LAUSR

Three cationic dinuclear Au(I) complexes containing acetonitrile (AN) as an ancillary ligand were synthesized: [μ-LMe(AuAN)2]·2BF4 (1), [μ-LEt(AuAN)2]·2BF4 (2), and [μ-LiPr(AuAN)2]·2BF4 (3) (LMe = {1,2-bis[bis(2-methylphenyl)phosphino]benzene}, LEt = {1,2-bis[bis(2-ethylphenyl)phosphino]benzene}, and LiPr = {1,2-bis[bis(2-isopropylphenyl)phosphino]benzene}). The unique structures of complexes 1-3 with two P-Au(I)-AN rods bridged by rigid diphosphine ligands were determined through X-ray analysis. The Au(I)-Au(I) distances observed for complexes 1-3 were as short as 2.9804-3.0457 Å, indicating an aurophilic interaction between two Au(I) atoms. Unlike complexes 2 and 3, complex 1 incorporated CH2Cl2 into the crystals as crystalline solvent molecules. Luminescence studies in the crystalline state revealed that complexes 1 and 2 mainly exhibited bluish-purple phosphorescence (PH) at 293 K: the former had a PH peak wavelength at 415 nm with the photoluminescence quantum yield ΦPL = 0.12, and the latter at 430 nm with ΦPL = 0.13. Meanwhile, complex 3 displayed near-white PH, that is dual PH with two PH bands centered at 425 and 580 nm with ΦPL = 0.44. The PH spectra and lifetimes of complexes 2 and 3 were measured in the temperature range of 77-293 K. The two PH bands observed for complex 3 were suggested to originate from the two emissive excited triplet states, which were in thermal equilibrium. From theoretical calculations, the dual PH observed for complex 3 is explained to occur from the two excited triplet states, T1H and T1L: the former exhibits a high-energy PH band (bluish-purple) and the latter exhibits a low-energy PH band (orange). The T1H state is considered 3ILCT with a structure similar to that of the S0-optimized structure. Conversely, the T1L state is assumed to be a 3MLCT with a T1-optimized structure, which has a short Au(I)-Au(I) bond and two bent rods (Au-AN). The thermal equilibrium between the two excited states is discussed based on computational calculations and photophysical data in the temperature range of 77-293 K. With regard to the crystal of complex 1, we were unable to precisely measure the temperature-dependent emission spectra and lifetimes, particularly at low temperatures, because the cooled crystals became irreversibly turbid over time.