具有穿插结构的金属钴配合物的合成、结构及电化学性质

Synthesis,Structure and Electrochemical Properties of Metal Cobalt Complexes with Interpenetrating Structures

在溶剂热体系中合成了3个中心金属为钴离子的具有穿插结构的金属有机配合物{[Co LB]·H_2O}_n(1),{[Co_2L_2(bimp)_(0.5)]·3H_2O}_n(2)和{[Co_2L_2B'_2]·2DMF}_n(3)[H_2L=4,4'-三苯胺二甲酸;B=1,3-二(咪唑基)苯,bimp=3,5-二(1-咪唑)吡啶,B'=1,4-双(咪唑基)苯].通过单晶及粉末X射线衍射和热重分析对这3个配合物进行了表征.结果表明,配合物1~3均结晶于单斜晶系,其中配合物1属C2/c空间群,配合物2属P2/n空间群,配合物3属P2_1空间群;在配合物1和3中Co^(2+)为四配位模式,而在配合物2中Co^(2+)为五配位,并以双核桨轮形的结构单元[Co_2(CO_2)_4]存在;配合物1和2均为二重穿插结构的三维超分子网络,配合物3是一个四重穿插的三维超分子网络.电化学性质研究结果表明,配合物1~3是电化学活性物质,电化学可逆性较好.

Using multidenate 4,4＇-（phenylazanediyl）dibenzoic acid（H2L）and 1,3-bis（imidazol-l-yl）benzene（B）,3,5-bis（imidazol-l-yl）pyridine（bimp）or 1,4-bis（imidazol-l-yl）benzene（B＇）as ligands under solvothermal conditions,three new metal-organic frameworks with interpenetrating structure,{[Co LB]·H2O}n（1）,{[Co2L2（bimp）（0.5）]·3H2O}n（2）and{[Co2L2B＇2]·2DMF}n（3）,were synthesized.The complexes were characterized by single-crystal X-ray diffraction（XRD）,thermal analysis and powder X-ray diffraction（PXRD）.Complexes 1—3 all crystallize in the monoclinic system,with C2/c（complex 1）,P2/n（complex 2）and P21（complex 3）space group,respectively.In complexes 1 and 3,Co（2＋）forms a tetracoordinate geometry,whereas it forms a five-coordinated geometric configuration and exists as a dual-core paddleshaped structural unit[Co2（CO2）4]in complex 2.Complexes 1 and 2 give a 2-fold interpenetrating threedimensional（3D）supramolecular networks,while complex 3 exhibits a 4-fold interpenetrating 3D framework.The results of electrochemical studies show that complexes 1—3 are electrochemically active substances with good electrochemical reversibility.