title: 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.
abstract: 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.
authors.affiliation: MOE Key Laboratory of Theoretical Environmental Chemistry, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510631, P. R. China. luoqiong@scnu.edu.cn and Institute of Chemical Physics, Beijing Institute of Technology, Beijing 100081, P. R. China. leen04@163.com.
authors.forename: Jinmei
authors.initials: J
authors.lastname: Mai
authors.affiliation: Collaborative Innovation Center for Marine Biomass Fiber Materials and Textiles, College of Chemical Science and Engineering, Shandong Sino-Japanese Center for Collaborative Research of Carbon Nanomaterials, Laboratory of Fiber Materials and Modern Textiles, the Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071, P. R. China.
authors.forename: Shida
authors.initials: S
authors.lastname: Gong
authors.affiliation: Institute of Chemical Physics, Beijing Institute of Technology, Beijing 100081, P. R. China. leen04@163.com.
authors.forename: Nan
authors.initials: N
authors.lastname: Li
authors.affiliation: MOE Key Laboratory of Theoretical Environmental Chemistry, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510631, P. R. China. luoqiong@scnu.edu.cn.
authors.forename: Qiong
authors.initials: Q
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, P. R. China.
authors.forename: Zhiru
authors.initials: Z
authors.lastname: Li
mesh_terms: D004583:Electrons; D005029:Ethylenediamines / Q000737:chemistry*; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D011188:Potassium / Q000737:chemistry*; D011789:Quantum Theory; D012492:Salts / Q000737:chemistry; D012964:Sodium / Q000737:chemistry*
chemical_list: D005029:Ethylenediamines; D012492:Salts; C031234:ethylenediamine; D008094:Lithium; D012964:Sodium; D011188:Potassium