由氮杂环配体控制结构的从三维骨架到二维层的Mn(Ⅱ)配位聚合物

Mn(Ⅱ)Coordination Polymers from 3D Framework to 2D Layer Controlled by Nitrogen Heterocyclic Ligands

在溶剂热体系中,将5-羟甲基间苯二甲酸(H_(2)HIPA)和4,4′-二(1H-咪唑-1-基)-1,1′-联苯(4,4′-DIB)与Mn(Ⅱ)离子组装得到配合物Mn[(HIPA)(4,4′-DIB)](1).单晶结构分析表明,配合物1结晶于单斜的P 2_(1)/c空间群,包含二核的Mn_(2)(CO_(2))_(4)结构单元.HIPA 2-连接Mn_(2)(CO_(2))_(4)形成二维结构,4,4′-DIB进一步将该二维结构连接成pcu型的柱层式框架.在相似的合成条件下,用(E)-1,2-双(吡啶-4-基)乙烯(DPEE)代替4,4′-DIB,得到配合物Mn[(HIPA)(4,4′-DIB)]·x Guest(2).配合物2结晶于单斜的P 21/c空间群,结构中的Mn(Ⅱ)中心与羧基形成Mn_(2)(CO_(2))_(4)次级结构单元.配合物2的结构是一个具有sql网络的二维结构.氮杂环配体的结构差异使Mn_(2)(CO_(2))_(4)单元在配合物1中是立体构型,而在配合物2中为平面结构;Mn_(2)(CO_(2))_(4)的不同构型导致配合物1和2的结构特征不同.

Under the solvothermal system,5-(hydroxymethyl)isophthalic acid and nitrogen heterocyclic ligand 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl(4,4′-DIB)reacted with Mn(Ⅱ)ions to obtain complex Mn[(HIPA)(4,4′-DIB)](1).Crystallographic analysis indicates that complex 1 crystallizes in the monoclinic P 21/c space group.In the complex 1,HIPA 2-ligands connect dinuclear Mn_(2)(CO_(2))_(4)units to form a two-dimensional(2D)structure,and then the adjacent layers are further connected together by 4,4′-DIB to obtain a three-dimensional(3D)pillar-layered framework with six connected pcu net.When auxiliary ligand 4,4′-DIB is replaced by(E)-1,2-di(pyridin-4-yl)ethene(DPEE),another complex Mn[(HIPA)(DPEE)]·x Guest(2)is obtained in the same reaction system.Complex 2 crystallizes in monoclinic P 2_(1)/c space group with Mn_(2)(CO_(2))_(4)units.The structure of complex 2 is a 2D structure with sql net,Mn_(2)(CO_(2))_(4)unit is stereoscopic in complex 1,and planar structure in complex 2.The different configurations of Mn_(2)(CO_(2))_(4)lead to different structural characteristics of complexes 1 and 2.