Designing Alkalides with Considerable Nonlinear Optical Responses and High Stability Based on the Facially Polarized Janus <i>all</i>-<i>cis</i>-1,2,3,4,5,6-Hexafluorocyclohexane

The first synthesis of facially polarized all-cis-1,2,3,4,5,6-hexafluorocyclohexane (1) was a tour de force of organic chemistry and opened up new possibilities for molecular design. In view of its large facial polarization, 1 was first utilized as a complexant to design a series of organic alkalides, namely M+·1·M′– (M, M′ = Li, Na, K), in this work. The alkalide identities of these proposed species were guaranteed by their HOMOs and VIE values, as well as NBO analysis. Our computational results show that these novel alkalides possess large complexation energies and thus exhibit high stability due to the strong electrostatic interaction between the alkali-metal ions and the axial fluorine or hydrogen atoms of 1. In particular, it is revealed that these novel alkalides possess remarkably large nonlinear optical responses with the first hyperpolarizabilities (β0) up to 1.45 × 106 au. Moreover, the feasibility of using 1 to design superalkali-based alkalide and superalkalide was also examined. We hope that this work will promote further application of 1 and, on the other hand, attract more research interest and efforts in designing and synthesizing new alkalides.