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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
A highly conducting mixed-valence nickel bis(dithiolene) salt [Et4N][Ni(Me-thiazSe-dt)2]2 with selone substitution
Hadi Hachem1, Olivier Jeannin1, Hengbo Cui2,3
1Université de Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), F-35000 Rennes, France. marc.fourmigue@univ-rennes1.fr.
Abstract:
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 Et4N+ salt crystallize with a rare cis arrangement of the two dithiolene ligands around the Ni atom. In the 1 : 2 [Et4N][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.
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