TY - JOUR
T1 - Spectroscopic and quantum chemical study on a non-linear optical material 4-[(1E)-3-(5-chlorothiophen-2-yl)-3-oxoprop-1-en-1-yl] phenyl4-methylbenzene-1-sulfonate
AU - Kumar, Rajesh
AU - Karthick, T.
AU - Srivastava, Anubha
AU - Gangopadhyay, Debraj
AU - Parol, Vinay
AU - Tandon, Poonam
AU - Gupta, Archana
AU - Kumar, Amit
AU - Subrahmanya Bhat, K.
N1 - Funding Information:
Poonam Tandon reports financial support was provided by Science and Engineering Research Board, New Delhi, India. T. Karthick reports financial support was provided by Department of Science and Technology, New Delhi, India. Debraj Gangopadhyay reports financial support was provided by IOCB, Prague, Czechia.
Funding Information:
PT acknowledges the financial support from Department of Science and Technology, Science and Engineering Research Board (DST-SERB, Ref. no. CRG/2019/006671). TK acknowledges the management of SASTRA Deemed University, Thanjavur, Tamil Nadu, and India for providing necessary infrastructure and computational facilities and acknowledges the financial support by Department of Science and Technology, New Delhi, India under DST-FIST project (Project No: SR/FST/PS-1/2020/135). Debraj Gangopadhyay acknowledges Institute of Organic Chemistry and Biochemistry, Prague, Czechia for providing financial assistance under postdoctoral fellowship scheme.
Publisher Copyright:
© 2021
PY - 2022/1/15
Y1 - 2022/1/15
N2 - Chalcone derivatives are known for their characteristic non-linear optical efficiency. In the present work, the relation between the molecular structure and non-linear optical properties of a synthesized chalcone derivative 4-[(1E)-3-(5-chlorothiophen-2-yl)-3-oxoprop-1-en-1-yl] phenyl4-methylbenzene-1-sulfonate (4TPMS) have been investigated by combined experimental and theoretical approaches. The title compound 4TPMS was characterized by spectroscopic techniques viz. Raman, FT-IR, UV-vis, and 1H NMR. Further, the experimental findings were validated by quantum chemical computations. The crystalline geometry of 4TPMS was optimized to energy minima by employing density functional theory (DFT) with B3LYP/6-311++G(d,p) approximation level. Harmonic vibrational frequencies were calculated and the spectral assignments have been done by potential energy distribution (PED) analysis. Significant non-linear optical (NLO) responses of chalcone are mainly caused by charge delocalization between lone pair and antibonding molecular orbitals within the molecule. Hence, natural bond orbital (NBO) was performed to analyze the charge delocalization along with the stability of the molecule. The population analysis based on Charges from Electrostatic Potentials using a Grid based method (CHELPG) was employed to understand the electrophilic/nucleophilic reaction sites. Moreover, the time-dependent density functional theory (TD-DFT) was employed to predict the energies, absorption wavelengths (λmax) and oscillator strengths (f) of the electronic transitions. The TD-DFT calculation successfully reproduces the experimental UV-Vis spectrum of 4TPMS. The chemical shifts observed in 1H-NMR and the calculated GIAO shielding tensors also showed good agreement. A vibrational contribution to the NLO activity and the effect of charge delocalization on the NLO response were illustrated by comparing the similar kind of chalcone derivatives.
AB - Chalcone derivatives are known for their characteristic non-linear optical efficiency. In the present work, the relation between the molecular structure and non-linear optical properties of a synthesized chalcone derivative 4-[(1E)-3-(5-chlorothiophen-2-yl)-3-oxoprop-1-en-1-yl] phenyl4-methylbenzene-1-sulfonate (4TPMS) have been investigated by combined experimental and theoretical approaches. The title compound 4TPMS was characterized by spectroscopic techniques viz. Raman, FT-IR, UV-vis, and 1H NMR. Further, the experimental findings were validated by quantum chemical computations. The crystalline geometry of 4TPMS was optimized to energy minima by employing density functional theory (DFT) with B3LYP/6-311++G(d,p) approximation level. Harmonic vibrational frequencies were calculated and the spectral assignments have been done by potential energy distribution (PED) analysis. Significant non-linear optical (NLO) responses of chalcone are mainly caused by charge delocalization between lone pair and antibonding molecular orbitals within the molecule. Hence, natural bond orbital (NBO) was performed to analyze the charge delocalization along with the stability of the molecule. The population analysis based on Charges from Electrostatic Potentials using a Grid based method (CHELPG) was employed to understand the electrophilic/nucleophilic reaction sites. Moreover, the time-dependent density functional theory (TD-DFT) was employed to predict the energies, absorption wavelengths (λmax) and oscillator strengths (f) of the electronic transitions. The TD-DFT calculation successfully reproduces the experimental UV-Vis spectrum of 4TPMS. The chemical shifts observed in 1H-NMR and the calculated GIAO shielding tensors also showed good agreement. A vibrational contribution to the NLO activity and the effect of charge delocalization on the NLO response were illustrated by comparing the similar kind of chalcone derivatives.
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U2 - 10.1016/j.molstruc.2021.131540
DO - 10.1016/j.molstruc.2021.131540
M3 - Article
AN - SCOPUS:85115893965
SN - 0022-2860
VL - 1248
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
M1 - 131540
ER -