Mixed-Valence, Layered, Cation Radical Salts of the Ethane-Bridged Dimeric Tetrathiafulvalene [(EDT-TTF-CH2-)2
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- 作者：Cé ; cile Mé ; ziè ; re ; Marc Fourmigué ; Enric Canadell ; Rodolphe Clé ; rac ; Klaus Bechgaard ; and Pascale Auban-Senzier
- 刊名：Chemistry of Materials
- 出版年：2000
- 出版时间：August 2000
- 年：2000
- 卷：12
- 期：8
- 页码：2250 - 2256
- 全文大小：129K
- 年卷期：v.12,no.8(August 2000)
- ISSN：1520-5002
文摘
The synthesis and X-ray crystal structure of the ethane-linked dimeric tetrathiafulvalene[(EDT-TTF-CH2)2], 1,2-bis(ethylenedithiotetrathiafulvalenyl)ethane (1), is reported. Itoxidizes reversibly at 0.45 and 0.90 V vs SCE. Electrocrystallization in the presence of[n-Bu4N][FeCl4] or [n-Bu4N][GaCl4] affords isostructural, mixed-valence conducting 1:1 salts[1
+][FeCl4-][THF]0.5 and [1+][GaCl4-][THF]0.5 whose X-ray crystal structures are described.The intercalation of the tetrahedral anions within the organic slabs and the resulting slidingof the molecular diads on top of each other give rise to both 1D- and 2D-type HOMO···HOMO interactions whose origin is correlated with the details of the peculiar overlap patternsobtained with those dimeric tetrathiafulvalenes. The weak paramagnetism observed in theGaCl4- salt due to the organic spins of the conducting slabs is hidden in the FeCl4- salt bythe S = 5/2 Fe(III) contribution. The absence of sizable magnetic interactions between theorganic and FeCl4- sublattices is accompanied by weak antiferromagnetic FeCl4-/FeCl4-interactions, attributable to a short Cl···Cl interanion distance at 3.419(17) Å.
+][FeCl4-][THF]0.5 and [1+][GaCl4-][THF]0.5 whose X-ray crystal structures are described.The intercalation of the tetrahedral anions within the organic slabs and the resulting slidingof the molecular diads on top of each other give rise to both 1D- and 2D-type HOMO···HOMO interactions whose origin is correlated with the details of the peculiar overlap patternsobtained with those dimeric tetrathiafulvalenes. The weak paramagnetism observed in theGaCl4- salt due to the organic spins of the conducting slabs is hidden in the FeCl4- salt bythe S = 5/2 Fe(III) contribution. The absence of sizable magnetic interactions between theorganic and FeCl4- sublattices is accompanied by weak antiferromagnetic FeCl4-/FeCl4-interactions, attributable to a short Cl···Cl interanion distance at 3.419(17) Å.