Sun Wei-Ming, Li Ying, Li Xiang-Hui, Wu Di, He Hui-Min, Li Chun-Yan, Chen Jing-Hua, Li Zhi-Ru
Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P. R. China.
The School of Pharmacy, Fujian Medical University, Fuzhou, 350108, P. R. China.
Chemphyschem. 2016 Sep 5;17(17):2672-8. doi: 10.1002/cphc.201600389. Epub 2016 Jun 7.
Guided by density functional theory (DFT) computations, a new series of superalkali-based alkalides, namely FLi2 (+) (aza222)K(-) , OLi3 (+) (aza222)K(-) , NLi4 (+) (aza222)K(-) , and Li3 (+) (aza222)K(-) were designed with various superalkali clusters embedded into an aza222 cage-complexant. These species possess diverse isomeric structures in which the encapsulated superalkalis preserve their identities and behave as alkali metal atoms. The results show that these novel alkalides possess larger complexation energies and enhanced hyperpolarizabilities (β0 ) compared with alkali-metal-based and previous superalkali-based clusters. Especially, a prominent structural dependence of β0 is observed for these studied compounds. Hence, the geometric factors that affect the nonlinear optical (NLO) response of such alkalides is elucidated in detail in this work. This study not only provides novel candidates for alkalides, it also offers an effective way to enhance the NLO response and stability of alkalides.
在密度泛函理论（DFT）计算的指导下，设计了一系列新型的基于超碱的碱化物，即FLi2(+) (aza222)K(-)、OLi3(+) (aza222)K(-)、NLi4(+) (aza222)K(-) 和Li3(+) (aza222)K(-)，其中各种超碱簇嵌入到aza222笼状配合物中。这些物种具有多种异构结构，其中封装的超碱保留了它们的特性，并表现得如同碱金属原子。结果表明，与基于碱金属的簇和先前基于超碱的簇相比，这些新型碱化物具有更大的络合能和增强的超极化率（β0）。特别是，对于这些研究的化合物，观察到β0对结构有显著依赖性。因此，本工作详细阐明了影响此类碱化物非线性光学（NLO）响应的几何因素。这项研究不仅为碱化物提供了新的候选物，还提供了一种增强碱化物NLO响应和稳定性的有效方法。
