Synthesis and Electroconductive Properties of Radical Salts Derived from Tetrathiafulvalene Dimers

✍ Scribed by Masahiko Iyoda; Kenji Hara; Eiji Ogura; Takahiro Takano; Masashi Hasegawa; Masato Yoshida; Yoshiyuki Kuwatani; Hiroyuki Nishikawa; Koichi Kikuchi; Isao Ikemoto; Takehiko Mori

• Book ID: 102606809
• Publisher: Elsevier Science
• Year: 2002
• Tongue: English
• Weight: 392 KB
• Volume: 168
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.2002.9757

✦ Synopsis

Palladium(II)-or copper(II)-catalyzed homo-coupling reaction of either trimethylstannyltetrathiafulvalene or tetrathiafulvalenylzinc chloride produces symmetrical bitetrathiafulvalenes (bi-TTFs) in good yields, whereas palladium(0)catalyzed cross-coupling reaction of tetrathiafulvalenylzinc chloride with 4-iodotetrathiafulvalenes leads to the corresponding unsymmetrically substituted bi-TTFs in moderate-to-high yields. The X-ray analysis of bi-TTF derivatives showed planar structures, and the cyclic voltammetry suggested that bi-TTFs have good donor ability comparable to that of BEDT-TTF. The symmetrical bi-TTFs formed the corresponding CT-complexes and cation radical salts. These CT-complexes and radical salts were found to be metallic or semiconducting, reflecting the effect of stoichiometry control in the dimeric TTF system. The X-ray structures of two cation radical salts revealed a unique stacking, and the precise conducting path in BEDO-bi-TTF . ClO 4 was discussed on the basis of MO calculations. # 2002 Elsevier Science (USA)