Theoretical Investigation of Jack-in-the-Box Electro-Optical Compounds: In-Silico Design of Mixed-Argon Benzonitriles Towards the Template of Clusters

Abstract: This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 113, 3576–3587, 2009) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path. Herein, the effect of donor and acceptor substitutions on the geometrical parameters, electronic, optical and reactivity of argon in organic matrices has been computed by computational methods. The 6–311 ++ g(2d,2p) basis set and second order Moller–Plesset perturbation theory are used to explore mixed-argon benzonitrile compounds (1–7) namely; hydrogen argon cyanide, methyl argon cyanide, phenyl argon cyanide, cyano-phenyl argon cyanide, hydroxy-phenyl argon cyanide, nitro-phenyl argon cyanide and methoxy-phenyl argon cyanide respectively. Mullikan population analysis, natural bonding orbital (NBO) analysis, frontier molecular orbital analysis, molecular electrostatic potential surface analysis, polarizability and hyperpolarizability of noble gases in organic matrices have been studied. The results indicate that the electron donating groups (hydroxy, methoxy, phenyl and methyl) and electron withdrawing groups (nitro and cyano) fine tune the HOMO–LUMO orbitals and nonlinear optical properties. NBO analysis confirmed that these donor–acceptor groups support the charge transfer in our investigated jack-in-the-box compounds. The linear polarizability and first hyperpolarizability results suggest that all the studied compounds are good candidates for NLO response and associated applications. Graphic Abstract: [Figure not available: see fulltext.]