mesophase by hydrogen bond directed self-assembly between barbituric acid and melamine derivatives
ELSEVIER
Synthetic
Formation
Metals
71 (1995) 2107-2108
of Mesophase by Hydrogen Bond Directed Self-Assembly Between Barbituric Acid and Melamine Derivatives
W.-S.Yanga, S.-G.Chen”, X.-D.Chaia>b*, Y.-W.Cno”, R.Lu”, W-P.Chai”, Y.-S.Jiang”, T.-J.Li a and J.-M.Lehnb* “Department of Chcmistr):, Jilin Ilnivcrsity,
Cl~angchun,
130023, P.R. China
bCllinlir: dcs Intc~-actions Molkulail-es, Colltigc dc France, 11 Place Mar&in Bcrthelot, 75005 Paris, France Abstract The 1:l nmoplwx
was fomlcd though molcculnr sclIlasscmbly dlrcckd hh, h\,drogcn bonding between light active barbituric acid derivative, j-[4-dodccylos~bcl~/!,lidcnz]-2,4, h,-( I I I, 31I)-p!,rilnidillctriolll: (13) and mclaminc derivative, 4-amino-2, &didodecylamino1, 3, 5-triazine (Mj. It was found through te,npcraturc-dcpclldcllt lI< spectra that thcrc are three kinds of hydrogen bonds with different strength in this mcsophasc. M’hcn dispcrscd in chloroform, this mcsophasc sho\\~s a double helical structure. 1. INTRODUCTION
It has been realized by Ircccnt rcsearchcs that supratttolccular species with desired architectural and functional fcaturcs can be obtained by molecular self-nsscmbl~ through manipulatinp the type and orientation of noncovalcnt intcractious hctwecn the molecular coml~o~i~~its[ I, 21. Among the bonds and interactions applicable to molecular sclI-assembling, hvdrogcn bonds Itavc received much attention due to their strong directional nature: [3, 41. Many acll-delincd shapes or pattcms have been construckd by hydrogen bond dircctcd self-assembly bct\vccn complcmentary molecular components, the formation of variable molecular ribbons composed of ac)~laminopyridil~e and acid 151; extended sheet structures of urcylcncdicarbosylic a&s [6]; and molecular strands ]7] or q’clic aggrcgatcs 18, 91 or ordci-cd bilayer membranes [IO] made up of alternating mclaminc and barbiturate derivative components. hi this work i: pair of coml~lcmcntar! componciits, light active j-[4-dodcc~los!,bc,l~~,lidclic]-2, -1, 6.-i I I I. 31I)-p!‘lrlinidinetrione (B) and 4-amino-2, h-dlclotlcc~lalllino- I, 3, 5-triazinc (M) were designed and synthesized. It has been kno\\~ that supran~olecular species can bc fonncd hct\\,ccn barbituric acid and melamine dcrivativcs through triple hydrogen bonds 171. Thus the present molecular components, 13 and M, are cspcctcd to construct supcnnolecular spccics 13.M U’itli nonlinear, electron transfer or liquid crystal propcrtics. 2. EXPERIMENTAL Melting points \\‘crt: measured \\itll a Microscopic Melting Point Meter. Infrared spectra \\‘erc recorded on a Nlcolct 51)X FT-IR Spcctromctcr. I‘EM csperimcnts \\crc pert’onr~od \vith a
0379-6779/95/$09.500 1995 Elsevier Science S.A. All rights reserved SSDl
0379-6779(94)03189-D
li?OI, KM-1200C Electron Microscope. stained by uranyl acetate.
The samples were H
7 ,e\
‘N-R
:
1-I
N-R H’ R= C12H25
(B)
(M)
Synthcscs of the two complementary molecules B and M used in this work were reported in reference [ 111. Both of them ai-c quite soluble in chloroform. The melting points B and M are 80-8 I “C and 226-227°C respectively.The resulting mesophase \\‘a~ obtained as yellow precipitates (B,M) when B were mixed \\,~th one crluivalcnt of M in chloroform. The melting point of this mcsol~l~asc is 167-172°C. Elemental analysis shows that the ratio of 13and M in the resulting mesophase is 1:l. 3. RESULTS
AND DISCUSSIONS
‘l’hc tcmpcrature-dependent IR spectra (KBr) of B.M are given in Fig. 1. The spectrum at 25 ‘C in Fig. l(a) shows that the N-II stretching bands of B,M are at 3402 cm-l, 3351 cm-l and 3 3 IO cm-‘. Before B and M were mixed, the N-H stretching band of 13 is at 3198 cm-l belonging to associated form. lR spcct~-urn of M contains N-H stretching bands at 3360 cm-l and 326X cn~-’ \\hich are also due to its self-association. The N-H srrctching bands of B.M are different from those observed both for 13and M. The lR changes suggest that triple complementary
2108
W-S.
