- AMER CHEMICAL SOC
Twelve kinds of bis(ethylenedithio)tetrathiafulvalene (BEDTTTF or ET) cation radical salts with tetrahedrally coordinated zinc(II) complex anions were obtained by electrocrystallitaticn; most of them were produced via the additional reaction of Lem/is-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 werepredorninantly categorized into four groups: (A) isolated ET.+ dimers or tetramers, (B) infinite ET.+ ribbon, (C) infinite layers either with a peculiar EV's+ arrangement of ET molecules with partial charges other than +0.5, and (E)_ infinite layers of EV's' 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)](2)Br-2(2-) 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 0421,40 -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.
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- DOI : 10.1021/acs.cgd.6b01294
- ISSN : 1528-7483
- eISSN : 1528-7505
- Web of Science ID : WOS:000387094600059