DEVELOPMENT OF NEW ORGANIC NONLINEAR OPTICAL MATERIELS

新型有机非线性光学材料的开发

• 批准号: 03555186
• 负责人: TANIGUCHI Hiroshi
• 金额: $ 9.79万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555186/
• 关键词: ORGANIC OPTICAL MATERIAL; AMPHIPHILE HAVING HETEROCYCLE; STRUCTURE OF MONOLAYER; LANGMUIR-BLODGETT FILM; MOLECULAR ASSEMBLY; THEORY ON INTERMOLECULAR FORCE; MULTIPOLE-MULTIPOLE INTERACTION; LIQUID CRYSTAL; 液晶; 複素環両親媒性化合物; 分子間力の分子軌道; 異積膜; 分子集分体

This investigation was performed to develop optically non-linear organic thin films from newly designed compounds having long and polar heterocyclic chromophores. The important results obtained by this study are as follow :1. The amphiphiles having phenylpyrazine or phenylpyridazine chromophore were shown to be excellent amphiphiles to fabricate organic thin film by Langmuir-Blodgett (LB) technique. Comparison with related compounds suggested the excellence of pyrazine and pyridazine derivatives would be caused by electrostatic multipole-multipole interaction between these heterocycles in the layred structures. This consideration was supported by computer simulation based on 2-dimensional crystalline models. The molecular arrangement in the monolayr of a liquid crystalline material, alkoxyphenylpyrazine carbonitrile, could be observed by scanning tunneling microscope (STM) and the STM image was reproduced by same simulation, which revealed this simulation could be used as a guide line for the molecular design of compound to fabricate molecular assemblies.2. By introduction of acryloxy group at the end of the hydrophobic alkyl chain of an amphiphile having pyrazine ring, Z-type LB film was obtained. The Z-type LB film mechanically strengthened by photopolymerization showed strong second harmonic generation. The amphiphiles having MeO-, NC-, N_3- at the end of alkyl group also gave Z-type LB film, which revealed that introducing polar group at the end of alkyl chain caused Z-type deposition which is favorable for monlinear optical activity.3. Amphiphiles having acetylenic or diacetylenic linkage between two aromatic rings were also prepared. The LB-films of these compound were shown to be strong nonlinear optical material

本研究旨在利用新设计的具有长极性杂环发色团的化合物制备光学非线性有机薄膜。本研究取得的主要结果如下：1.利用LB技术研究了含苯基吡嗪或苯基哒嗪发色团的两亲分子在制备有机薄膜中的作用。与相关化合物的比较表明，吡嗪和哒嗪衍生物的优异性能可能是由于层状结构中这些杂环之间的静电多极-多极相互作用造成的。基于二维晶体模型的计算机模拟支持这一考虑。利用扫描隧道显微镜（STM）可以观察到液晶材料烷氧基苯基吡嗪腈单层膜中的分子排列，并通过相同的模拟再现了STM图像，揭示了该模拟可以作为化合物分子设计的指导思想，以制备分子阵列.通过在带有吡嗪环的两亲分子的疏水烷基链末端引入丙烯酰氧基，得到Z型LB膜。通过光聚合机械增强的Z型LB膜显示出较强的二次谐波产生。烷基末端含有MeO-、NC-、N_3-的两亲物也能形成Z型LB膜，说明在烷基末端引入极性基团导致了Z型沉积，有利于单线性光学活性的形成.还制备了在两个芳环之间具有炔键或二炔键的两亲物。这些化合物的LB膜是一种强非线性光学材料

项目成果

Kenji TAKEHARA: "Theoretical Study on the Effect of Heterocycles Reinforcing the Layered Structure" Thin Solid Films. 210/211. 169-171 (1992)

Kenji TAKEHARA：“杂环增强层状结构效应的理论研究”固体薄膜。

H.Taniguchi,K.Isomura,M.Matsumoto: "キラル置換基を有する非対称ピラジンの強誘電性液晶" 日本化学会誌. 1213-1219 (1992)

H. Taniguchi、K. Isomura、M. Matsumoto：“具有手性取代基的不对称吡嗪的铁电液晶”日本化学学会杂志 1213-1219 (1992)。

Kazami MATSUSHIGE: "Scanning Tunneling Microscope Observation of a Polar Liguid Crystal and its Computer Simulation" Jpn.J.Appl.Phys. 32. 1716-1721 (1993)

Kazami MATSUSHIGE：“极性液晶的扫描隧道显微镜观察及其计算机模拟”Jpn.J.Appl.Phys。

Kenji TAKEHARA: "UV Study on the Interaction of Amphiphilies Having Heterocyclic Chromophore" Thin Solid Films. 210/211. 124-126 (1992)

Kenji TAKEHARA：“具有杂环发色团的两亲物相互作用的紫外研究”固体薄膜。

Kenji Takehara, Katsumi Takehara, Kazukai Isomura, and Hiroshi Taniguchi: "Effect of Elongation of pi-Electron System on the Behaviors of Amphiphiles Containing Pyrazine Ring" Thin Solid Films. (in press).

Kenji Takehara、Katsumi Takehara、Kazukai Isomura 和 Hiroshi Taniguchi：“π 电子系统伸长对含有吡嗪环的两亲物行为的影响”固体薄膜。