L
.~._
_
__L__.._I~
_~~~
Figure 2. Ilcctron
~-2
micrograph
of an aqueous dispersion
of B.M.
3100.0
3366.7 3233.3
3500.0
Yang et al. / Synthetic Metals 71 (1995) 2107-2108
heating. In [act it has been reported
WAVENUMBERS(CM+
stretching
16OT
band around
and was related Therefore,
for barbituric
with intermolecular
this
acid the C=O
1670 cm -l only appeared
change
also
in solid state
hydrogen
indicates
that
bonding B.M
[12].
is formed
through hydrogen bond directed molecular self-assembly. Fi
is about
micrometer.
This
directed molecular ordcrcd
and the diameters
500 nm and its length means
that the pattern
self-assembly
and \\,cll-defined
in the mesophase
structure.
Further
of double
is in the scale of of hydrogen bond must be in a
researches
on this
point are being carried out.
-._ 1800.0 1566.7 _I-_--
--___
_~
WAlENUMBERS
(a) 3100 cn~-1-3500 cm-t
assembling spectrum conclusion.
bonds
were
formed
in accordance in region
REFERENCES
(c’d >
Figure 1. Tem1)cratrlrc-dependent
hydrogen
-1
1100.0
1333.3
1. J.-M. L&n, Angew. Chem. Int. Ed. Engl., 29 (1990) 1304. 2. G. M. Whitesides,
Infrared spectra of l3.M. (b) 1100 cn~-l-lXOO cm-’
between
I? and M via
1X00 cm-t
There are t\vo C=O stretching
also supports
sclfthis
bands at 3737 cm-
and 1670 cm-’ for B, but they are at 1715 cm-’ and 1672 cmwl for B.M. The N-H stretching
band at 33 IO cm-t and its shoulder band
at 3351 cm-l split into t\vo indcpendcnt decreases
while the temperature
3310 cm-l decrcascs
peaks and their strength
rise. The strength
of band at
more rapidly than that at 3351 cm-*. The
N-H stretching
band at 3402 cm-* also has similar behavior and it even disappears at higher temperature (> 120°C). Mean\\ bile,
a new band appears at 3425 cm -t \\+ich represents ii wca!icr hydrogen bond formed between 13 and M. From I:ig. I(b) it can be seen that the strength decreases
or C=O stretching
gradually and disappears
band at 1672 cm-’
at higher temperature
C. T. Seto, Science, 254
3. J. G. Stcvcn, C. Vicent, E. Fan and A. 1). Hamilton, Angew.
with the model [7]. The analysis 01‘II<
1600 cm“-
J. P. Mathias,
(1991) 1312.
when
Clmn.
ht. Ed. Engl., 32 (1993) 119.
4. M. C. litter, J. Phys. Chem., 95 (1991) 4601. 5. S J. Gelb, S. C. I-Iirst, C. Vicent, A.D. Hamilton, Sot., Chcni. Commun.,
J. Chem.
(1991) 1283.
6. X. Zhao, Y. -1~. Chang, F. W. Fowler, J. W. Lauher, J. Am. Clmn.
SOL, 112 (1990) 6627.
.I.-M.I,chn, M. Mascal, A. DeCian and J. Fisher, J. Chem. Sot., Chcm. Commun.,
(1990) 479.
C. T. Seto, G. M. Whitesides,
J. Am. Chem. Sot.,
115 (1993) 905; 1330; 1921. C ‘I‘. Seto, G. M. Whitesides,
J. Am. Chem. Sot.,
112(1990)6409; 113(1991)712; 114(1992)5473. IO. N.Kimizuka, T.Kawasaki and T. Kunitake, J. Am. Chem sot., 1I5 (1993)43X7. I I. Y. W Cao, X. D. Chai, S. G. Chen, T. .J. Li, Chemical Journal ot‘chincsc
Universities,
12. A. .I. T3anxs et al, J. ofMolecular
11 (1994), in the press. Structure,
56 (1979) 1.
