Exploration of CH⋯F & CF⋯H mediated supramolecular arrangements into fluorinated terphenyls and theoretical prediction of their third-order nonlinear optical response

In the present study, three novel fluorinated terphenyl compounds i.e., 2′,4,4′′,5′-tetrafluoro-1,1':4′,1′′-terphenyl (1), 2′,5′-difluoro-1,1':4′,1′′-terphenyl (2) and 2′,5′-difluro-4,4′′-diphenoxy-1,1:4′,1′′-terphenyl (3) have been synthesized by Suzuki Miyaura method. Single crystal XRD study reveals ð-ð stacking stabilization in molecular packing along with F⋯H and F⋯C interactions. This computational quantum chemical exploration was also done by using density functional theory (DFT) methods. The comparison of experimental (SC-XRD) and theoretical (DFT) investigations on structural parameters have been reported which shows reasonable agreements. Hirshfeld surface analysis explores the strength of intermolecular interactions present in the synthesized compounds. A substantial computational analysis of synthesized compounds is done for their optoelectronic and third-order nonlinear optical properties. The third-order NLO study was performed at M06/6-311G* level of theory. A comparative analysis of third-order polarizability of studied compounds is done with that of para-nitroaniline (p-NA) molecule which is often considered as a prototype NLO molecule. The third-order NLO analysis results suggest that all investigated compounds 1, 2 and 3 have significant potential as efficient third-order NLO molecules as compared to p-NA. The studied compounds 1, 2 and 3 possess about 13.7 times, 5.2 times and 5.17 times larger third-order polarizability amplitudes than that of p-NA (25.45 × 10(−36) esu) as calculated at same M06/6-311G* levels of theory. Time-dependent density functional theory (TD-DFT) calculations are performed for electronic excitation energies and their oscillator strengths. The studies of frontier molecular orbitals (FMO) analysis, total and partial density of states (DOS) were performed to investigate the intramolecular charge transfer (ICT) process in the entitled compounds.