Photophysics and bonding in neutral gold(I) organometallic complexes with an extended aurophilic supramolecular structure

This work represents a synergistic experimental/computational study of the molecular spectroscopy and bonding in Au(CO)Cl in solution and the solid state. The luminescence behavior for crystalline solids is similar for Au(CO)Cl and related (RNC)AuCl complexes that likewise stack in infinite chains, and both exhibit orange-red unstructured phosphorescence bands with extremely large Stokes shifts ((15-20) x 10(3) cm(-1)). The long aurophilic distances computed for the ground state (similar to 3.2 angstrom) are contracted in the phosphorescent excited state (similar to 2.6 angstrom), demonstrating excimeric Au-Au covalent bonds. The spectral data suggest phosphorescent species in which the excimeric Au-Au bonding is extended beyond two adjacent molecules in the solid state. Controlling the concentration in frozen solutions attains phosphorescent bands due to dimeric species for which the emission energies are higher (in the blue region) than those for crystalline solids and are reproduced by ab initio calculations. The spectral findings herein suggest that predictive information about the supramolecular structure may be obtained by the luminescnce behavior. This is exemplified by crystals of (1,1,3,3-Me4BuNC)AuCl, whose red-orange luminsecence anticipated an extended-chain supramolecular structure, which was later verified crystallographically, as the molecules were found to pack in zigzag chains with alternating short (3.418 angstrom) and long (4.433 angstrom) aurophilic distances. Solutions of Au(CO)Cl exhibit negative deviation from Beer's law for, higher-energy monomer bands with the appearance of lower-energy bands at high concentrations due to the dimerization of molecules. Time-dependent density-functional theory (TD-DFT) calculations for monomer and dimer models show good agreement with the experimental spectra and account for the major absorption bands. Ab initio calculations (CCSD(T)/cc-pVTZ) show a blue shift of similar to 23 cm(-1) in the nu(C rectangle O) frequency upon complexation, thus providing the first computational evidence of this anomalous blue shift known experimentally for Au(CO)Cl.