Preparation and oxidation of polarized Au(III) complexes having both the C-deprotonated-2-phenylpyridine (ppy) and a sulfur-rich dithiolate ligand and X-ray crystal structure of [Au(η2-C,N-ppy)(η2-S,S-C8H4S8)]·0.5DMF

[Au(ppy)(C8H4S8)] [ppy−=C-deprotonated-2-phenylpyridine(1-), C8H4S82−=2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-ditholate(2-)] and [Au(ppy)(C10–C6S8)] [C10–C6S82−=2-{bis(decylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5- dithiolate(2-)] were prepared. They showed an intense electronic absorption band due to an intramolecular mixed metal/ligand-to-ligand charge transfer transition which is sensitive to a solvent. They exhibit first oxidation potentials of −0.06 to +0.20 V (vs. Ag/Ag+) due to the dithiolate ligand-centered oxidation. They were oxidized by iodine or TCNQ (7,7,8,8-tetracyano-p-quinodimethane) to afford [Au(ppy)(C8H4S8)](I3) and [Au(ppy)(C10–C6S8)](I3) containing the I3− ion, [Au(ppy)(C8H4S8)](TCNQ)0.6 and [Au(ppy)(C10–C6S8)](TCNQ)0.5 containing the TCNQradical dot− radical anion. Their oxidized complexes behave as electrical conductors with electrical conductivities of 2.0×10−2– 4.0×10−2 S cm−1 measured for compacted pellets at room temperature. The X-ray crystal structure of [Au(ppy)(C8H4S8)]·0.5DMF revealed a two-dimensional array of the molecules with some sulfur–sulfur non-bonded contacts.