手性大环配位化合物的设计合成、组装及功能性质关系的研究

项目名称： 手性大环配位化合物的设计合成、组装及功能性质关系的研究

项目编号： No.20801031

项目类型： 青年科学基金项目

立项/批准年度： 2009

项目学科： 轻工业、手工业

项目作者： 张晓梅

作者单位： 山东大学

项目金额： 18万元

中文摘要： 利用手性、非手性或者外消旋配体构筑单一手性物种的研究，由于其广泛的生物相关性，使其得到了全世界科学工作者的密切关注。本课题以卟啉、酞菁作为基本的结构单元，依靠超分子和共价键相结合的方式组装了具有刚性和柔性面对面结构的一系列超分子体系，研究了这样的超分子体系中手性分子结构－手性纳米结构－器件性能之间的关系。取得的主要成果有：1.把各种手性以及功能基团修饰在卟啉、酞菁的周边，合成了几个系列的新颖的手性卟啉、酞菁类配合物。2.对其组装研究发现，平面型分子的聚集和其外沿的取代基的大小以及位置有密切的关系。取代基引起的分子平面的扭曲是影响聚集体的结构和表面形貌主要因素。3. 设计合成了首例光学活性的对称（不对称）的双层酞菁以及三层卟啉酞菁混杂配合物，发现手性可以有效的在整个大环体系内进行传递。4.分子的堆积方式对电子的传导产生明显的影响，证明可以通过正确的分子设计和调节适当的组装条件来改善聚集体的功能性质。共发表SCI 收录学术论文19 篇，撰写Willey 出版社出版国际专著一章。

中文关键词： 卟啉；酞菁；三明治；组装；手性

英文摘要： Due to the widely biological relativity, the research of building single chiral species depended on chiral, achiral or racemic ligands, has attracted intense attention of the chemist over the world. With porphyrin and phthalocyanine as the fundamental building block, we have prepared a series of face to face supramolecular systems with rigid and flexible structure depending on the combination of supramolecular and covalent bond and investigate the relationship among chiral molecular structure, chiral nanostructure and properties of devices. The main representative results are listed following: 1. Several series of novel chiral porphyrin and phthalocyanines complexes with various chiral and functional groups modified in porphyrin, phthalocyanine peripheral have been synthesized. 2. Investigation about the self-assembled behavior of these porphyrin and phthalocyanine derivatives indicates that for a plannar molecule, the self-aggregation will efficiently affacted by the prephreal side groups. The twisting of the plannar conformation caused by the side groups is main factor which influences the structure and surface morphology of the aggregate. 3. We synthesized the first example of optical activity symmetric (asymmetric) double-decker phthalocyaninato and triple-decker porphyrinato phthalocyaninato hybrid complexes and also observed that chiral can effectively transferred in the whole ring system. 4. The electronic transfer process was proven to be significantly affected by the molecular stacking style. This result suggests that the functional properties of aggregates can be improved depending on the correct molecular design and appropriate assembly conditions modulation. In general, nineteen papers which are collected by SCI database have been published. There is one chapter of one book which is published by Willey book concern.

英文关键词： porphyrin; phthalocyanine;sandwich;self-assembly; chirality