BEDT-TTF Salts Formed with Tetrahedrally Coordinated Zinc(II) Complex Anions

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説明

Twelve kinds of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) cation radical salts with tetrahedrally coordinated zinc(II) complex anions were obtained by electrocrystallization; most of them were produced via the additional reaction of Lewis-basic cyano-containing anions [N(CN)2–, C(CN)3–, and Au(CN)2–] with ZnX2 (X = Cl–, Br–, and SCN–) that occurred during electrocrystallization. On the basis of the charge and arrangement of ET molecules, these salts were predominantly categorized into four groups: (A) isolated ET•+ dimers or tetramers, (B) infinite ET•+ ribbon, (C) infinite layers either with a peculiar ET0.5+ arrangement of ET molecules with partial charges other than +0.5, and (D) infinite layers of ET0.5+ molecules. In A, zinc(II) complex anions including a unidentate-coordinated C(CN)3 or Au(CN)2 group spatially interrupt the infinite arrangement of ET molecules. The ET•+ ribbon in B runs parallel to the pseudopolymeric chain of disordered Zn[C(CN)3]2Br22– ions. In C, two salts are semico...

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