Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2023

Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone

Résumé

Highly conducting, mixed-valence, multi-component nickel bis(diselenolene) salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)(2)](-1) (Me-thiazds: N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (Et(4)N(+) and nBu(4)N(+) vs Ph(4)P(+), respectively). This behavior strongly differs from that of the corresponding monoanionic dithiolene complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands. The mixed-valence salts form highly dimerized or trimerized bi- and trimetallic units, rarely seen with such nickel complexes. Transport measurements under a high pressure (up to 10 GPa) and band structure calculations confirm the semiconducting character of [Ph(4)P][Ni(Me-thiazds)(2)](3) and the quasi metallic character of [Et(4)N][Ni(Me-thiazds)(2)](2) and [NBu(4)](x)[Ni(Me-thiazds)(2)](2) salts (0 < x < 1).

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Chimie
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Dates et versions

hal-04013829 , version 1 (27-11-2023)

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Hadi Hachem, Hengbo Cui, Reizo Kato, Pere Alemany, Enric Canadell, et al.. Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone. Inorganic Chemistry, 2023, 62, pp.4197. ⟨10.1021/acs.inorgchem.2c04300⟩. ⟨hal-04013829⟩
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