BEDT-TTF-based organic conductors with [MBr4]2− anions, M= Cd, Co, Zn, Mn, Hg. Effect of solvent

Zhilyaeva, E. I.; Dzyuba, K. A.; Torunova, S. A.; Flakina, A. M.; Шилов, Г. В.; Куликов, А. В.; Lyubovskaya, Rimma N.

doi:10.1016/j.synthmet.2015.07.023

Cited by 3 publications

(1 citation statement)

References 15 publications

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“…Thus far, ET salts formed with zinc(II) complex anions have been explored to a significantly lesser extent despite the fact that coordination bonds can be readily formed with zinc(II), affording new complex anions, attributed to the lability of zinc(II) species . To the best of our knowledge, zinc(II) complex anions combined with ET have been limited to discrete ZnX 4 2– (X = Cl , and Br , ), dimeric Zn 2 (SCN) 6 2– , , and one-dimensional (1D) polymeric [MZn(SCN) 4 – ] ∞ (M = Rb, Cs, and Tl). ,, Lewis basic monoanions (Y A – and Y B – ) readily react with zinc(II) (pseudo)halides ZnX 2 via nucleophilic addition, affording divalent ZnX 2 Y A Y B 2– ions in a hybrid sp 3 state in anhydrous media, attributed to the Lewis acidity of ZnX 2 . We expect that, in contrast to the planar trigonal coordination for copper(I)- or silver(I)-containing polymeric anions, tetrahedral coordination results in a nonplanar anionic surface, which would significantly affect the molecular arrangement in the ET layers.…”

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confidence: 99%

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

Yoshida

Itô

Nakamura

et al. 2016

Crystal Growth & Design

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12 kinds of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) cation 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-, Brand nd SCN-) occurred during electrocrystallization. Based on 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 ET 0.5+ arrangement or of ET molecules with partial charges other than +0.5, and (D) infinite layers of ET 0.5+ 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 pseudo-polymeric chain of disordered Zn[C(CN)3]2Br2 2ions. In C, two salts are semiconductive, whereas the remaining two salts behave 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 non-planar anionic layers. All salts

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