Synthetic
Formation
Metals
71 (1995) 2107-2108
of Mesophase by Hydrogen Bond Directed Self-Assembly Between Barbituric Acid and Melamine Derivatives
W.-S.Yanga, S.-G.Chen”, X.-D.Chaia>b*, Y.-W.Cno”, R.Lu”, W-P.Chai”, Y.-S.Jiang”, T.-J.Li a and J.-M.Lehnb* “Department of Chcmistr):, Jilin Ilnivcrsity,
Cl~angchun,
130023, P.R. China
bCllinlir: dcs Intc~-actions Molkulail-es, Colltigc dc France, 11 Place Mar&in Bcrthelot, 75005 Paris, France Abstract The 1:l nmoplwx
was fomlcd though molcculnr sclIlasscmbly dlrcckd hh, h\,drogcn bonding between light active barbituric acid derivative, j-[4-dodccylos~bcl~/!,lidcnz]-2,4, h,-( I I I, 31I)-p!,rilnidillctriolll: (13) and mclaminc derivative, 4-amino-2, &didodecylamino1, 3, 5-triazine (Mj. It was found through te,npcraturc-dcpclldcllt lI< spectra that thcrc are three kinds of hydrogen bonds with different strength in this mcsophasc. M’hcn dispcrscd in chloroform, this mcsophasc sho\\~s a double helical structure. 1. INTRODUCTION
It has been realized by Ircccnt rcsearchcs that supratttolccular species with desired architectural and functional fcaturcs can be obtained by molecular self-nsscmbl~ through manipulatinp the type and orientation of noncovalcnt intcractious hctwecn the molecular coml~o~i~~its[ I, 21. Among the bonds and interactions applicable to molecular sclI-assembling, hvdrogcn bonds Itavc received much attention due to their strong directional nature: [3, 41. Many acll-delincd shapes or pattcms have been construckd by hydrogen bond dircctcd self-assembly bct\vccn complcmentary molecular components, the formation of variable molecular ribbons composed of ac)~laminopyridil~e and acid 151; extended sheet structures of urcylcncdicarbosylic a&s [6]; and molecular strands ]7] or q’clic aggrcgatcs 18, 91 or ordci-cd bilayer membranes [IO] made up of alternating mclaminc and barbiturate derivative components. hi this work i: pair of coml~lcmcntar! componciits, light active j-[4-dodcc~los!,bc,l~~,lidclic]-2, -1, 6.-i I I I. 31I)-p!‘lrlinidinetrione (B) and 4-amino-2, h-dlclotlcc~lalllino- I, 3, 5-triazinc (M) were designed and synthesized. It has been kno\\~ that supran~olecular species can bc fonncd hct\\,ccn barbituric acid and melamine dcrivativcs through triple hydrogen bonds 171. Thus the present molecular components, 13 and M, are cspcctcd to construct supcnnolecular spccics 13.M U’itli nonlinear, electron transfer or liquid crystal propcrtics. 2. EXPERIMENTAL Melting points \\‘crt: measured \\itll a Microscopic Melting Point Meter. Infrared spectra \\‘erc recorded on a Nlcolct 51)X FT-IR Spcctromctcr. I‘EM csperimcnts \\crc pert’onr~od \vith a
0379-6779/95/$09.500 1995 Elsevier Science S.A. All rights reserved SSDl
0379-6779(94)03189-D
li?OI, KM-1200C Electron Microscope. stained by uranyl acetate.
The samples were H
7 ,e\
‘N-R
:
1-I
N-R H’ R= C12H25
(B)
(M)
Synthcscs of the two complementary molecules B and M used in this work were reported in reference [ 111. Both of them ai-c quite soluble in chloroform. The melting points B and M are 80-8 I “C and 226-227°C respectively.The resulting mesophase \\‘a~ obtained as yellow precipitates (B,M) when B were mixed \\,~th one crluivalcnt of M in chloroform. The melting point of this mcsol~l~asc is 167-172°C. Elemental analysis shows that the ratio of 13and M in the resulting mesophase is 1:l. 3. RESULTS
AND DISCUSSIONS
‘l’hc tcmpcrature-dependent IR spectra (KBr) of B.M are given in Fig. 1. The spectrum at 25 ‘C in Fig. l(a) shows that the N-II stretching bands of B,M are at 3402 cm-l, 3351 cm-l and 3 3 IO cm-‘. Before B and M were mixed, the N-H stretching band of 13 is at 3198 cm-l belonging to associated form. lR spcct~-urn of M contains N-H stretching bands at 3360 cm-l and 326X cn~-’ \\hich are also due to its self-association. The N-H srrctching bands of B.M are different from those observed both for 13and M. The lR changes suggest that triple complementary
2108
W-S.
