The structural stability and photoabsorption properties of Ni(II)-based metal-organic complexes with octahedral coordination having different planar ligand ring structures were investigated employing density functional theory (DFT) and its time-dependent extension (TD-DFT) considering the M06 exchange-correlation functional and the Def2-TZVP basis set. The results showed that the molecular composition of different planar cyclic ligand structures had significant influences on the structural stability and photoabsorption properties of metal-organic complexes. Only those planar ligands that contained aromatic rings met the basic criteria (thermal stability, structural reversibility, and appropriate excitation frequency domain) for light-induced excited spin state trapping, but their spin transition efficiencies were very different. While, in all three aromatic cases, the singlet electronic excitations induced charge distribution that could help in the singlet-to-triplet spin transition, and triplet excitations, which could assist in the backward (triplet-to-singlet) spin transition, was found only for one complex.
Keywords: TD-DFT; intersystem crossing; metal-ligand octahedral coordination; singlet-triplet spin transition; spin-orbit coupling.