有机氮羟基化合物构筑的配位聚合物及其功能性质研究

Recently，N-hydroxyphthalimide (NHPI) and analogues have drawn great attention because of their unique single electron transfer effect in the catalytic reactions. Particularly, the catalytic systems composed of NHPI or its analogues and transition metal ions, such as Co(II)、Mn(II)、Cu(II) and Fe(III) as well, can catalyze aerobic oxidation of hydrocarbons efficiently. However, to our knowledge, the coordination chemistry and structures of these N-OH metal complexes are seldom reported by now. In this proposal, we suppose to design and synthesize a series of organic N-OH bridging ligands and study the coordination chemistry of these ligands with various metal ions to construct coordination polymers with expected structures and specific functions. On the one hand, we are going to explore the controllable preparation and potential physical properties of these novel functional coordination complexes and study the electron transfer effect between the ligands and metal ions as well. On the other hand, for better understanding the likely mechanism and structure effect relationship of catalytic activity, catalytic selectivity and coordination geometry, we are going to study the coordination catalysis of organic compounds by using these coordination polymers as catalysts.

近年来，N-羟基邻苯二甲酰亚胺（NHPI）类有机氮羟基化合物因其在催化反应中特有的单电子传递作用，尤其是其与Co、Mn、Cu、Fe等过渡金属组成的复合催化体系可高效地催化各类烃的分子氧氧化，引起了人们极大的关注，但是该类有机氮羟基化合物与金属离子的配位作用以及所形成的配合物的结构到目前为止尚鲜见报道。本项目旨在设计合成一系列有机氮羟基桥联配体，研究其与不同金属离子的配位作用，以构筑具有预期结构和特定功能的配位聚合物。一方面，研究金属离子与配体间的电子传递作用，探索新型功能配合物的可控合成与潜在物理性能；另一方面，研究该类配位聚合物对有机化合物的催化作用，探索金属配位作用与催化活性、选择性之间的构效关系以及可能的催化机理。

我们利用氮羟基邻苯二甲酰亚胺(NHPI)、N,N-二氮羟基均苯四甲酰亚胺化合物（NDHPI）、氮羟基吡啶-2,3-二甲酰亚胺化合物(NHQI)和氮羟基吡嗪-2,3-二甲酰亚胺化合物(HPPDO)与低对称性的的季铵盐反应培养了一系列单晶，如C22H22N4O6(1)、C20H22N6O6(2)、C42H36N10O18(3)、C12H15N5O3(4)、C15H19Cl2N3O3(5)、C22H29N5O7(6)、C23H21N3O7(7)、C23H21N3O7(8)、C24H29N3O6(9),并对他们进行了核磁共振、X-ray单晶衍射、DSC、介电、紫外和SHG测试，其中C22H22N4O6(1)、C23H21N3O7(7)、C24H29N3O6(9)和C15H19Cl2N3O3(5)都具有非心空间群结构，具有SHG响应。并且化合物C15H19Cl2N3O3 (4)的SHG响应值达到4V,是最早应用的非线性光学晶体KDP的1.3倍。