CRYSTALLINE ZWITTERIONIC STILBAZOLIUM DERIVATIVES WITH LARGE QUADRATIC OPTICAL NONLINEARITIES
CRYSTALLINE ZWITTERIONIC STILBAZOLIUM DERIVATIVES WITH LARGE QUADRATIC OPTICAL NONLINEARITIES
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DOI：
10.1021/cm00044a039
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发表时间：
1994-08-01
影响因子：
8.6
通讯作者：
ZYSS, J
中科院分区：
文献类型：
--
作者：
SERBUTOVIEZ, C;NICOUD, JF;ZYSS, J
本文报道了一系列4-取代的4 '-（N-磺酸基烷基）芪类两性离子衍生物的合成及其二次非线性光学性质。在二次谐波产生（SHG）中最活跃的化合物是用3-磺酸基丙基获得的。通过SHG粉末测试选择4-甲硫基-4 '-（3-磺酸基丙基）芪、4-正丁基-4'-（3-磺酸基丙基）芪和（3-磺酸基丙基）芪（分别称为MTSPS、BSPS和SPS）用于进一步研究。它们根据重结晶条件呈现几种晶体变型。MTSPS提出了两个高度SHG活性的一水结晶相，分别为2.4和1.3倍以上的NPP在库尔茨和佩里粉末测试在1.06妈妈。最活跃的阶段的单晶X射线结构。MTSPS·H2O相I在单斜空间群P2（1）中结晶，每个晶胞具有两个分子，尺寸为a = 10.380埃，B = 11.124埃，c = 6.968埃，β = 99.93度。MTSPS分子的两性离子部分的构象与分子模拟计算结果吻合较好。水分子参与氢键网络，该氢键网络沿c轴沿着连接带状分子。此外，在片材内，超极化发色团被布置成使得分子间电荷转移是可能的。电场诱导的二次谐波产生（EFISH）和基态偶极矩测量更可溶MTSPS和SPS类似物已进行，导致第一次超极化率β值的这种两性离子物种。最后，MTSPS材料的二次非线性极化率已估计使用定向气体模型，给出的值与半定量SHG粉末测试推导出的实验值合理的协议。
The synthesis and quadratic nonlinear optical properties of a series of zwitterionic 4-substituted 4'-(n-sulfonatoalkyl)stilbazolium derivatives are described. The most active compounds in second harmonic generation (SHG) are obtained with the 3-sulfonatopropyl group. 4-Methylthio-4'-(3-sulfonatopropyl)stilbazolium, 4-n-butyl-4'-(3-sulfonatopropyl)stilbazolium and (3-sulfonatopropyl)stilbazolium (further called MTSPS, BSPS, and SPS, respectively) were selected by the SHG powder test for further investigations. They present several crystal modifications depending on recrystallization conditions. MTSPS presents two highly SHG-active monohydrated crystalline phases, respectively, 2.4 and 1.3 times more than NPP in the Kurtz and Perry powder test at 1.06 mum. The single-crystal X-ray structure of the most active phase is presented. MTSPS.H2O phase I crystallizes in the monoclinic space group P2(1), with two molecules per unit cell, with dimensions of a = 10.380 angstrom, b = 11.124 angstrom, c = 6.968 angstrom, beta = 99.93-degrees. The conformation of the zwitterionic part of MTSPS molecule agrees well with molecular modeling calculations. The water molecule is involved in a hydrogen bond network linking the ribbonlike molecules along the c axis. In addition, within a sheet the hyperpolarizable chromophores are arranged so that an intermolecular charge transfer is possible. The electric-field-induced second-harmonic generation (EFISH) and ground-state dipole moment measurements of more soluble MTSPS and SPS analogs have been performed, leading for the first time to the hyperpolarizability beta values of such zwitterionic species. Finally the quadratic nonlinear susceptibilities of MTSPS materials have been estimated by using the oriented gas model, giving values in reasonable agreement with the experimental ones deduced from semiquantitative SHG powder tests.