基于半刚性乳酸衍生物的单一手性配位聚合物的合成、 结构与性质

在溶剂热反应条件下, 用预先合成的乳酸衍生物(R)-H₂CBA和(S)-H₂CBA分别与含氮辅助配体(E)-1,2-二(4-吡啶基)乙烯(DPEE)和1,4-二(1H-咪唑-1-基)苯(1,4-DIB)组合, 制备出2对不同结构的单一手性配位聚合物Cd₂((R)-CBA)₂(DPEE)(H₂O)₂]_n(1-D), Cd₂((S)- CBA)₂(DPEE)(H₂O)₂]_n(1-L), Cd((R)-CBA)(1,4-DIB)]·H₂O(2-D)和Cd((S)-CBA)(1,4-DIB)]·H₂O(2-L). 其中1-D和1-L是由梯形Cd-CBA链和DPEE配体连接成的二维框架结构; 而2-D和2-L是三维超分子框架结构, 包含3种不同类型的对映手性螺旋链. 对上述化合物进行了粉末X射线衍射、 热重分析和圆二色谱分析, 并对其荧光性质进行了讨论.

Synthesis,Structures and Properties of Homochiral Coordination Polymers Assembled from Semirigid Lactic Acid Derivatives†

Under the solvothermal reaction condition, two pairs of homochiral coordination polymers, namely Cd2((R)-CBA)2(DPEE)(H2O)2]n(1-D), Cd2((S)-CBA)2(DPEE)(H2O)2]n(1-L), Cd((R)-CBA)(1,4-DIB)]·H2O(2-D) and Cd((S)-CBA)(1,4-DIB)]. H2O(2-L)DPEE=(E)-1,2-di(pyri-din-4-yl) ethene; 1,4-DIB=1,4-di(1H-imidazol-1-yl) benzene; (R)-H2CBA=(R)-4-(1-carboxyethoxy) benzoic acid;(S)-H2CBA=(S)-4-(1-carboxyethoxy)benzoic acid], have been prepared from synthetic lac-tic acid derivative ligands ( R)-H2 CBA and( S)-H2 CBA] , auxiliary ligands and Cd2+ions. Among these com-plexes, 1-D and 1-L have ladder-like Cd-CBA2- chains, which are further linked by DPEE ligands to form a 2D framework. Complexes 2-D and 2-L feature three-dimensional supramolecular structure with hydrogen bonds, containing three kinds of homochiral helical chains. Moreover, the thermal stabilities, solid-state circu-lar dichroism( CD) and photoluminescent properties of the complexes were also investigated.