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

Reaction of a phosphane-decorated benzenedithiol (pbdtH2) with coinage metal salts furnished polynuclear complexes [M2(pbdtH)2] (M=AuI) or [cat][M5(pbdt)3] (cat=unipositive cation, M=AgI, CuI), which were characterized by analytical and spectroscopic techniques single-crystal X-ray diffraction studies. Furthermore, double salt an anion [Ag5(pbdt)3(PPh3)]− that proved unstable in solution was crystallographically. The crystallographic data revealed the Cu(I) Ag(I) exhibit, despite their like stoichiometric composition, isomeric molecular structures. observed disparities reproduced DFT dinuclear Au(I) complex found to undergo air-oxidation furnish mixed-valent [(AuIII)2(AuI)2(pbdt)4]. copper(I) – but not silver(I) showed luminescence solid state.