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DOI: 10.1039/A606026I (Paper) Reference Section for: J. Mater. Chem., 1997, 7, 377-380

Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh3P] [Ni(dmit)2]3

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Anthony E. Pullen, Hsiang-Lin Liu, D. B. Tanner, Khalil A. Abboud and John R. Reynolds

Abstract

Electrooxidation of [Ni(dmit)2 ]-(dmit=C3S52- =4,5-dithiolate-2-thione-1,3-dithiole) in 3:1 acetonitrile–acetone at a Pt wire anode in the presence of methyltriphenylphosphonium bromide electrolyte yields the radical anion salt complex [MePh3P][Ni(dmit)2 ]3 . Black shiny platelet crystals were harvested. They belong to the monoclinic space group P21 /c, M=1631.41, a=21.0872(1), b=17.4930(2), c=15.7203(2) Å, β=107.072(1)°, V=5543.4(1) Å3 and Z=4. The crystal packing structure consists of columns of Ni(dmit)2 units of width one unit separated by columns of MePh3P+ counter-ions. The Ni(dmit)2 columns are composed of dimers of Ni(dmit)2 units with non-bonding interactions with six other pairs of Ni(dmit)2 units. The arrangement of the dimers with respect to each other in the columns has been seen in other phosphonium-based Ni(dmit)2 complexes and is similar to the packing of κ-BEDT-TTF radical cation salts which have shown superconductivity. Single-crystal temperature-dependent conductivity measurements have shown that this material is semiconducting with a room-temperature conductivity of 0.1 S cm-1 and a thermal activation energy of 0.22 eV.

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