Vinylogous Tetrathiafulvalene (TTF) -Electron Donors and Derived Radical Cations: ESR Spectroscopic, Magnetic, and X-ray Structural Stu
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- 作者：Martin R. Bryce and ; Adrian J. Moore ; Brian K. Tanner ; Roger Whitehead ; William Clegg ; Fabian Gerson ; Axel Lamprecht ; and Susanne Pfenninger
- 刊名：Chemistry of Materials
- 出版年：1996
- 出版时间：June 1996
- 年：1996
- 卷：8
- 期：6
- 页码：1182 - 1188
- 全文大小：275K
- 年卷期：v.8,no.6(June 1996)
- ISSN：1520-5002
文摘
The properties of new 2,2'-ethanediylidene(1,3-dithiole)derivatives 5, 6, and8-11 arereported. Cyclic voltammetric studies establish that they areefficient donor molecules, withthe extended conjugation resulting in stabilization of dications,relative to tetrathiafulvaleneTTF (1). Radical cations are generated by oxidation ofthe neutral compounds withtrifluoroacetic acid or anhydrous silver perchlorate indichloromethane, and their ESR andproton ENDOR spectra are reported. The bulk of the spin populationresides in the centralS2C=C-C=CS2 part of the 
chars/pi.gif" BORDER=0 >-system.The X-ray crystal structure of donor 6 revealsthatthe 2,2'-ethanediylidene(1,3-dithiole) framework is planar.Donor 6 forms a crystalline 1:1charge-transfer complex with TCNQ, the X-ray crystal structure of whichshows a mixedstack structure. A solution of this complex in acetonitrileexhibits ESR spectra of both radicalions, 6·+ and TCNQ·-.Static susceptibility data are reported for TCNQ complexes ofsomeof these donors.
chars/pi.gif" BORDER=0 >-system.The X-ray crystal structure of donor 6 revealsthatthe 2,2'-ethanediylidene(1,3-dithiole) framework is planar.Donor 6 forms a crystalline 1:1charge-transfer complex with TCNQ, the X-ray crystal structure of whichshows a mixedstack structure. A solution of this complex in acetonitrileexhibits ESR spectra of both radicalions, 6·+ and TCNQ·-.Static susceptibility data are reported for TCNQ complexes ofsomeof these donors.