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

本项目的目的是制备一种粘土和金属络合物的超薄膜，用于二次谐波(SHG)。蒙皂石粘土由于用作离子交换材料、催化剂和修饰电极而引起了科学和技术上的兴趣。其中一个突出的性质是将极性或离子分子同时并入层间空间(插层)。由于蒙皂石粘土中一层的两侧是相同的，插层分子自然倾向于抵消任何取向的各向异性；例如，极性分子在相邻位置以相反的方式取向以抵消单个偶极矩。在本项目中，我们采取了一种全新的方法，将人工分层应用于粘土矿物，使人们能够制备出具有非中心对称结构的新型插层化合物。根据该方法，两亲性Ru(II)络合阳离子的单分子膜已被h…在亚相中更多地与粘土颗粒混合。带有负电荷的粘土小片被静电吸附到浮动单分子膜的底部。用水平浸渍法制备了多层膜，通过测量二次谐波(SHG)测试了多层膜的非中心对称性。结果表明，从杂化的LB膜中成功地观察到倍频现象，表明倍频强度与层数呈二次关系。结果表明，整个Ru配位离子在粘土层之间以不对称的方式排列。我们的研究小组(北海道大学)和肖恩海德教授的团队(比利时鲁汶天主教大学)共同完成了上述工作。我们认为，尽管研究工作正在进行，但我们认为本项目的成功完全在于相互理解和密切联系。衷心感谢舍恩海特教授和他的合作者。较少

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