Structures and Considerable Static First Hyperpolarizabilities: New Organic Alkalides (M+@n6adz)M'- (M, M' = Li, Na, K; n = 2, 3) with Cation Inside and
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- 作者：Fang-Fang Wang ; Zhi-Ru Li ; Di Wu ; Bing-Qiang Wang ; Ying Li ; Zong-Jun Li ; Wei Chen ; Guang-Tao Yu ; Feng Long Gu ; Yuriko Aoki
- 刊名：Journal of Physical Chemistry B
- 出版年：2008
- 出版时间：January 31, 2008
- 年：2008
- 卷：112
- 期：4
- 页码：1090 - 1094
- 全文大小：190K
- 年卷期：v.112,no.4(January 31, 2008)
- ISSN：1520-5207
文摘
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 areobtained with all real frequencies. They exhibit very large static first hyperpolarizabilities (
0) up to 3.2 ×105 au, which exceeds the record value of 0 = 1.7 × 105 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 0values (1.6 × 105-3.2 × 105 au) much larger than the 0 value (3.6 × 104 au) of the previously designedcuplike alkalide Li+(calix[4]pyrrole)K- [J. Am. Chem. Soc. 2006, 128, 1072]. This shows that the 26adz and36adz cage complexants are preferable to cuplike calix[4]pyrrole complexant in enhancing the firsthyperpolarizability. The effect of cage size of the complexant on the first hyperpolarizability is also presentedhere: in most cases, the smaller cage complexant corresponds to the larger 0 value. Moreover, the crucialrole by the alkali-metal anion in the large first hyperpolarizability of these alkalides is revealed. These resultsmay provide new means for designing high-performance nonlinear optical materials.
0) up to 3.2 ×105 au, which exceeds the record value of 0 = 1.7 × 105 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 0values (1.6 × 105-3.2 × 105 au) much larger than the 0 value (3.6 × 104 au) of the previously designedcuplike alkalide Li+(calix[4]pyrrole)K- [J. Am. Chem. Soc. 2006, 128, 1072]. This shows that the 26adz and36adz cage complexants are preferable to cuplike calix[4]pyrrole complexant in enhancing the firsthyperpolarizability. The effect of cage size of the complexant on the first hyperpolarizability is also presentedhere: in most cases, the smaller cage complexant corresponds to the larger 0 value. Moreover, the crucialrole by the alkali-metal anion in the large first hyperpolarizability of these alkalides is revealed. These resultsmay provide new means for designing high-performance nonlinear optical materials.