Application of Clay-Metal Complex Hybrid Films to Non-linear Optical Materials

粘土-金属复合杂化薄膜在非线性光学材料中的应用

• 批准号: 10044046
• 负责人: YAMAGISHI Akihiko
• 金额: $ 2.69万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10044046/
• 关键词: Inorganic-organic hybrid; LB films; SHG; Clay minerals; 粘土鉱物; 単分子膜; 非線型光学

The purpose of the present project is to prepare an ultra-thin film of a clay and a metal complex for the use of second harmonic generation (SHG). Smectite clays have been of scientific and technological interest because of their use as ion-exchange materials, catalysts and modified electrodes. One of the outstanding properties is the simultaneous incorporation of polar or ionic molecules into interlayer spaces (intercalation). Since both sides of a layer in a smectite clay are identical, intercalated molecules naturally tend to cancel any orientational anisotropy; polar molecules, for example, orient in the opposite ways at the adjacent sites to cancel out individual dipole moments.In the present project, we take a completely a new approach, in which the application of artificial layering to clay minerals allows one to prepare a novel intercalation compound with non-centrosymmetric structures. According to the method, a monolayer of amphiphilic ruthenium(II) complex cations has been h … More ybridized with clay particles in a subphase. Clay platelets with the negative charge are adsorbed electrostatically onto the bottom of a floating monolayer. The hybrid monolayers thus formed are deposited onto a substrate by horizontal dipping to prepare a multilayered film.Non-centrosymmetricity of the multilayered LB film has been examined by measuring secondary harmonic generation (SHG). As a result, SHG was observed successfully from the hybrid LB films, showing the quadratic dependence of intensity on layer number. The results have confirmed that the whole Ru complex ions order in an asymmetric way between the clay layers. A difference in SHG was also found between the hybrid LB film of racemic complex ion and that of enantiomeric one.The above project has been accomplished with the close collaboration between our group (Hokkaido University) and Prof. Schoonheydt's grouy (Leuven Catholic University, Belgium). We believe the success of the present project absolutely lies in the mutual understanding and close connection although the research works. Sincere thanks are due to Prof. Schoonheydt and his collaborators. Less

本项目的目的是准备粘土和金属复合物的超薄薄膜，用于使用第二谐波生成（SHG）。由于它们用作离子交换材料，催化剂和修饰的电极，因此蒙脱石粘土一直是科学和技术兴趣。出色的特性之一是极性分子或离子分子在层间空间中的同时工业化（插入）。由于晶状体粘土中一层的两侧都是相同的，因此自然而然的分子倾向于取消任何定向各向异性。极性分子以相反的方式在相邻位点取消单个偶极矩的方式。在本项目中，我们采用了一种完全的新方法，其中人造分层在粘土矿物上的应用允许一个人准备一种新型的互互插入化合物，该化合物具有非中心对称结构。根据该方法，两亲二氮的单层（II）复合阳离子已成为H…在亚相中用粘土颗粒更脑化。负电荷的粘土血小板静电上吸附到浮动单层的底部。这样形成的杂种单层通过水平浸入以制备多层膜上沉积到基材上。通过测量次级谐波产生（SHG），已经检查了多层LB膜的非中心对称性。结果，从混合LB膜成功观察到SHG，显示了强度对层数的二次依赖性。结果已经证实了整个RU复合离子在粘土层之间的不对称方式以下。除了外围复合物离子的混合LB薄膜和对映体的薄膜之间也发现了SHG的差异。上述项目是通过我们的小组（北海道大学）与Schoonheydt教授（比利时卢文天主教大学）之间的密切合作完成的。我们认为，尽管研究有效，但本项目的成功绝对在于相互理解和紧密的联系。衷心感谢Schoonheydt教授及其合作者。较少的

项目成果

山岸晧彦(編集): "Nanostructural Materials in Biological and Artificial Systems" Elsevier.Oxford.UK, 444 (1998)

Akihiko Yamagishi（编辑）：“生物和人工系统中的纳米结构材料”Elsevier.Oxford.UK，444 (1998)

田村堅志: "Formation of Layer-by Layer Composite Films by the Langmuir-Blodgett Technique : Smectite-Amphophilic Ruthenium (II) Complex Systems"Clay Sciences. 10. 409-415 (1999)

Kenshi Tamura：“通过 Langmuir-Blodgett 技术形成逐层复合膜：蒙脱石-两亲性钌 (II) 复合体系”Clay Sciences，10. 409-415 (1999)。

田村堅志: "Application of the Langmuir-Blodgett technique to Prepare a Clay-Metal Complex Hybrid Film"Langmuir. 15. 6915-6920 (1999)

Kenshi Tamura：“应用 Langmuir-Blodgett 技术制备粘土-金属复合物混合薄膜”Langmuir。15. 6915-6920 (1999)

田村、堅志: "A Clay-Metal Complex Ultra-thin Film as Prepared by the Langmuir-Blodgett Techinique" Chemistry Letters. 121-122 (1999)

Tamura, Kenshi：“通过 Langmuir-Blodgett 技术制备的粘土金属复合物超薄膜”化学快报 121-122 (1999)。

Kenji Tamura: "A Clay-Metal Complex Ultra-thin Film as Prepared by the Langmuir-Blodgett Technique"Chemistry Letters. 121-122 (1999)

Kenji Tamura：“通过 Langmuir-Blodgett 技术制备的粘土金属复合物超薄膜”化学快报。