Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Property and Molecular Nonlinearity

Abstract

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future. File list (2) download file view on ChemRxiv Manuscript.pdf (917.60 KiB) download file view on ChemRxiv Supporting Information.pdf (1.07 MiB)

Tuning Electronic Structure and Optical Properties of Li@cyclo[18]carbon Complex via Switching Doping Position of Lithium Atom

“…There is no significant difference between the α iso of Li@C 18 in and Li@C 18 out , which is similar to the law of polarizability between the analogues of many other types of compounds we have studied [41][42][43][44]. However, the change in the way of binding of Li atom not only causes the magnitude of β vec to vary, but also alters the sign of it.…”

“…The (hyper)polarizability density analysis, which graphically exhibits the spatial contribution of electrons in a molecule to electric response properties, is helpful to gain a deep insight into the physical nature of molecular (hyper)polarizability [17,[41][42][43][44]. The (hyper)polarizability densities, namely the local contributions to the respectively, for comparison.…”

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

“…32 Our theoretical calculation for the same systems not only perfectly reproduced the electronic absorption spectra and first-order hyperpolarizabilities observed in experiment, but more importantly, it deeply revealed the essences of the optical properties of these mesoionic molecules from the electronic structure level. 33 At the same time, we also found that Lyra and collaborators had theoretically predicted the first-order static hyperpolarizability on a variety of mesoionic compounds including the above-mentioned three ones by employing the semi-empirical time-dependent Hartree-Fock (AM1-TDHF) method. 34 However, due to the constraints of the level of calculation adopted, the response properties of these molecules obtained by them are obviously different from the measurements of the experiment and those calculated by us with a more reliable strategy.…”

“…34 However, due to the constraints of the level of calculation adopted, the response properties of these molecules obtained by them are obviously different from the measurements of the experiment and those calculated by us with a more reliable strategy. 32,33 In view of the fact that the influence of external field wavelength and solvent usually used to adjust the optical properties of organic materials has not been reported yet for mesoionic systems, in this work, we selects an electronic push-pull mesoionic compound, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate (hereinafter referred to as MIC), that possessing substituents with strong electron-donating/accepting capacity and also involving in previous calculation studies 34 as the research object to explore the influence of environments on the optical properties of this kind of organic molecules.…”

Tuning Electronic Structure and Optical Properties of Li@cyclo[18]carbon Complex via Switching Doping Position of Lithium Atom

“…The (hyper)polarizability density analysis, which graphically exhibits the spatial contribution of electrons in a molecule to electric response properties, is helpful to gain a deep insight into the physical nature of molecular (hyper)polarizability [17,[41][42][43][44]. The (hyper)polarizability densities, namely the local contributions to the (hyper)polarizabilities, in x direction […”