68182-80-9Relevant articles and documents
BEDT-TTF Salts Formed with Tetrahedrally Coordinated Zinc(II) Complex Anions
Yoshida, Yukihiro,Ito, Hiroshi,Nakamura, Yuto,Ishikawa, Manabu,Otsuka, Akihiro,Hayama, Hiromi,Maesato, Mitsuhiko,Yamochi, Hideki,Kishida, Hideo,Saito, Gunzi
, p. 6613 - 6630 (2016)
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 semiconductive, whereas the remaining two salts behave as metallic at room temperature and undergo a metal-insulator transition on cooling. The ET molecules in D are arranged in a θ42+40-like packing motif, due to the nonplanar anionic layers. All salts are semiconductive and exhibit a gradual evolution in their superstructures with cooling associated with charge disproportionation.
