Theoretical studies on metal-metal interaction and intrinsic (1,3)[sigma*(d)sigma(s/p)] excited states of dinuclear d(10) complexes with bridging phosphane Ligands

摘要

CIS-optimized structures, the TD-DFT (B3LYP) method was employed to calculate the emission spectra of such complexes. For 3, the phosphorescent emissions were calculated at 424 and 514 nm in the solid state and acetonitrile, which is comparable to the experimental data of 475 and 480 nm, respectively. The comparison between the gas-phase and solution emissions for 1-3 reveals that the N -> M coordination results in a large red-shift of the emission wavelength. Taking previous studies into account, we found that the M-M distances are linearly correlated with the M-M stretching frequencies for the dinuclear d(10) complexes. (c) Wiley-VCH Verlag GmbH & Co.