While oxidation of d8 anionic gold bis(dithiolene) complexes most often affords the corresponding neutral radical single-component conductor, an original gold bis(diselenolene) complex isolated as a Ph4P+ salt affords upon electrocrystallization a mixed-valence 1 : 2 salt, [Ph4P][Au(Me-thiazds)2]2 (Me-thiazds: 2-methyl-1,3-thiazoline-2-thione-4,5-diselenolate).
This salt exhibits a rare charge alternation associated with the simultaneous presence of both cis and trans isomers of the gold complex in the conducting layers. The salt is semiconducting (σRT = 3 × 10−2 S cm−1, Eact = 0.137 eV) but, in contrast with other 1 : 2 gold bis(dithiolene) salts, turns metallic under pressure (>10 GPa). [Ph4P][Au(Me-thiazds)2]2 is thus the first metallic, fully characterized, 1 : 2 mixed-valence gold complex, opening the door for the preparation of highly conducting solids of this type.
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Mixed-valence gold bis(diselenolene) complex turning metallic under pressure
Yann Le Gal, HengBo Cui, Pere Alemany, Enric Canadell, * Reizo Kato, Thierry Roisnel, Vincent Dorcet, Marc Fourmigué and Dominique Lorcy *
