Chalcone-based molecules: Experimental and theoretical studies on the two-photon absorption and molecular first hyperpolarizability

Luis M G Abegão; Francisco A Santos; Ruben D Fonseca; André L B S Barreiros; Marizeth L Barreiros; Péricles B Alves; Emmanoel V Costa; Gabriella B Souza; Márcio A R C Alencar; Cleber R Mendonça; Kenji Kamada; Leonardo De Boni; José Joatan Rodrigues Jr

doi:10.1016/j.saa.2019.117772

Chalcone-based molecules: Experimental and theoretical studies on the two-photon absorption and molecular first hyperpolarizability

Spectrochim Acta A Mol Biomol Spectrosc. 2020 Feb 15:227:117772. doi: 10.1016/j.saa.2019.117772. Epub 2019 Nov 6.

Affiliations

¹ Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE, Brazil; Department of Radiology & Biomedical Imaging, School of Medicine, Yale University, 300 Cedar Street, New Haven, CT 06520, USA. Electronic address: luis.abegao@yale.edu.
² Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE, Brazil.
³ Universidad Popular del Cesar, Departamento de Fisica, Barrio Sabana, 2000004 Valledupar, Cesar, Colombia; Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, 13560-970 São Carlos, SP, Brazil.
⁴ Departamento de Química, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE, Brazil.
⁵ Departamento de Química, Universidade Federal do Amazonas, 69077-000 Manaus, AM, Brazil.
⁶ Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, 13560-970 São Carlos, SP, Brazil.
⁷ National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka 563-8577, Japan.

PMID: 31707018
DOI: 10.1016/j.saa.2019.117772

Abstract

Five chalcone-based molecules denominated by C-3 ((E)-1-(4-methoxyphenyl)-3-phenylprop-2-en-1-one), C-4 ((E)-1,3-bis(4-methoxyphenyl)prop-2-en-1-one), C-5 ((E)-1-(benzo[d][1,3]dioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one), C-6 ((E)-3-(naphthalen-1-yl)-1-phenylprop-2-en-1-one) and C-7 ((E)-1-(4-methoxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one) were synthesized by Claisen-Schmidt reaction in solution of NaOH in water/ethanol 2:1. The aldehydes used were benzaldehyde, anisaldehyde, and β-naphthaldehyde, while the used ketones were acetophenone, p-methoxyacetophenone, and 3,4-methylenedioxyacetophenone. Z-scan and hyper-Rayleigh scattering techniques were used to study the nonlinear optical properties of these compounds in dichloromethane medium. By using Z-scan technique with femtosecond pulses, two-photon absorption cross-sections (σ^TPA) were determined, while the first molecular electronic hyperpolarizabilities (β^HRS) were evaluated by the hyper-Rayleigh scattering technique, with picosecond pulses. From the recorded two-photon absorption spectra, it was identified that compound C-7 presented the highest σ^TPA, regarding the HOMO-LUMO transition, with a value of 40 GM, while C-6 achieved the lowest value for the same transition with 13 GM. Concerning the values of the first molecular hyperpolarizability, compound C-4 presented the highest value, 38 × 10^-30 cm⁴ statvolt^-1, while C-3 presented the lowest β^HRS value of about 16 × 10^-30 cm⁴ statvolt^-1. Time-dependent density functional theory calculations were used to simulate the one- and two-photon absorption spectra, as well to predict the theoretical value of β^HRS in dichloromethane and vacuum medium.

Keywords: Chalcones; First hyperpolarizability; Hyper-Rayleigh scattering; Nonlinear optics; Two-photon absorption; Z-scan.