Designing Excess Electron Compounds by Substituting Alkali Metals to a Small and Versatile Tetracyclic Framework: A Theoretical Perspective

[Image: see text] Organic compound-based nonlinear optical (NLO) materials have sparked a lot of attention due to their multitude of applications and shorter optical response times than those of inorganic NLO materials. In the present investigation, we designed exo-exo-tetracyclo[6.2.1.1(3,6).0(2,7)]dodecane (TCD) derivatives, which were obtained by replacing H atoms of methylene bridge carbon with alkali metals (Li, Na, and K). It was observed that upon the substitution of alkali metals at bridging CH(2) carbon, absorption within the visible region occurred. Moving from 1 to 7 derivatives, the maximum absorption wavelength of the complexes exhibited a red shift. The designed molecules showed a high degree of intramolecular charge transfer (ICT) and excess electrons in nature, which were responsible for rapid optical response time and significant large molecular (hyper)polarizability. Calculated trends also inferred that the crucial transition energy decreased in order that also played a key role in the higher nonlinear optical response. Furthermore, to examine the effect of the structure/property relationship on the nonlinear optical properties of these investigated compounds (1–7), we calculated the density of state (DOS), transition density matrix (TDM), and frontier molecular orbitals (FMOs). The largest first static hyperpolarizability (β(tot)) of TCD derivative 7 was 72059 au, which was 43 times greater than that of the prototype p-nitroaniline (β(tot) = 1675 au).