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

本项目的目的是制备用于二次谐波产生（SHG）的粘土和金属络合物的超薄膜。蒙皂石粘土由于其作为离子交换材料、催化剂和修饰电极的用途而引起科学和技术的兴趣。其中一个突出的性能是同时纳入极性或离子分子进入层间空间（插层）。由于蒙皂石粘土层的两侧是相同的，插入分子自然倾向于抵消任何取向各向异性;例如，极性分子在相邻的位置以相反的方式取向，以抵消单个的偶极矩。在本项目中，我们采取了一种全新的方法，其中对粘土矿物应用人工分层允许制备具有非中心对称结构的新型插层化合物。根据该方法，一个单分子层的两亲性钌（II）配合物阳离子已被用来作为一个单一的， ...更多信息 在亚相中与粘土颗粒混合。带负电荷的粘土片晶被静电吸附到浮动单分子层的底部。用水平浸渍法在基底上制备多层LB膜，通过测量二次谐波产生（SHG）来研究多层LB膜的非中心取向性。结果表明，在混合LB膜中成功地观察到了二次谐波，其强度与层数成二次关系。结果表明，整个钌络合物离子在粘土层间以不对称的方式有序排列。本课题是本课题组（北海道大学）与Schoonheydt教授（比利时鲁汶天主教大学）密切合作完成的。我们相信，本项目的成功，绝对在于研究工作中的相互理解和密切联系。衷心感谢Schoonheydt教授和他的合作者。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