两种氨基四齿配体的合成、表征及单晶结构

Synthesis, Characterization, and Single-Crystal Structures of Two Amino Tetradentate Ligands

通过取代反应,以柔性四羧酸链分别替换1,2-二(2-氨基苯氧基)乙烷、邻苯二胺分子中的氨基氢原子,得到两种氨基四齿配体1,2-二(2-氨基苯氧基)乙烷-N,N,N′,N′-四乙酸甲酯(Ⅳ)与1-N,N-2-N′,N′-四乙酸甲酯基-1,2-二氨基苯(Ⅴ),采用核磁共振氢谱、红外光谱、高分辨质谱、X-射线单晶衍射等技术对配体结构进行表征。单晶结构解析显示,配体Ⅳ属于三斜晶系,■中心对称空间群,每个非中心对称结构单元包含30个分子;配体Ⅴ属于单斜晶系,P2空间群,每个非中心对称结构单元包含4个分子,两种配体分子均排布规整、具有一定的对称性,柔性四羧酸链形成了一定的包合空腔,符合预期结构设计。

Through substitution reaction, four amino hydrogen atoms in 1,2-bis(2-aminophenoxy)ethane and o-phenyleneamine molecules were replaced by a flexible tetracarboxylic acid chain.We synthesized two amino tetradentate ligands 1,2-bis(2-aminophenoxy)ethane-N,N,N′,N′-acetic acid methyl ester(Ⅳ) and phenylenediamine-1-N,N-2-N′,N′-acetic acid methyl ester(Ⅴ),and characterized the structures of the two ligands by ~1HNMR,IR,HRMS,and X-ray single-crystal diffraction.Single-crystal structure analysis shows that the ligand Ⅳ belongs to the triclinic system with ■ centrosymmetric space group, and each non-centrosymmetric structure unit contains 30 molecules.While the ligand Ⅴ belongs to the monoclinic system with P2space group, and each non-centrosymmetric structure unit contains 4 molecules.Both the two ligand molecules are arranged in a regular manner with certain symmetry, and the flexible tetracarboxylic acid chain forms a certain clathration cavity, which conforms to the expected structure design.