Correlation between Second Ionization Potential and Nonlinear Optical Properties of Bivalent Transition-Metal Complexes: A Quantum Chemical Study

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)L^<i>i</i> 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.