Heterochiral Self‐Discrimination Driven Dimerization of Polynuclear Gold(I)‐Sulfido Complexes with Enhanced Phosphorescence

Abstract Decanuclear chiral gold(I) sulfido clusters ( S SDP ‐Au 10 and R SDP ‐Au 10 ) have been assembled by taking advantage of the judiciously selected SDP ligands (SDP = 7,7′‐bis(diphenylphosphino)‐1,1′‐spirobiindane). Interestingly, an achiral heterodimer icosanuclear meso ‐cluster ( meso SDP ‐Au 20 ) has been obtained by simply mixing S SDP ‐Au 10 and R SDP ‐Au 10 in a 1:1 ratio. These gold(I) complexes have been found to display intense near‐infrared (NIR) luminescence with an emission maximum at around 750 nm in the solid state. The photoluminescence quantum yield (PLQY) of meso SDP ‐Au 20 in drop‐cast solid‐state thin film has been found to show a significant enhancement from 8 % in the S SDP ‐Au 10 and R SDP ‐Au 10 to 25 %. In addition, the dimerization process with heterochiral self‐discrimination has been found to be sensitive to the solvent polarity and configuration of the diphosphine ligand. This work has provided a platform for the investigation and mechanistic understanding of heterochiral self‐sorting and assembly processes.