Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Honeycomb Sheet Structures Achieving High Electrical Conductivities in Alkyl-Substituted Thiazolium Bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III) Complex Salts
Etsuko TomiyamaKazuaki TomonoDaisuke HashizumeTatsuo WadaKazuo Miyamura
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2009 Volume 82 Issue 3 Pages 352-357

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Abstract

A series of [Ni(dmit)2] (1) (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) complex salts with 3,4-dimethylthiazolium (2), 2,3,4-trimethylthiazolium (3), and 3,4,5-trimethylthiazolium (4) cations (I, II, and III, respectively) were synthesized and characterized by single-crystal X-ray analysis and conductivity. The molecular structures of 1 were the same in all three complex salts. In the structure of I, the anions were arranged in hexagonal structures. Neighboring hexagons formed honeycomb sheet structures as the result of S···S interactions in the (001) plane. The sheets of the honeycomb structures were arranged along the c axis with translational symmetries that form columnar honeycomb channels along the &bcsj_2009_352; direction. In the structures of II and III, honeycomb sheet structures were formed as in I. But in contrast to I, the relative position of the stacked sheets in II and III was slightly dislocated, forming zig-zag channels instead. The IR spectra of I, II, and III show that the C=C stretching band is slightly red-shifted to 1337–1339 from 1350 cm−1 for [Ni(dmit)2], caused by the partial oxidation of the anion. The measured values of the electrical conductivities were 0.20, 0.094, and 0.16 S cm−1 for I, II, and III, respectively. These high conductivities may be ascribed to the partially oxidation of the anion. The S···S interactions regulate the honeycomb sheet structure of the crystal and should work as conduction pathways effectively.

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© 2009 The Chemical Society of Japan
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