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DOI: 10.1039/A903821C (Paper) Reference Section for: J. Mater. Chem., 1999, 9, 2413-2417

Properties of Pt(II) complexes with a sulfur-rich dithiolate ligand having alkyl chains and of their oxidized species. The X-ray crystal structure of [NBun4]2[Pt{C6S8(C10H21)2}]

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Takeo Nakazono, Motohiro Nakano, Hatsue Tamura and Gen-etsu Matsubayashi

Abstract

Reactions of [NBun4]2[PtCl4] with Na2[C6S8R2] [C6S8R22– = 2-{bis(alkylthio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2–); R = C10H21, C14H29 or C18H37] in methanol afforded [NBun4]2[Pt(C6S8R2)2]. The crystal structure of [NBun4]2[Pt{C6S8(C10H21)2}2] was determined by X-ray analysis. The crystal packing structure consists of columns of anion units assembled through the association of alkyl chains, where the metal-center units are separated by the bulky cations. These complexes exhibit oxidation potentials of –0.25 to +0.35 V vs. SCE. They were oxidized by bromine or iodine to yield essentially two-electron oxidized species [Pt(C6S8R2)2]0, with ligand-centered oxidation. The oxidized complexes (R = C10H21 and C14H29) exhibit electrical conductivities (σ) of 1.4 × 10–2 to 4.9 × 10–2 S cm–1 measured for compacted pellets at room temperature, while the oxidized species with R = C18H37 behaves as an insulator (σ < 10–8 S cm–1). Electronic states and molecular interactions of the complexes in the solid state are discussed based on EPR, XPS, electronic absorption and reflectance spectra.

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