Substituent and solvent effects on electronic structure and spectral property of ReCl(CO)3(N∧N) (N∧N = glyoxime): DFT and TDDFT theoretical studies.

The ground- and excited-state structures of five Re(I) halide glyoxime complexes ReCl(CO)(3)(N(∧)N) (N(∧)N = glyoxime (DHG 1), dimethylglyoxime (DMG 2), cyclohexane dione glyoxime (CHDG 3), dibromoglyoxime (DBG 4), and dimethylformylgloxime (DMFG 5)) have been studied with density functional theory (DFT) and configuration interaction with single excitations (CIS) methods. Time-dependent density functional theory/polarized continuum model (TDDFT/PCM) was carried out to predict the absorption and emission spectra in different media. The effect of substituent and solvent has been researched. It is found that electron-donating groups increase the lowest unoccupied molecular orbital (LUMO) energy resulting in the increased highest occupied molecular orbital (HOMO)-LUMO energy gap. The change leads to their absorption spectra blue shifts in the order 1 > 2 > 3, which arises from the HOMO-1 → LUMO. Just the opposite, electron-withdrawing groups lead to the spectra red shifts (5 > 4 > 1) because of the decreased HOMO-LUMO energy gap. The reorganization energy (λ) calculations show that the relatively balanceable charges transfer abilities of 2 will result in the higher efficiency of organic light emitting devices (OLEDs). In addition, both the absorption and the emission spectra display red shifts in different extents with the decrease of solvent polarity.