The photoluminescence (PL) properties of several recently synthesized ligand-stabilized polynuclear gold(I)
selenide complexes were investigated. [Au18Se8(dppe)6]Br2 {dppe = bis(diphenylphosphanyl) ethane} (I) is
distinguished by the bright-red long-lived PL (phosphorescence) in the solid state, photosensitization of singlet
oxygen, 1O2, in solution, and high photostability. The quantum yield of PL, φPL, is (7.5 ± 0.5) × 10-2 for the
polycrystalline I at 293 K (determined using an integrating sphere) and increases up to ∼0.8 at 77 K. The
quantum yield of 1O2 is 0.17 ± 0.02 in O2-saturated dichloromethane solutions. [Au10Se4(dpppe)4]Br2 {dpppe
= bis(diphenylphosphanyl)pentane} (II) shows a broad near-infrared PL at 880 nm in dichloromethane [φPL
= (4 ± 1) × 10-3], which is shifted up to ∼1020 nm in the solid II at 77 K (φPL ∼ 3 × 10-3). Although the
quantum efficiency of II as a luminophor is quite moderate, it is comparable to that of organic infrared laser
dyes such as Styryl-20 and IR26. A particular configuration of the Au10Se4 core appears to be crucial for the
near-infrared PL: the “isomeric” complexes [Au10Se4(dppm)4]Br2 {dppm = bis(diphenylphosphanyl) methane}
(III) and [Au10Se4(depe)4]Cl2 {depe = bis(diethylphosphanyl) ethane} (IV) show no significant PL.