A highly conducting mixed-valence nickel bis(dithiolene) salt [Et(4)N][Ni(Me-thiazSe-dt)(2)](2) with selone substitution
Résumé
The prototypical [Ni(dmit)(2)] complex (dmit: 1,3-dithiole-2-thione-4,5-dithiolate) is modified here by combining the N-R substitution found in [Ni(R-thiazdt)(2)] complexes (R-thiazdt: N-alkyl-thiazoline-2-thione-4,5-dithiolate) and the selone substitution found in [Ni(dmiSe)(2)] complex (dmiSe: 1,3-dithiole-2-selone-4,5-dithiolate) to give a novel N-methyl substituted, radical anionic complex formulated as [Ni(Me-thiazSe-dt)(2)](1-) (Me-thiazSe-dt: N-methyl-thiazoline-2-selone-4,5-dithiolate). Both this anionic complex and its mixed-valence Et(4)N(+) salt crystallize with a rare cis arrangement of the two dithiolene ligands around the Ni atom. In the 1 : 2 [Et(4)N][Ni(Me-thiazSe-dt)(2)](2) salt, the complexes organize into dimerized chains well isolated from each other, giving the salt a strong one-dimensional character. It shows however a high RT conductivity of 4.6 S cm(-1) and small activation energy of 33 meV, indicating a possible Mott insulator behavior, which is not suppressed under pressures up to 10 GPa.
Domaines
Chimie organiqueOrigine | Fichiers éditeurs autorisés sur une archive ouverte |
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