Crystal and electronic structures of new molecular conductors tetramethylammonium and tetramethylarsonium complexes of Pd(dmit)2

Abstract
The synthesis, structural characterization and electrical conductivity measurements of α-,β-[(CH3)4N][Pd(dmit)2]2 and [(CH3)4As][Pd(dmit)2]2 are reported. They have similar crystal structures made of stacked Pd(dmit)2 dimers. The mode of the intra-dimer molecular overlapping is that of the eclipsed type. Pd atoms deviate from the planes formed by ligand S atoms by 0.07–0.08 Å to approach to each other. Simple tight-binding band calculations were made on these three Pd(dmit)2 salts. Each energy band is made up of two energy branches separated by a large mid-gap. The lower energy branch is a narrow half-filled band which seems to be consistent with the weakly metallic or semiconducting behaviour of these compounds around room temperature.

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