title: Structures and considerable static first hyperpolarizabilities: new organic alkalides (M+@n6adz)M'- (M, M'=Li, Na, K; n=2, 3) with cation inside and anion outside of the cage complexants.
abstract: Eighteen structures of new organic alkalides (M+@n6adz)M'- (M, M'=Li, Na, K; n=2, 3) with the alkali-metal cation M+ lying near the center of the adz cage and the alkali-metal anion M'- located outside are obtained with all real frequencies. They exhibit very large static first hyperpolarizabilities (beta0) up to 3.2x10(5) au, which exceeds the record value of beta0=1.7x10(5) au for nonlinear optical compounds [Chem.-Eur. J. 1997, 3, 1091]. All potassides (M+@n6adz)K- (M=Li, Na, K; n=2, 3) have considerably large beta0 values (1.6x10(5)-3.2x10(5) au) much larger than the beta0 value (3.6x10(4) au) of the previously designed cuplike alkalide Li+(calix[4]pyrrole)K- [J. Am. Chem. Soc. 2006, 128, 1072]. This shows that the 26adz and 36adz cage complexants are preferable to cuplike calix[4]pyrrole complexant in enhancing the first hyperpolarizability. The effect of cage size of the complexant on the first hyperpolarizability is also presented here: in most cases, the smaller cage complexant corresponds to the larger beta0 value. Moreover, the crucial role by the alkali-metal anion in the large first hyperpolarizability of these alkalides is revealed. These results may provide new means for designing high-performance nonlinear optical materials.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China.
authors.forename: Fang-Fang
authors.initials: FF
authors.lastname: Wang
authors.forename: Zhi-Ru
authors.initials: ZR
authors.lastname: Li
authors.forename: Di
authors.initials: D
authors.lastname: Wu
authors.forename: Bing-Qiang
authors.initials: BQ
authors.lastname: Wang
authors.forename: Ying
authors.initials: Y
authors.lastname: Li
authors.forename: Zong-Jun
authors.initials: ZJ
authors.lastname: Li
authors.forename: Wei
authors.initials: W
authors.lastname: Chen
authors.forename: Guang-Tao
authors.initials: GT
authors.lastname: Yu
authors.forename: Feng Long
authors.initials: FL
authors.lastname: Gu
authors.forename: Yuriko
authors.initials: Y
authors.lastname: Aoki