Face specific doping of Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane with superalkalis and alkaline earth metals leads to enhanced static and dynamic NLO responses

The first synthesis of all-cis-1,2,3,4,5,6-hexafluorocyclohexane (C6H 6 F 6 = 1), a facially polarized molecule, opened up new avenues for designing novel nonlinear optical (NLO) materials. In the present work, face specific superalkali based alkaline earthides M3O+-1-M’₋ (M = Li,Na,K & M’ = Be,Mg,Ca) have been designed theoretically. The NBO analysis and HOMOs electron density confirmed their alkaline earthide nature. The thermodynamic stability was confirmed by their interaction energies (−16.11 to −115.51 kcal/mol). Non-covalent interactions were confirmed through NCI and QTAIM analyses. The maximum absorption in UV-VIS-NIR region confirmed that the complexes are deep UV transparent. The maximum first and second hyperpolarizabilities of 5.2 × 106 au and 5.7 × 108 au confirmed their enhanced NLO response. The maximum SHG, EOPE and hyper-Rayleigh scattering coefficient (βHRS) are 1.41 × 107 au, 3.13 × 106 au and 2.1 × 106 au, respectively. The EFISHG and EOKE at 4.17 × 1011 au and 1.51 × 1011 au have been obtained. The results of quadratic nonlinear refractive index up to 2.16 × 10−7 au indicated their increased NLO response. These results suggest that designed complexes provide a new insight towards the rational design of stable high performance NLO materials. [Display omitted] •Superalkali based alkaline earthides have been designed theoretically by using DFT simulations.•NBO analysis and HOMOs electron density confirmed the alkaline earthide nature.•These complexes have maximum absorption in UV-VIS-NIR region and are deep UV transparent.•The high NLO responses of 5.2 × 106 au and 5.72 × 108 au for first and second hyperpolarizabilities are observed.•Hyper-Rayleigh Scattering (βHRS) and quadratic nonlinear refractive indices (n2) reflect outstanding NLO response.