The impact of position and number of methoxy group(s) to tune the nonlinear optical properties of chalcone derivatives: a dual substitution strategy

Abstract

Using the state-of-art computational techniques, we limelight a structure-property relationship for the position and number of methoxy group(s) to tune the optical and nonlinear optical (NLO) properties (first hyperpolarizability) of chalcone derivatives. Based on our previously synthesized chalcones [system 1 ((E)-1-(2,5-dimethylthiophen-3-yl)-3-(2-methoxyphenyl)prop-2-en-1-one and system 4 (E)-1-(2,5-dimethylthiophen-3-yl)-3-(2,4,5-trimethoxyphenyl)prop-2-en-1-one)], we systematically design several novel derivatives with tuned optical and NLO properties. For instance, the rotation of methoxy group substitutions at three different possible ortho, meta, and para positions on phenyl ring show significant changes in NLO properties of these chalcones derivatives. The system 3 has shown β tot amplitude of 1776 a.u. with terminal 4-methoxyphenyl group (para-methoxy substitution), which is ~2.2 and 2.4 times larger than that of ortho- and meta-methoxyphenyl systems 1 and 2, respectively. Additionally, systems 3a and 4a, which are cyano derivatives of the systems 3 and 4 show significantly large β tot amplitudes of 3280 and 4388 a.u., respectively, which are about 3 and 4 times larger than that of para-nitro aniline (PNA) molecule (a typical donor-acceptor molecule) at the same LC-wPBE/6-311G** level of theory. The origin of larger β tot amplitudes has been traced in lower transition energies and higher oscillator strengths for crucial transitions of designed derives. Thus, our investigation reveals that the chalcones derivatives with para-methoxyphenyl groups possess reasonably large amplitudes of their first hyperpolarizability and good optical transparency (3.0-4.7 eV), which can make them attractive candidates for nonlinear optical applications.

Nonlinear Optical Study in a Set of Dibenzylideneacetone Derivatives with Potential for Optical Frequency Conversion

“…Similar compounds tend to change their NLO response magnitude with the position of the substituents on the phenyl ring. Such an effect was previously studied and confirmed elsewhere [46,47]. In those studies, the methoxy group influenced the NLO response when placed in different positions (para, ortho, and meta) of the phenyl ring, achieving the highest response when placed in the para-position of the phenyl ring.…”

First-principles study of nitrogen-doped nanographene as an efficient charge transport and nonlinear optical material

“…Over the past some years, several investigations have been performed on routine push-pull chromophores to explore their potential for optical and nonlinear optical properties. 32,33 Unlike the previous investigations, in present study, we chose the N-doped graphene that has already well-characterized structure.…”

Pyrene Based NLOphoric D‐π‐A‐π‐D Coumarin‐Chalcone and Their Red Emitting OBO Difluoride Complex: Synthesis, Solvatochromism, Z‐scan, and Detailed TD‐DFT Studies

“…The first‐order hyperpolarizability (β) value for 6 is 208.14 is 325.22 folds higher than urea (0.64 x10 −30 esu, at B3LYP/6‐31G (d) level of theory) and the second‐order hyperpolarizability (γ) for 6 is 3028.93 is 2704.40 folds higher than urea (1.12 x 10 −36 esu, at B3LYP/6‐31G (d) basis set) ( Supplementary information Table S6 ). Moreover, the β and γ values of these compounds were compared with the reported donor‐π‐acceptor coumarin‐chalcones and their BF 2 complexed dyes, we found that β values of these dyes are lower and γ values are higher than the reported donor‐π‐acceptor coumarin‐chalcones and their BF 2 complexed dyes and also the β and γ values of these compounds were compared with the reported chalcone derivatives and found that the β and γ values of synthesized compounds are found to higher than the reported chalcone derivatives ( Supplementary information Table S7 ). The CAM−B3LYP functionals work better for calculations, which has 19–65% HF exchange percentage compared to 20%, 50% for B3LYP and BHHLYP respectively .…”