The cation radical salt based on unsymmetrical metal-dithiolene complexes [Au(ppy)(C 8H 4S 8)] 2[PF 6] (1) is a semiconductor with small activation energy under ambient pressure, and shows metallic behavior under high pressure. On the other hand, [Au(ppy)(C 8H 4 S 6O 2)] 2[BF 4] (2) is an insulator in spite of the structural similarity. Effective conduction pathways through the S⋯S contacts were found in the crystal structure of 1. However, the crystal of 2 contains no such conduction pathways. Comparison of the energy band structures of 1 and 2 suggests that even a subtle difference in cation arrangements makes a remarkable difference between the electrical properties of 1 and 2.
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