L
.~._
_
__L__.._I~
_~~~
Figure 2. Ilcctron
~-2
micrograph
of an aqueous dispersion
of B.M.
3100.0
3366.7 3233.3
3500.0
Yang et al. / Synthetic Metals 71 (1995) 2107-2108
heating. In [act it has been reported
WAVENUMBERS(CM+
stretching
16OT
band around
and was related Therefore,
for barbituric
with intermolecular
this
acid the C=O
1670 cm -l only appeared
change
also
in solid state
hydrogen
indicates
that
bonding B.M
[12].
is formed
through hydrogen bond directed molecular self-assembly. Fi
is about
micrometer.
This
directed molecular ordcrcd
and the diameters
500 nm and its length means
that the pattern
self-assembly
and \\,cll-defined
in the mesophase
structure.
Further
of double
is in the scale of of hydrogen bond must be in a
researches
on this
point are being carried out.
-._ 1800.0 1566.7 _I-_--
--___
_~
WAlENUMBERS
(a) 3100 cn~-1-3500 cm-t
assembling spectrum conclusion.
bonds
were
formed
in accordance in region
REFERENCES
(c’d >
Figure 1. Tem1)cratrlrc-dependent
hydrogen
-1
1100.0
1333.3
1. J.-M. L&n, Angew. Chem. Int. Ed. Engl., 29 (1990) 1304. 2. G. M. Whitesides,
Infrared spectra of l3.M. (b) 1100 cn~-l-lXOO cm-’
between
I? and M via
1X00 cm-t
There are t\vo C=O stretching
also supports
sclfthis
bands at 3737 cm-
and 1670 cm-’ for B, but they are at 1715 cm-’ and 1672 cmwl for B.M. The N-H stretching
band at 33 IO cm-t and its shoulder band
at 3351 cm-l split into t\vo indcpendcnt decreases
while the temperature
3310 cm-l decrcascs
peaks and their strength
rise. The strength
of band at
more rapidly than that at 3351 cm-*. The
N-H stretching
band at 3402 cm-* also has similar behavior and it even disappears at higher temperature (> 120°C). Mean\\ bile,
a new band appears at 3425 cm -t \\+ich represents ii wca!icr hydrogen bond formed between 13 and M. From I:ig. I(b) it can be seen that the strength decreases
or C=O stretching
gradually and disappears
band at 1672 cm-’
at higher temperature
C. T. Seto, Science, 254
3. J. G. Stcvcn, C. Vicent, E. Fan and A. 1). Hamilton, Angew.
with the model [7]. The analysis 01‘II<
1600 cm“-
J. P. Mathias,
(1991) 1312.
when
Clmn.
ht. Ed. Engl., 32 (1993) 119.
4. M. C. litter, J. Phys. Chem., 95 (1991) 4601. 5. S J. Gelb, S. C. I-Iirst, C. Vicent, A.D. Hamilton, Sot., Chcni. Commun.,
J. Chem.
(1991) 1283.
6. X. Zhao, Y. -1~. Chang, F. W. Fowler, J. W. Lauher, J. Am. Clmn.
SOL, 112 (1990) 6627.
.I.-M.I,chn, M. Mascal, A. DeCian and J. Fisher, J. Chem. Sot., Chcm. Commun.,
(1990) 479.
C. T. Seto, G. M. Whitesides,
J. Am. Chem. Sot.,
115 (1993) 905; 1330; 1921. C ‘I‘. Seto, G. M. Whitesides,
J. Am. Chem. Sot.,
112(1990)6409; 113(1991)712; 114(1992)5473. IO. N.Kimizuka, T.Kawasaki and T. Kunitake, J. Am. Chem sot., 1I5 (1993)43X7. I I. Y. W Cao, X. D. Chai, S. G. Chen, T. .J. Li, Chemical Journal ot‘chincsc
Universities,
12. A. .I. T3anxs et al, J. ofMolecular
11 (1994), in the press. Structure,
56 (1979) 1.