Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Synthesis and Structures of Neutral Crystals and Charge-Transfer Salts of Selenium Containing TMET-TTP Derivatives
Minoru AshizawaHirofumi NiiTakehiko MoriYohji MisakiKazuyoshi TanakaKazuo TakimiyaTetsuo Otsubo
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2003 Volume 76 Issue 11 Pages 2091-2097


TMET-TTP derivatives in which one or both of the outer 1,3-dithiole rings are replaced by 1,3-diselenole rings (1a1d) have been prepared (TMET-TTP: 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-5-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene). The neutral crystal of 1c has β-type uniform stacks, whereas 1a shows a θ-type molecular arrangement in the neutral crystal. The AsF6 salts of 1a and 1d have a θ-type structure similarly to other TMET-TTP salts. In spite of the relatively small dihedral angle (117°), the conductivity is weakly semiconductive from room temperature. Selenium substitution causes unbalance of the diagonal intermolecular interactions, which may be the origin of a deviation from the universal phase diagram of the θ-phase.

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© 2003 The Chemical Society of Japan
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