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

Abstract

Three cationic dinuclear Au(I) complexes containing acetonitrile (AN) as an ancillary ligand were synthesized: [μ-L_Me(AuAN)₂]·2BF₄ (1), [μ-L_Et(AuAN)₂]·2BF₄ (2), and [μ-L_iPr(AuAN)₂]·2BF₄ (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 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 Φ_PL = 0.12, and the latter at 430 nm with Φ_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 Φ_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 ³ILCT with a structure similar to that of the S₀-optimized structure. Conversely, the T_1L 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.