Spontaneous Redox Synthesis of the Charge Transfer Material TTF4[SVMo11O40]

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• 作者：Qi Li ; Jinzhen Lu ; John F. Boas ; Daouda A. K. Traore ; Matthew C. J. Wilce ; Fuzhi Huang ; Lisandra L. Martin ; Tadaharu Ueda ; Alan M. Bond
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：December 3, 2012
• 年：2012
• 卷：51
• 期：23
• 页码：12929-12937
• 全文大小：481K
• 年卷期：v.51,no.23(December 3, 2012)
• ISSN：1520-510X

文摘

The charge-transfer material TTF-SV^IVMo₁₁O₄₀ (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu₄N)₃[SV^VMo₁₁O₄₀] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF₄[SVMo₁₁O₄₀]路2H₂O路2CH₂Cl₂, with the single V atom positionally disordered with eight Mo atoms over the whole 伪-Keggin polyanion [SVMo₁₁O₄₀]^4-. Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu₄N)₃[SV^VMo₁₁O₄₀] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-SV^IVMo₁₁O₄₀ materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-SV^IVMo₁₁O₄₀ material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.