Nonlinear optical response of facially polarized all cis-1,3,5-trifluorocyclohexane doped with transition metals and calcium

Herein, the Janus type complexes have been designed that have the fame as potential candidates in nonlinear optical (NLO1) materials due to excess electrons. In present work, novel class of excess electronic compounds termed as transition metalides AE-1-TM2 complexes (AE = Ca, Fe/Co/Ni/Cu/Zn)3 have been designed theoretically using highly polarized all axially cis-1,3,5-trifuorocyclohexane 1 (C6H9F3) as complexant bearing a larger dipole moment of 5.42 D. The electronic, thermodynamic and geometric features of Ca-1-TM were studied using M06-2x|6-31++G(d,p) level of theory. More distinctively, transition metalide nature of the complexes has been verified by NBO4 (Natural Bond Orbital) and HOMOs5 (Highest Occupied Molecular Orbital) density distribution analysis. The thermodynamic stability of transition metalides is evident from large values of interaction energies (-6.99 to-25.01 kcal/mol). The designed complexes showed low excitation energies (2.09-4.01 eV) and high first hyperpolarizabilities (beta o) up to 2.16 x 105 (au). Moreover, hyper rayleigh scattering (beta HRS) was computed for evaluation of NLO response of complexes. Dipolar and octupolar nature of Ca -1-TM complexes have also been confirmed by the depolarization ratio (DR6). The higher values of hyperpolarizabilities provided evidences for the existence of excess electrons around transition metals. Two-level model approach was used for rationalization of hyperpolarizabilities. The results illustrated that the generation of these complexes is a novel entry in the metalide that can be recognized as preferable way for designing NLO materials.