Influence of substituent at the para position of tetraphenylethylene on static and dynamic nonlinear optical properties: In-silico approach

Abstract

In this study, tetraphenylethylene (TPE) derivatives with various substituents (F, OH, OMe, CN, NO2, and NO) at the para position were selected for the non-linear optical properties. Non-centrosymmetric behavior and charge distribution of these derivatives were evaluated using natural bond orbital (27.24 kcal/mol orbital interaction energy in case of πC6-C10 → π*N46-O47 for TPE-NO), HOMO-LUMO diagrams, and molecular electrostatic potential analyses (OH, 34.15 kcal/mol and CN, −35.39 kcal/mol). TPE derivatives with electron-withdrawing groups displayed higher hyperpolarizability values (molecular, time and frequency dependent values) compared to electron-donating ones. TPE-NO have shown highest values for static (52.73 × 10-30 esu) and molecular (288.43 × 10-30 Debye.esu). TPE with withdrawing groups showed higher limit of first order hyperpolarizability ranging from 1050 × 10-30 to 1530 × 10-30 esu. βHRS1064 >βHRS1340 >βHRS1460 > βHRS1907 and βTD1064 <βTD1340 <βTD1460 < βTD1907 are the order of computed Hyper-Rayleigh scattering and time-dependent first order dynamic hyperpolarizability respectively.