Table Of ContentMaterial Designs and New Physical Properties
in MX- and MMX-Chain Compounds
.
Masahiro Yamashita (cid:129) Hiroshi Okamoto
Editors
Material Designs and
New Physical Properties
in MX- and MMX-Chain
Compounds
Editors
MasahiroYamashita HiroshiOkamoto
DepartementofChemistry Kashiwa
TohokuUniversity Japan
Sendai
Japan
ISBN978-3-7091-1316-5 ISBN978-3-7091-1317-2(eBook)
DOI10.1007/978-3-7091-1317-2
SpringerWienHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2012953272
#Springer-VerlagWien2013
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Preface
Material Designs and New Physical Properties
in MX- and MMX-Chain Compounds
The history of quasi-one-dimensional halogen-bridged Pt complexes began at the
end of the nineteenth century when Wolffram reported a Cl-bridged complex,
Pt(etn) Cl ·2H O (etn¼ethylamine), which is called Wolffram’s red salt because
4 3 2
ofitslustrousredcolor.ThiscomplexwasconsideredtobeaPtIIIcomplex,butit
has been shown that it is actually a PtII–PtIV mixed valence complex [Pt(etn) ]
2
[PtCl (etn) ]Cl ·4H O. Since then, many Pt complexes as well as Pd complexes
2 4 4 2
havebeensynthesized.In1981,Ni(chxn) Br (chxn¼1R,2R-diaminocyclohexane)
2 3
was synthesized. X-ray structure analysis revealed that it was not a NiII–NiIV
complex, but a NiIII complex. Theoretically, these compounds are thought to be
extendedPeierls–Hubbardsystems,wheretheelectron–phononinteraction(S),the
transfer integral (T), and the on-site and nearest-neighbor Coulomb repulsion
energies(UandV,respectively)stronglycompetewitheachother.Theelectronic
states of these complexes depend mainly on the competition between U and S.
WhenSislargerthanU,M(II)–M(IV)mixedvalencestatesorchargedensitywave
states (CDW), where the bridging halide ions are displaced from the midpoints
between two neighboring metal ions, (represented as –X–MII–X–MIV–X–), are
stabilized. On the other hand, when U is larger than S, an M(III) average valence
or Mott–Hubbard (MH) state, where the bridging halide ions are located at the
midpoint between two neighboring metal ions (represented as –XIII–X–MIII–X–),
becomes stable. These Pt, Pd, and Ni complexes show very interesting chemical
and physical properties, such as intense and dichroic charge transfer bands,
progressive overtones in resonance Raman spectra, midgap absorptions attributed
tosolotonsandpolarons,andgiganticthird-ordernonlinearopticalsusceptibilities,
andhaveapplicationsinfieldeffecttransistor(FET)devices.
In the 1980s, a new type of complex composed of binuclear metal complexes
and bridging halogens, represented as –M–M–X–M–M–X–, was reported. They
v
vi Preface
haveavarietyofelectronicstatesandundergovariousphasetransitionsbytemper-
ature,pressure,aswellasphotoirradiation.
In this book, we describe these complexes, including experimental results
andtheoreticaltreatments.
MasahiroYamashita
(TohokuUniversity)
HiroshiOkamoto
(UniversityofTokyo)
Contents
1 GeneralIntroduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
S.TakaishiandM.Yamashita
PartI MX-ChainCompounds
2 StructuresandOpticalPropertiesofPtandPdCompounds
withCharge-Density-Waves. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
HiroshiOkamotoandHiroyukiMatsuzaki
3 Ni(III)Mott–HubbardCompounds. . . . . . . . . . . . . . . . . . . . . . . . . 31
S.TakaishiandM.Yamashita
4 Pd(III)Mott–HubbardCompounds. . . . . . . . . . . . . . . . . . . . . . . . 39
S.TakaishiandM.Yamashita
5 PhotoinducedPhaseTransitionsinMX-ChainCompounds. . . . . . 55
HiroyukiMatsuzakiandHiroshiOkamoto
6 NonlinearElectricalConductivity,CurrentOscillationand
ItsControlinHalogen-BridgedNickel(III)Compounds. . . . . . . . . 83
HideoKishidaandAraoNakamura
7 Third-OrderOpticalNonlinearityofHalogen-BridgedNickel(III)
Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
HideoKishidaandHiroshiOkamoto
8 TheoryofMXChainCompounds. . . . . . . . . . . . . . . . . . . . . . . . . . 111
KaoruIwano
vii
viii Contents
PartII MMX-ChainCompounds
9 CrystalStructuresandPropertiesofMMX-Chain
CompoundsBasedonDithiocarboxylato-BridgedDinuclear
Complexes. . . . .. . . . . . . . .. . . . . . . . . .. . . . . . . . .. . . . . . . . . .. 151
MinoruMitsumi
10 POP-TypeMMX-ChainCompoundswithBinary
CountercationsandVapochromism. . . . . . . . . . . . . . . . . . . . . . . . 207
HiroakiIguchi,ShinyaTakaishi,andMasahiroYamashita
11 PhotoinducedPhaseTransitionsinMMX-Chain
Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
HiroyukiMatsuzakiandHiroshiOkamoto
12 TheoryofMMX-ChainCompounds. . . . . . . . . . . . . . . . . . . . . . . . 243
KenjiYonemitsu
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Contributors
Hiroaki Iguchi Department of Chemistry, Graduate School of Science, Tohoku
University,Sendai,Japan
Kaoru Iwano Institute of Materials Structure Science, High Energy Accelerator
ResearchOrganization(KEK),Tsukuba,Japan
HideoKishida DepartmentofAppliedPhysics,NagoyaUniversity,Nagoya,Japan
Hiroyuki Matsuzaki Department of Advanced Materials Science, Faculty of
FrontierSciences,UniversityofTokyo,Chiba,Japan
Research Institute of Instrumentation Frontier, National Institute of Advanced
IndustrialScienceandTechnology(AIST),Ibaraki,Japan
Minoru Mitsumi Department of Material Science, Graduate School of Material
Science,UniversityofHyogo,Hyogo,Japan
AraoNakamura JSTCREST,Tokyo,Japan
Hiroshi Okamoto Department of Advanced Materials Science, Faculty of
FrontierSciences,UniversityofTokyo,Chiba,Japan
DepartmentofAdvancedMaterialsScience,GraduateSchoolofFrontierSciences,
UniversityofTokyo,Kashiwa,Japan
ShinyaTakaishi DepartmentofChemistry,GraduateSchoolofScience,Tohoku
University,Sendai,Japan
Masahiro Yamashita Department of Chemistry, Graduate School of Science,
TohokuUniversity,Sendai,Japan
KenjiYonemitsu DepartmentofPhysics,ChuoUniversity,Tokyo,Japan
Department of Functional Molecular Science, Graduate University for Advanced
Studies,Okazaki,Japan
JST,CREST,Tokyo,Japan
ix
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