Three-dimensionally-modified tetracyanoquinodimethanes and their charge-transfer complexes with tetrathiafulvalene derivatives having a wide range of ionicity.
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概要
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Eight different 1:1 charge-transfer(CT) complexes were prepared using tetrahydrobarreleno-tetracyanoquinodimethane(THBTCNQ), dihydrobarreleno-tetracyanoquinodimethane(DHBTCNQ), monobenzobarreleno-tetracyanoquinodimethane(MBBTCNQ), and dibenzobarreleno-tetracyanoquinodimethane(DBBTCNQ) as tetracyanoquinodimethane(TCNQ)-type acceptors, and tetrathiafulvalene(TTF), bis(tetramethyene)-tetrathiafulvalene(OMTTF), and tetramethyl-tetrathiafulvalene(TMTTF) as TTF-type donors. The complexes can be classified into three distinct groups, I–III, on the basis of the magnitude of both the degree of CT and the electrical resistivity of compacted powders. Group-I complexes are characterized by a small band gap semiconductivity and moderate CT, group-II complexes by low conductivity and small CT, and group III complexes by low conductivity and complete CT. The stacking mode of the three groups of complexes are discussed, by comparing the electronic absorption spectra of the three groups of CT complexes with those of the complexes for which the crystal structures are known. A crystal structure analysis of OMTTF–DBBTCNQ revealed that it is the first example of a highly ionic CT complex of a TTF–TCNQ type with a regular mixed stacking mode. These three groups of complexes containing bulky acceptor groups will be of theoretical interest in studying the crystal properties of organic CT complexes.
- 公益社団法人 日本化学会の論文
著者
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Murata Ichiro
Department Of Cardiovascular Medicine Graduate School Of Medicine
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Inokuchi Hiroo
Institute For Molecular Science
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Yamochi Hideki
Department Of Chemistry Faculty Of Science Kyoto University
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Tanaka Jiro
Department Of Biomaterials Okayama University Graduate School Of Medicine Dentistry And Pharmaceutic
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Enoki Toshiaki
Institute For Molecular Science
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KASAI Nobutami
Department of Applied Chemistry, Faculty of Engineering, Osaka University
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Kasai Nobutami
Department Of Applied Biological Science Tokyo University Of Science
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Harada Shigeharu
Department Of Applied Biology Kyoto Institute Of Technology
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Yamamura Kimiaki
Department Of Chemistry College Of General Education Kobe University
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Nakasuji Kazuhiro
Department Of Chemistry Graduate School Of Science Osaka University
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SAITO Gunzi
Institute for Molecular Science
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Nakatsuka Masakatsu
Department of Chemistry, Faculty of Science, Osaka University
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