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

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.