Preparation of metallic BEDT-TTF charge transfer complex of 3,3',5,5'- tetranitro-4,4'-biphenyldiol dianion (TNBP2-) having flexible molecular shape

Kazukuni Nishimura, Tetsuo Kondo, Olga O. Drozdova, Hideki Yamochi, Gunzi Saito

研究成果: Contribution to journalArticle査読

11 被引用数 (Scopus)

抄録

Two kinds of 3,3',5,5'-tetranitro-4,4'-biphenyldiol dianion (TNBP2-) molecules having different dihedral angles (φ) between the two phenyl rings exist in the tetrabutylammonium salt of TNBP2- (φ = 0°and 35°), while only one kind of TNBP2- molecule exists in the tetraphenylphosphonium salt (φ = 0°). The 4: 1 cation radical salt of BEDT-TTF (ET) with TNBP2- as a counter anion is metallic down to 3 K. The ET molecules form a two- dimensional conducting layer which is sandwiched by the layers of flat TNBP2- molecules (φ = 0°). The crystal structure indicates the β''432-type stacking of tetramerized ET molecules which is caused by hydrogen bonds between the CH groups of ET and the oxygen atoms (nitro and phenol) of TNBP2-. The optical spectra in a KBr pellet are consistent with both the highly conductive and distorted structural nature. The magnetic susceptibility at room temperature is high (X= 6.7 x 10-4 emu spin-1) compared with the conventional organic metal based on ET (X=3.4-5.5 x 10-4 emu spin-1) indicating strong electron correlation in the 4:1 complex. The temperature dependence of the magnetic susceptibility suggests a semimetallic nature which is consistent with the calculated Fermi surface. The calculated band width is comparable to the estimated effective on-site Coulomb repulsive energy. A semiconductive behavior with high conductivity is observed in the nearly 2: 1 ET complex of TNBP2-. A partial charge transfer state of the ET molecules is supported by the optical spectra. The high conductivity and optical data suggest that the 2: 1 salt is not (ET1 +)2(TNBP2-) but most plausibly (ET0.5 +)2(HTNBP1-).

本文言語英語
ページ(範囲)911-919
ページ数9
ジャーナルJournal of Materials Chemistry
10
4
DOI
出版ステータス出版済み - 1 1 2000
外部発表はい

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry

フィンガープリント 「Preparation of metallic BEDT-TTF charge transfer complex of 3,3',5,5'- tetranitro-4,4'-biphenyldiol dianion (TNBP<sup>2-</sup>) having flexible molecular shape」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

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