A novel class of compounds—superalkalides: M+(en)3M3′O− (M, M′ = Li, Na, and K; en = ethylenediamine)—with excellent nonlinear optical properties and high stabilities. Issue 43 (8th October 2015)

• Record Type: Journal Article
• Authors: Mai, Jinmei; Gong, Shida; Li, Nan; Luo, Qiong; Li, Zhiru
• Is Part Of: Physical chemistry chemical physics. Volume 17:Issue 43(2015)
• Page Start: 28754
• Page End: 28764
• Publication Date: 2015-10-08
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c5cp03635f
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : A novel class of inorganic salts wherein the superalkali occupies the anionic site, termed superalkalides, M + (en)3 M3 ′O − (M, M′ = Li, Na, and K) have been designed and predicted to be candidates for NLO materials. Abstract : With the aid of ab initio calculations at the MP2 level of theory, we designed a novel class of inorganic salts, M + (en)3 M3 ′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)3 M3 ′O − superalkalides are very similar to those of the corresponding M + (en)3 M′ − alkalides which have been reported by Zurek ( J. Am. Chem. Soc., 2011, 133, 4829). In this study, the calculated NLO properties of M + (en)3 M3 ′O − and M + (en)3 M′ − (M, M′ = Li, Na, and K) show that both superalkalides and alkalides have significantly large first hyperpolarizabilities ( β 0 ) 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)3 M3 ′O − and M + (en)3 M′ − demonstrate that the M + (en)3 M3 ′O − superalkalides are preferably stable than the corresponding M + (en)3 M′ − alkalides because of the presence of hydrogen bonds in M + (en)3 M3 ′O − . Therefore, the designed superalkalides, M + (en)3 M3 ′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.