In silico screening of ethyl 4-[(E)-(2-hydroxy-4-methoxyphenyl)methyleneamino]benzoate and some of its derivatives for their NLO activities using DFT

Abstract

The nonlinear optical (NLO) properties of ethyl 4-[( E )-(2-hydroxy-4-methoxyphenyl)methyleneamino]benzoate (EMAB) and some of its derivatives are investigated herein using the density functional theory (DFT) and time-dependent (TD)-DFT methods. The density functionals B3LYP, CAM-B3LYP, M06-2X and ω B97XD, and basis sets 6-31 + G**, 6-311 + + G** and Def2-TZVPP have been used. From the results, EMAB and its substituted derivatives studied are promising candidates for NLO materials. In all cases, the static first and second hyperpolarizabilities (31.7–86.5 × 10 −30 and 84.4–273 × 10 −36 electrostatic units (esu), respectively) and the frequency-dependent NLO properties are found to be significantly larger (about 43–103 and 28–76 times greater) than those of the NLO prototypical molecule, para -nitroaniline. Furthermore, the maximum absorption wavelengths of the molecules fall within the UV region of the electromagnetic spectrum. Relative to EMAB, the derivatives have shown improved transparency–nonlinearity trade-offs. Natural bond orbital (NBO) and density of states (DOS) analyses herein revealed effective charge transfer within the molecules studied, especially those with stronger electron donors than that in EMAB (methoxy group). Among the molecules studied, the derivative obtained by substituting EMAB's methoxy group with the pyrrolyl group was found to exhibit the best NLO properties. Conclusively, the NLO activities of EMAB can be significantly improved through the substitution of its methoxy group with stronger electron donors.

Enhancing the charge transport and luminescence properties of ethyl 4-[(E)-(2-hydroxy-4-methoxyphenyl)methyleneamino]benzoate through complexation: a DFT and TD-DFT study

“…Results from Table 1 have revealed excellent agreement between experimental data and data obtained from calculations studies at the B3LYP/6-311++g**. 44,55 Moreover, the Cu-N and Cu-O bond lengths obtained theoretically fall within the range of acceptable values of 1.9-2.1 Å and 1.8-2 Å respectively. 69 Since these geometrical parameters fall within the acceptable range, we proceeded to use the PBE0-D3(BJ)/Def2-TZVP level of theory to predict the parameters of the modelled complexes.…”

“…51,53,54 The PBE0 functional has been used herein owing to its accurately and agreement with previous experimental results as well as theoretical results obtained at the B3LYP/6-311++g** level of theory in estimating geometrical parameters of EMAB. 44,55 Moreover, literature indicates that the PBE0 functional, especially when combined with the Def2-TZVP basis set yields good energies for transition metals. 9,51 Long-range dispersion corrections were done via the Grimme's dispersion correction along with the Becke-Johnson damping D3(BJ) scheme.…”

“…Table 1 Some selected theoretical geometrical parameters of EMAB and its copper complex, optimized at the PBE0-D3(BJ)/def2-TZVP level of theory, alongside the theoretical parameters of EMAB calculated at the B3LYP/6-311++g** level of theory 55 From the values of bond angles in Table 2, it is clear that the geometry adopted by the metal complexes is approximately square planar apart from the [Zn(EMAB) 2 ] which is nearly tetrahedral. In all cases, the geometries of the complexes slightly deviate from the 90°bond angles of perfect square planar species and 109.5°of perfect tetrahedral structures.…”

Computational Evaluation of the Structural, Topological, and Solvent Effects on the Nonlinear Optical Properties of 1-Methylurea Butanedioic Acid Crystal

“…Despite signifcant advances in the use of NLO materials in areas such as photonics, laser technology, and optoelectronics, where light is utilized for information transmission, the search for novel NLO systems that can better meet the needs of these sectors continues to be a major focus [1,[7][8][9][10]. Current literature indicates some developments in new and improved NLO materials (organic, semiorganic, and inorganic) with good optical damage tolerances and the ability for optical bandwidth conversion [8][9][10][11][12][13][14][15]. In general, factors such as conjugated length, molecule conformation, and intramolecular charge transfer infuence NLO features [16].…”

Opto-Electronics and Nonlinear Optical Properties of Isoindoline-1,3-Dione-Fullerene20-Isoindoline-1,3-Dione Using Density Functional Theory

“…The electro-optical and nonlinear optical (NLO) materials have received considerable attention due to their wide range of potential applications Kiven et al (2023). When the donor and acceptor groups are present at opposite ends, it leads to significant change and plays an essential role in materials D-A systems; introducing potent electron-donor groups raises the HOMO levels.…”