Syntheses and physical properties of quasi-one-dimensional halogen-bridged Cuii-Ptiv mixed-metal MX-chain compounds

ELSEVIER

Synthetic Metals 103 (1999) 2648-2649

Syntheses and Physical Properties of Quasi-One-Dimensional Mixed-Metal MX-Chain Compounds T. Kawashima”, Hosokoshi’,

T. Manabe”,

M. Yamashita”,

K. Toriumi”,

Halogen-Bridged

H. Kitagawa’,

T. Mitani”,

H. Okamoto”,

Cul’-Pt’V

K. Inoue’,

Y.

M. Shiro’ “Graduate

School

of Human

“Department

Informatics,

of Material

“Japan

Science, Himeji,

Advanced

i( Graduate

Nagoya

Institute

Harima

Science Park

The University

for Molecular

‘Rigaku

& PRESTO(JST),

of Science Technology,

School of Engineering, ‘Institute

Univ

Science,

co, Akishima,

464-8601,

City, Hyogo,678-12

Ishikawa

923-12,

of Tokyo, Hongo Okazaki

Tokyo

Nagoya

Japan

Japan

Japan

Tokyo, Japan

444, Jgpan

196-8966,

Japan

Abstract We synthesized magnetic

new halogen-bridged

susceptibilities.

repeating

units,

The

which

dimensional(2-D)

mixed-metal

structures

have

tight

hydrogen-bond

complexes

[Cu(chxn)d

of [Cu(chxn),]ptX,(chxn),]X,

hydrogen-bonds

network.

between

Magnetic

[PtX,(chxn),]X, consist

ligands

susceptibility

and

(X=Cl,

of linear

counter

chains

anions

measurements

Br), with

and

show

and measured

weak

Cu”~*=X-Pt’

construct

a two-

a&ferromagnetic

behavior.

Keywords : RiIaanetic measurements

1. Introduction

compound

and Br-compound

temperature Quasi-one-dimensional valence compounds because intense

they

show

intervalence

Stokes-shift,

halogen-bridged have attracted very

interesting

change

third-order

M” -M”mixedmuch attention properties

transfer, nonlinear

such

luminescence optical

properties temperature as

and

at

were

150K,

were investigated to 2K. Resonance

were measured

determined

respectively.

at room Magnetic

by SQUID, from- room Rsman spectra anid XPS

at room temperature.

with

properties,

3. Results

and discussion

soliton, polaron, etc ]1,2,3]. The compounds with ClO; as counteranions have 1-D charge density wave state, while

These compounds are orthorhombic I222. crystal structures of [Cu(chxn),]fPtX,(chxn)dX,

the compounds

are isomorphous to [Pt(chxn),]FtX,(chxn),]X, [5]. The a-axis, the b-axis and the c-axis correspond to the

2-D

charge

interchain synthesized [Cu(chxn),] X=Cl

with density

haloge’n wave

ions as counteranions

state

hydrogen-bonds. new mixed-metal FtX,(chxn),]X,

and Br) and investigated

because

of very

have strong

In this study we have compounds formulate-d as

inter-chain metal-metal

(chxn=cyclohexandiamine; their physical properties.

direction The

distance in the direction of chxn ligands, the distance and the inter-chain distance. in the of counterion,

compounds

[Cu(chxn)$* 2. Experiment

structures. along

These

compounds

were

prepared

stoichiometric

amount

of

ptX,(chxn),]X,

[4], followed

with

(x%1,

Br) in aqueous

solutions.

by

[Cu(chxn)AX, excess amount Crystal

structures

mixing and of LiX of Cl-

consist

and The

chains

respectively. of

alternating

fPtX,(chxn),]“‘,

forming

hydrogen-bonds but

also

hydrogen-bonds networks Both Pt”-X and M”**.X

among

stacks

longer

than those in Cu compounds, of Pt ion. (Table

2)

of

linear-chain

are observed not only chains,

forming

[6]= (Fig: 1) distance in Pt compounds

radius

0379-6779/99/$ - see front matter 0 1999 Elsevier Science S.A. All rights reserved. PII: SO379-6779(98)00664-X

(Table 1) The &=Cl, Br)

due to the larger

2-D are ionic

T. Kuwashima

Table 1 Crystallographic [

Data of ~(chxn)~~tX~(chxn)~X,

CIA

VI.&<

Table 2 Relevant Interatomic

Distances for ~(chxn)~~tX,(chxn)~X,

[Cu(chxn)~~tClz(chxn)~C1, ~t(chxn)~~tC&(chxn)~Cl~ [Cu(chxn)dptBrz(chxn)dBr, pt(chxn),]ptBrti(chxn)dBrd

Fig. 1 Structure

103 (1999)

2648-2649

orthorhomobic 1222

t(chxn). tBrg(chxn)l]Br orthorhomobic 1222

2 23.700(8) 5.344(5) 6.978(4) 883.8(S)

2 23.865 5.372(2) 7.022(l) 900.3(4)

X=Cl, Br)

MN-X

(M=Cu, Pt M”...X

M -N

R=l,&

2.302(2) 2.324(2) 2.446(2)

2.808(2) 2.834(2) 2.898(3)

2.042(3) 2.056(4) 2.050(5)

2.490(l)

2.952(l)

2.059(3)

0.82 0.82 0.84 0.86

of [Cu(chxn)z]~tCl.,(chxn)~C1,

Fig. 2 Magnetic susceptibilities

of [Cu(chxn)d~tX,(chxn)~X,,

[Z] M.Yamashita,

T.Ito, Y.Wada,

I.Ikemoto, We

measured

magnetic

[Cu(chxn)dJptX,(chxn),]X,,

from

As

these

show

in

Fig.2,

susceptibilities

results

interactions

between

the

Resonance

Raman

indicate Pt”Pt”

that the interactions

Pi?’ compounds compounds

of

between

are stronger

than

show

weak

Cu”sites spectra M”

through and

and Pt’

XPS in the

those in the Cu”-

[3] T.Manabe,

4,References

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2649

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Metals

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