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Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

Yukihiro Yoshida, Mitsuhiko Maesato, Yuto Nakamura, Manabu Ishikawa, Hideki Yamochi, Gunzi Saito, Hideo Kishida, Hiroshi Kitagawa

Inorg Chem. 2019 Dec 16;58(24):16703-16711.

PMID: 31773954

Abstract:

Rational control of the molecular arrangement in solids has been the subject of intense research for many years. In particular, the structural control of bis(ethylenedithio)tetrathiafulvalene (ET) radical cations has attracted special interest because of the primary effect on the electronic properties of the salts. In this study, we obtained the first ET cation radical salts formed with nonuniform silver(I) complex polyanions, which involve multiple kinds of openings in the anionic layer, by an electrocrystallization method. θ-(ET)2Ag2(CN)[N(CN)2]2 (1) with a θ-type ET packing motif contains double helical chains composed of AgN(CN)2, whereas α″-(ET)2Ag2(CN)(SCN)2 (2) with an α″-type ET packing motif contains zigzag ladders composed of AgSCN. Both silver(I)-based tube-like assemblies are connected to each other by a cyano group, affording nonuniform polyanionic structures. Although both salts show semiconducting behavior, there is a distinct difference in their spin geometry, with an S = 1/2 Heisenberg antiferromagnetic square lattice in 1, which is associated with charge disproportionation or dynamical charge fluctuation in the ET layers, and an S = 1/2 Heisenberg anisotropic triangular lattice in 2, which results in spin frustration in the ET layers. The ability of the nonuniform polymeric structures in the anionic layers to act as templates for various arrangements of ET radical cations is demonstrated.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP66946483	Bis(ethylenedithio)tetrathiafulvalene		66946-48-3	Price

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