Theoretically designed M@diaza[2.2.2]cryptand complexes: the role of non-covalent interactions in promoting NLO properties of organic electrides

Organic excess electron compounds with significant nonlinear optical (NLO) properties are widely employed in optoelectronic applications. Herein, single-alkali metals with diaza[2.2.2] cryptand (M@crypt,M=Li, Na, and K) are investigated for optoelectronic and NLO properties by using the density functional theory. Thermodynamic and kinetic stabilities of present complexes are computed through interaction energy (E-int) and ab-initio molecular dynamic (AIMD) simulations. M@crypt complexes carry excess electrons and mimic molecular electrides. Quantum theory of atoms in molecules (QTAIM) analysis and reduced density gradient (RDG) spectra demonstrate the roles of the weak van der Waals (vdW) interactions between metal and complexant. The remarkable hyperpolarizability (beta(o)) value up to 1.41 x 10(6) au may be credited to the presence of loosely bound excess electrons. The hyper Rayleigh scattering hyperpolarizability (beta(HRS)) is recorded up to 1.31 x 10(6) au for the K@crypt. Furthermore, frequency-dependent first-order and second-order hyperpolarizability is more prominent at the applied frequency of omega = 0.042823 au. The electron localizing function (ELF) and localized orbital locator (LOL) analysis further disclose the nature of interaction between alkali metal and complexant. The TD-DFT method is adopted to get excited state parameters and absorbance properties. An electron density difference map (EDDM) is exploited to evaluate the orbital contributions in excited states. Hence, the studied electride may become a promising candidate for NLO materials. We anticipate that the present work will provide insight into further development of molecular electride for optoelectronic applications.