Photoluminescence of Doped Superatoms M@Au_12 (M = Ru, Rh, Ir) Homoleptically Capped by (Ph_2)PCH_2P(Ph_2): Efficient Room-Temperature Phosphorescence from Ru@Au_12

摘要

A series of doped gold superatoms M(a)Au_12 (M = Ru, Rh, Ir) was synthesized by capping with the bidentate ligand (Ph_2)PCH_2P(Ph_2). A single-crystal X-ray diffraction analysis showed that all the M@Au_12 superatoms had icosahedral motifs with a significantly higher symmetry than that of the pure Au_13 counterpart due to different coordination geometries. The Ru@Au_12 superatom exhibited a room-temperature phosphorescence with the highest quantum yield of 0.37 in deaerated dichloromethane. Density functional theory calculations suggested that the efficient phosphorescence is ascribed to a rapid intersystem crossing due to the similarity between the singlet and triplet excited states in terms of structure and energy.