新型三维有序卟啉复合薄膜的设计、自导向组装及其光电性能

项目名称： 新型三维有序卟啉复合薄膜的设计、自导向组装及其光电性能

项目编号： No.21301118

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 李向清

作者单位： 上海应用技术学院

项目金额： 24万元

中文摘要： 本项目主要围绕三维有序卟啉复合物薄膜的自导向组装及其光电性能研究为主线展开，制备系列能在三维方向自导向组装的笼形倍半硅氧烷修饰的新型金属卟啉单体。利用卟啉单体自身的结构特点，经共轭双齿桥联配体诱导，促使单体定向排列并以配位键(轴向，卟啉环中心的金属离子与桥联配体配位)和共价键(水平方向，卟啉周边硅氧烷的水解-聚合)为主要推动力进行自导向组装形成溶胶，通过自旋涂覆到基片上的溶胶的凝胶化实现卟啉单体在三维方向的有序组装，获得层间距和层数可控(调节桥联配体的量和尺寸)、稳定且光电性能优越的三维有序的卟啉复合物薄膜。 通过系统地结构表征和性能测试，摸索出卟啉单体在三维方向自导向组装的条件，深入研究单体的组装机理，进而揭示单体在三维方向的组装行为对复合薄膜的微观结构、形貌和性能的影响，阐明其光电活性产生的机制。为有目的地设计和开发结构新颖、性能优异的光电器件提供理论指导和崭新的思路。

中文关键词： 三维有序；卟啉；复合薄膜；自导向组装；光电性质

英文摘要： This project is carried out according to self-directed assembly and photoelectronic property of three-dimensional porphyrin composite thin films. Several serials of new types of metalloporphyrin monomers modified with sisesquioxane(spacer length is tunable) are prepared, and the monomers can self-directedly assemble in three-dimensional directions. In the process of self-directed assembly of the porphyrin composite thin films, the central metal ion of porphyrin macrocycle coordinates with conjugate bidentate-bridged ligand in axial direction, and forms an axially ordered porphyrin oligomer in one step. Then the oligomer is transferred onto a moist substrate and further self-directedly assembles in the horizontal direction by the hydrolysis-polymerization of sisesquioxanes linking on the periphery of porphyrin microcyle. Consequently, the three-dimensionally ordered porphyrin composite thin films can be achieved on various substrates by the simple process. The composite thin film possesses tunable interlayer spacing and thickness (by controlling the size and the quantity of the conjugate bidentate-bridged ligand), stable and high photoelctronic transformation efficiency. The conditions of self-directed assembly of porphyrin monomer in three-dimensional directions are explored by structure characterization and pro

英文关键词： three-dimensional order；porphyrin；composite thin film；self-directed assembly；photoelectronic property