基于D-A-D-A型不对称共轭四联氮杂环配体构筑的配体介导型金属有机骨架材料的研究

项目名称： 基于D-A-D-A型不对称共轭四联氮杂环配体构筑的配体介导型金属有机骨架材料的研究

项目编号： No.21201152

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 无机化学

项目作者： 武杰

作者单位： 郑州大学

项目金额： 25万元

中文摘要： 研究发现，具有推-拉电子结构的不对称共轭多氮杂环配体与金属离子键合生成的配体介导型金属有机骨架材料在非线性光学材料、分子二极管等光电功能材料和器件领域有着广阔的应用前景。然而，由于推-拉电子结构的多样性以及具有推-拉电子结构的配体与得失电子能力不同的金属离子作用的复杂性，使得对于该类金属有机骨架材料的研究仍然很欠缺。本项目以吡咯、哒嗪、三氮唑、吡啶和四嗪五种π-轨道能量不同的氮杂环为基础，设计D-A-D-A型不对称共轭四联氮杂环配体，并用该类配体与具有氧化还原活性的过渡金属和某些配合物前驱体反应来构筑配体介导型金属配合物。并对他们的三阶非线性光学性能、电化学和荧光性能进行测试；运用量化计算等手段对配合物的非线性光学性能进行分析；探讨并阐明D-A-D-A型不对称共轭四联氮杂环配体与得失电子能力不同的金属离子键合后的电子转移规律及其对三阶非线性性能的影响。

中文关键词： 金属有机骨架结构；推拉电子；非均相催化；晶体工程；构效关系

英文摘要： It was found that the ligand-mediated MOFs made from asymmetric conjugated multi-N-heterocyclic ligands with donor-acceptor (D/A) systems can be widely used in NLO, molecular diode materials, and so on. However, due to the diversity of the D/A systems and the complexity of the ligands reacting with metals with different electron donating ability, it is still deficient in studying the MOFs based on the asymmetric conjugated multi-N-heterocyclic ligands with D/A system. In this work, three donor-acceptor-donor-acceptor asymmetric conjugated tetra-N-heterocyclic aromatic ligands based on five N-heterocycles (pyrrole, pyridazine, triazole, pyridine, and tetrazine) with different π-orbital energies have been designed. Some novel ligand-mediated MOFs will be prepared by reaction of ligands with redox-active metal ions and precursor complexes. We will study the three-order NLO, electrochemical and fluorescent properties of these MOFs and analyze the three-order NLO properties with the molecular orbital calculations. Furthermore, we will explore and clarify the influence of the electron transfer processes in MOFs on the three-order NLO properties.

英文关键词： metal-organic frameworks；Electron-donor-accepter；Heterogeneous Catalysis；Crystal Engineering；Structure-activity relationship