Near-white light emission from single crystals of cationic dinuclear gold(i) complexes with bridged diphosphine ligands

Three cationic dinuclear Au(I) complexes containing acetonitrile (AN) as an ancillary ligand were synthesized: [mu-L-Me(AuAN)(2)]middot2BF(4) (1), [mu-L-Et(AuAN)(2)]middot2BF(4) (2), and [mu-L-iPr(AuAN)(2)]middot2BF(4 )(3) (L-Me = {1,2-bis[bis (2-methylphenyl)phosphino]benzene}, L-Et = {1,2-bis[bis(2-ethylphenyl)phosphino]benzene}, and L-iPr = {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 & Aring;, 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 Phi(PL) = 0.12, and the latter at 430 nm with Phi(PL )= 0.13. Meanwhile, complex 3 displayed near-white PH, that is dual PH with two PH bands centered at 425 and 580 nm with Phi(PL )= 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, T-1H and T-1L: the former exhibits a high-energy PH band (bluish-purple) and the latter exhibits a low-energy PH band (orange). The T-1H state is considered (ILCT)-I-3 with a structure similar to that of the S-0-optimized structure. Conversely, the T-1L state is assumed to be a (MLCT)-M-3 with a T-1-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.