Transition metalides based on facially polarized all-cis-1,2,3,4,5,6-hexafluorocyclohexane – a new class of high performance second order nonlinear optical materials

Abstract

Continuous attempts are being made to discover new approaches to design materials with extraordinary nonlinear optical responses. Herein, for the first time, we report the geometric, electronic, and nonlinear optical properties of novel Janus transition metalides AM-J-TM (where AM = Li, Na and K, and TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) containing alkali metals as a source of excess electrons for transition metals to generate metalides. The Janus organic complexant used for the study is all cis 1,2,3,4,5,6-hexafluorocyclohexane F₆C₆H₆ (J). These complexes contain the unique involvement of alkali metals (AM = Li, Na and K) as a source of excess electrons, which significantly affects the hyperpolarizability values of the resulting transition metalides. The NBO analysis reveals the charge transfer from alkali metals to the transition metals, thereby confirming the metalide behavior of the complexes. Moreover, the metalide nature of these complexes is validated through frontier molecular orbital (FMO) analysis. The values of interaction energies, vertical ionization potential (VIP) and vertical electron affinity (VEA) illustrate the stability of the metalide complexes. Ultimately, the hyperpolarizability values confirm the excellent nonlinear optical response of the designed transition metalides. The remarkable static first hyperpolarizability (β₀) response up to 4 × 10⁸ a.u. is observed for complexes of vanadium. Similarly, the complexes of AM-J-Mn and Li/Na-J-Sc show significantly high NLO response. These compounds besides providing a new entry into excess electron compounds will also pave the way for the design and synthesis of further novel NLO materials.