Aggregation-Induced Emission with Alkynylcoumarin Dinuclear Gold(I) Complexes: Photophysical, Dynamic Light Scattering, and Time-Dependent Density Functional Theory Studies

[Image: see text] Aggregation-induced emission (AIE) has gained a remarkable amount of interest in the past 20 years, but the majority of the studies are based on organic structures. Herein, three dinuclear gold(I) complexes, with the general formula [PPh(2)XPPh(2)-Au(2)-Coum(2)], where the Au(I) atom is linked to three different diphosphanes [PPh(2)XPPh(2); DPPM for X = CH(2) (1.1), DPPP for X = (CH(2))(3) (1.2), and DPPA for X = C≡C (1.3)] and the propynyloxycoumarin precursor (1, 4-methyl-substituted coumarin), have been synthesized. The compounds present AIE characteristics, AIEgens, with high luminescence quantum yields in the solid state when they are compared to dilute solutions. Photophysical studies (steady-state and time-resolved fluorescence) were obtained, with AIE being observed with the three gold(I) complexes in acetonitrile/water mixtures. This was further corroborated with dynamic light scattering measurements. Time-dependent density functional theory (TDDFT) electronic calculations show that the compounds have different syn and anti conformations (relative to the coumarin core) with 1.1 syn and 1.2 and 1.3 both anti. From time-resolved fluorescence experiments, the augment in the contribution of the longer decay component is found to be associated with the emission of the aggregate (AIE effect) and its nature (involving a dimer) rationalized from TDDFT electronic calculations.