Small Variations, Big Impact: Structural Diversity of the Complexes of a Phosphane-Decorated Benzenedithiol with Group-11 Metals

Reaction of a phosphane-decorated benzenedithiol (pbdtH(2)) with coinage metal salts furnished polynuclear complexes [M-2(pbdtH)(2)] (M=Au-I) or [cat][M-5(pbdt)(3)] (cat=unipositive cation, M=Ag-I, Cu-I), which were characterized by analytical and spectroscopic techniques and single-crystal X-ray diffraction studies. Furthermore, a double salt with an anion [Ag-5(pbdt)(3)(PPh3)](-) that proved unstable in solution was characterized crystallographically. The spectroscopic and crystallographic data revealed that the Cu(I) and Ag(I) complexes exhibit, despite their like stoichiometric composition, isomeric molecular structures. The observed disparities were reproduced by DFT studies. The dinuclear Au(I) complex was found to undergo air-oxidation to furnish a mixed-valent complex [(Au-III)(2)(Au-I)(2)(pbdt)(4)]. The copper(I) - but not the isomeric silver(I) complexes - showed luminescence in the solid state.

Automated summary

A series of polynuclear complexes containing phosphane-decorated benzenedithiol were synthesized experimentally, with the gold(I) complex undergoing oxidation to form a mixed-valent gold complex, and the copper(I) complex exhibiting luminescent properties in the solid state.