Mixed-valence gold bis(diselenolene) complex turning metallic under pressure
Résumé
While oxidation of d(8) 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 (sigma(RT) = 3 x 10(-2) S cm(-1), E-act = 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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Le gal et al - 2021 - Mixed-valence gold bis(diselenolene) complex.pdf (2.39 Mo)
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Le Gal_d1tc02751d1.pdf (344.18 Ko)
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