The Nonlinear Optics Property Research Of The Electride Molecules With Cage And Cup Shaped Complexant

It is well known that electride is an ionic salt in which the excess electron is the anion. Researching the nonlinear optics charactistics of electrides is a new research field. A very good idea to improve the electron stability is to construct the electride with electron trappted in cage. However, this is a challenge to chemists.In this thesis, the nonlinear optics properties were researched for the electride molecules with cage and cup shaped complexant. The main work concerned are listed as follows:(1) We select the perfluorinated fullerene cage C20F20 as the hole of electron and take the alkali metal atoms(M = Na, K) and superalkali atoms(M3O, M = Na, K)with smaller vertical detachment energy(VDE) value as the source of the electrons,constructing new organic single-caged electride salt molecules M+(e@C20F20)- and(M3O)+(e@C20F20)- due to the long-range charge transfer from(super)alkali to inside the cage forming an electron-hole pair in molecule. For the nonlinear optical response,static first hyperpolarizabilities(?0) and the superalkali effect on ?0 are exhibited for these new molecules. The ?0 values are 400 and 600 for M+(e@C20F20)- << 13000 and10000 au for(M3O)+(e@C20F20)-. It is revealed that the superalkali effect on ?0 values is dramatic and the ?0 value is increased about 20-30 times. New single-caged electride salt(M3O)+(e@C20F20)- molecules have not only large nonlinear optical(NLO) property but also higher stability. They may become potential high-performance nonlinear optical material.(2) Novel cup-saucer-cage shaped sandwich electride molecules calix[4]pyrrole···K3O+···e@Cn Fn-,(n = 8, 10, 14, 20 and 36) with an excess electron protected inside Cn Fn cage are constructed theoretically. In the sandwich structures,the below calix[4]pyrrole cup pushes the valence electron of sandwiched superalkali atom K3 O saucer forming an excess electron and which is further pulled and protected inside the above Cn Fn cage, thus an electron-transfer relay occurs. In particular, owing to the unusual electron transfer, an unusual and fortunate phenomenon is discovered that increasing Cn Fn cage size enhances not the only nonlinear optical response(?0)but also electron stability(VIP). Then Thus, a new strategy of simultaneously enhancing ?0 and VIP values is found for the first time, namely by increasing Cn Fn cage size in novel cup-saucer cage-shaped sandwich electride molecules with the excess electron protected inside cage.(3) An electride molecule e–???K(1)+???calix[4]pyrrole???K(2)+???e– as an external electric field(F) driving nonlinear optical(NLO) switch is designed theoretically. It is also first singlet diradical of electride. A switching mechanism of electronic structure isomerization emerges. A small electric field driving can lead to an excess electron transfer from one side K(1) through the middle calix[4]pyrrole to the other side K(2) forming a lone excess electron pair of s-type and quenching the singlet diradical. This brings a very large contrast of static first hyperpolarizability(?0): from 0(F = 0, Off form) to 4.060 × 105 au(F = 5 × 10-4 au, On form). F = 30 ×10-4au brings the largest ?0 value of 3.147 × 106 au. This work opens a new research field of electric field NLO switch of electride molecule.