利用具有双金属夹的荧光二吡唑连接体的金属大环配合物的自组装和主客体相互作用。

Self-assembly and host-guest interaction of metallomacrocycles using fluorescent dipyrazole linker with dimetallic clips.

机构信息

Laboratory for Self-Assembly Chemistry, Department of Chemistry, Renmin University of China, Beijing 100872, China.

出版信息

Inorg Chem. 2010 Sep 6;49(17):7783-92. doi: 10.1021/ic100724r.

PMID:20690696

Abstract

By employing diimine ligands coordinated dimetallic clips ((bpy)2Pd2(NO3)22 or (phen)2Pd2(NO3)22, where bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) as the corner and anthracene-, naphthalene-, and benzene-based dipyrazolate dianions as the linker, a series of positively charged metallomacrocycles ([M4L2]4+ or [M8L4]8+) have been synthesized through a directed self-assembly method in aqueous solution. Every macrocycle has a cavity to bind solvent molecules or anions. The structures were characterized by elemental analysis, 1H and 13C NMR, electrospray ionization mass spectrometry, and single crystal X-ray diffraction analysis for compound 1 x 4 PF6(-) (1 = {[(bpy)Pd]4L(1)2}4+), 3 x 4 PF6(-) x 8 CH3CN x H2O (3 = {[(bpy)Pd]4L(2)2}4+), and 7 x 4 PF6(-) x 6 H2O (7 = {[(bpy)Pd]4L(5)2}4+). The 1:1 host-guest complexation for anthracene-based dipyrazolate-bridged macrocycles with aromatic guests was investigated via UV-vis and fluorescent titration.

摘要

通过采用二亚胺配体配位的双金属夹((bpy)2Pd2(NO3)22 或 (phen)2Pd2(NO3)22，其中 bpy=2,2′-联吡啶，phen=1,10-菲咯啉)作为角，蒽基、萘基和苯基二吡唑二阴离子作为连接体，通过在水溶液中的定向自组装方法合成了一系列带正电荷的金属大环([M4L2]4+或 [M8L4]8+)。每个大环都有一个空腔，可以结合溶剂分子或阴离子。通过元素分析、1H 和 13C NMR、电喷雾电离质谱和单晶 X 射线衍射分析，对化合物 1 x 4PF6(-) (1 = {[(bpy)Pd]4L(1)2}4+)、3 x 4PF6(-) x 8CH3CN x H2O (3 = {[(bpy)Pd]4L(2)2}4+)和 7 x 4PF6(-) x 6H2O (7 = {[(bpy)Pd]4L(5)2}4+)进行了结构表征。通过紫外-可见和荧光滴定研究了蒽基二吡唑桥联大环与芳香客体的 1:1 主客体络合作用。