A new strategy for simultaneously enhancing nonlinear optical response and electron stability in novel cup-saucer(+)-cage(-)-shaped sandwich electride molecules with an excess electron protected inside the cage

作者：Wang, Jia-Jun; Zhou, Zhong-Jun; Bai, Yang; He, Hui-Min; Wu, Di; Li, Ying; Li, Zhi-Ru^*; Zhang, Hong-Xing

来源：Dalton Transactions, 2015, 44(9): 4207-4214.

DOI：10.1039/c4dt03282a

• DENSITY-FUNCTIONAL-THEORY
• STATIC 1ST
• CHARGE-TRANSFER
• C20F20 CAGE
• LI
• NA
• COMPLEXES
• ALKALIDES
• ANION
• HYPERPOLARIZABILITIES

Novel cup-saucer-cage-shaped sandwich electride molecules calix[4]pyrrole center dot center dot center dot K3O+center dot center dot center dot e@CnFn-, (n = 8, 10, 14, 20, and 36) with an excess electron protected inside the CnFn cage are constructed theoretically. In the sandwich structures, the below calix[ 4] pyrrole cup pushes the valence electron of the sandwiched superalkali atom K3O saucer, forming an excess electron, which is further pulled and protected inside the above CnFn cage, thus an electron-transfer relay occurs. In particular, owing to the unusual electron transfer, an unusual and fortunate phenomenon is discovered that increasing the CnFn cage size enhances not only the nonlinear optical response (beta(0)), but also the electron stability (VIP). Thus, a new strategy of simultaneously enhancing beta(0) and VIP values is found for the first time, namely by increasing the CnFn cage size in novel cup-saucer-cage-shaped sandwich electride molecules, with the excess electron protected inside the cage.

• 出版日期2015
• 单位吉林师范大学; 吉林大学