ABSTRACT
Discovering new materials with excellent nonlinear optical responses has recently become a very interesting research topic in the different domains of materials science. Currently, density functional theory (DFT) has been shown to be a powerful tool in the explanation and prediction of the performance of novel nonlinear optical (NLO) materials. Quantum chemical calculations using DFT/TD-DFT with the B3LYP exchange-correlation functional are reported to study the NLO properties of 26 bivalent transition-metal (TM) complexed by six acyclic hexadentate ligands providing pyridyl/pyrazine-amide-thioether/ether coordination and differing by the nature of the methylene dichalcogenate spacer between the rings. However, the geometry parameters and the theoretically predicted UV-vis absorption spectra of the optimized compounds M(II)Li are in excellent agreement with the experiment, when available, the trends among the nature of the TM, the importance of the ligand spacer, and of the substituents of the pyridine/pyrazine amide ligand are discussed. To the best of our knowledge, our work evidences for the first time that the hyper-polarizability, second harmonic generation, and hyper-Rayleigh scattering response of TM coordination complexes can be correlated to the second ionization potential of metal and spin state of complexes.
