A novel class of compounds--superalkalides: M⁺(en)₃M'₃O⁻ (M, M' = Li, Na, and K; en = ethylenediamine)-with excellent nonlinear optical properties and high stabilities.

With the aid of ab initio calculations at the MP2 level of theory, we designed a novel class of inorganic salts, M(+)(en)3M3'O(-) (M, M' = Li, Na, and K), by using the M3'O superalkalis. These compounds are the first examples of inorganic salts wherein the superalkali occupies the anionic site, and termed superalkalides. The electronic structural features of the M(+)(en)3M3'O(-) superalkalides are very similar to those of the corresponding M(+)(en)3M'(-) alkalides which have been reported by Zurek (J. Am. Chem. Soc., 2011, 133, 4829). In this study, the calculated NLO properties of M(+)(en)3M3'O(-) and M(+)(en)3M'(-) (M, M' = Li, Na, and K) show that both superalkalides and alkalides have significantly large first hyperpolarizabilities (β0) with the values in the range of 7.80 × 10(3) to 9.16 × 10(4) a.u. and 7.95 × 10(3) to 1.84 × 10(5) a.u., respectively. Computations on the stabilities of M(+)(en)3M3'O(-) and M(+)(en)3M'(-) demonstrate that the M(+)(en)3M3'O(-) superalkalides are preferably stable than the corresponding M(+)(en)3M'(-) alkalides because of the presence of hydrogen bonds in M(+)(en)3M3'O(-). Therefore, the designed superalkalides, M(+)(en)3M3'O(-) (M, M' = Li, Na, and K), with excellent nonlinear optical properties and high stabilities are greatly promising candidates for NLO materials. We hope that this article could attract more research interest in superatom chemistry and for further experimental research.