Tetrathiafulvalene Derivatives Linking a Dichalcogenolane Ring through the -Bond: New Donor Components for Organic Metals

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• 作者：Jun-ichi Yamada ; Rika Oka ; Takashi Mangetsu ; Hiroki Akutsu ; Shin'ichi Nakatsuji ; Hiroyuki Nishikawa ; Isao Ikemoto ; and Koichi Kikuchi
• 刊名：Chemistry of Materials
• 出版年：2001
• 出版时间：May 2001
• 年：2001
• 卷：13
• 期：5
• 页码：1770 - 1777
• 全文大小：127K
• 年卷期：v.13,no.5(May 2001)
• ISSN：1520-5002

文摘

A synthetic study of the dioxolane derivatives of methylenedithio(ethylenedithio)tetrathiafulvalene (MET), bis(methylenedithio)tetrathiafulvalene (MT), and methylenedithiotetrathiafulvalene, their dithiolane analogues, and the oxathiolane derivative of METhas been undertaken to explore new organic metals. A practically useful preparation of thebiheterocycle-fused 1,3-dithiol-2-ones as building blocks for these dichalcogenolane-linkedtetrathiafulvalene (TTF) donors has been realized via the newly developed BF₃-promotedreactions. The effect of the additional linked dichalcogenolane ring on the electron-donatingability is investigated by cyclic voltammetry. An X-ray crystallographic analysis of theoxathiolane-linked MET reveals that its molecular structure is isostructural with that ofits dithiolane analogue but not bulkier than that of its dioxolane analogue. Several of thepresent TTF donors have produced metallic charge-transfer materials, two of which arecharacterized by X-ray crystallography. In the crystal structure of the 7,7,8,8-tetracyanoquinodimethane complex of the dioxolane-linked MT that exhibits metallic-like behavioraround room temperature, the donor molecules are stacked head-to-tail to form the dimers,which are connected by C-H···O hydrogen bonds. On the other hand, in the metallic AsF₆salt of the dioxolane-linked MET stable down to 2.0 K, the donor molecules are stackedhead-to-head to form two-dimensional sheets despite the dioxolane ring being perpendicularlyattached to the MET molecule.