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 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.

Structural, Electronic, Thermodynamic, Optical and Nonlinear Optical Properties of Curcumin Complexes with Transition Metals: DFT and TD‐DFT Study

“…Therefore, it may be considered as a descriptor to represent the charge movement across the molecule. The high charge mobility in the system is explained by the high values of dipole moment which are at the origin of NLO properties of investigated systems (see, e. g [58] …”

Bis-TTF-Ge derivatives: promising linear and nonlinear optical properties, a theoretical investigation

“…In current years, quantum chemical calculations have become a widely accepted method for predicting new NLO materials. 20,21 For the NLO calculation we carried out a test on T36 with the 6-311++G and 6-311G(d,p) basis set, but did not find significant differences (see Fig. S3, ESI †).…”

“…Numerous techniques for developing new high-performance NLO materials have been proposed, including diradical characterization, 13 synthesis of molecular structures of electron-donor (D)–π–electron-acceptor (A) (D–π–A), 14 reinforcing push–pull effects, 15,16 designing octupolar compounds, 17,18 multidecker sandwich complexes, 19 asymmetric coordination complexes, 20–23 excess electrons, 24–29 etc. Among the studied NLO materials the inorganic compounds have attracted exceptional interest because of their physicochemical stability and thermal stability.…”

“…This is due to their important applications in different areas such as in photonic devices such as molecular switching, frequency doubling, telecommunications and optical information processing. [6][7][8][9][10][11][12] Numerous techniques for developing new high-performance NLO materials have been proposed, including diradical characterization, 13 synthesis of molecular structures of electrondonor (D)-p-electron-acceptor (A) (D-p-A), 14 reinforcing pushpull effects, 15,16 designing octupolar compounds, 17,18 multidecker sandwich complexes, 19 asymmetric coordination complexes, [20][21][22][23] excess electrons, [24][25][26][27][28][29] etc. Among the studied NLO materials the inorganic compounds have attracted exceptional interest because of their physicochemical stability and thermal stability.…”

The effect of resonance-assisted hydrogen bond on the second-order nonlinear optical properties of pyridine hydrazone photoswitches: a quantum chemistry investigation

“…These compounds have a wide range of applications in different fields, such as optical communication, optical computing, optical memory, and all-optical signal processing. 6–11 Photochromic compounds, such as stilbenes, azobenzenes, 12–14 diarylethenes, 15 spiropyrans, 16 and fulgides, 4,17 have excellent nonlinear optical responses (high hyperpolarizability). The combination between these two properties (photochromic and nonlinear optical) empowers generations of switchable second-order NLO materials.…”