亚硝基桥连配位聚合物的合成、结构和催化性能研究

Synthesis,structures and catalytic properties of nitrito-bridged coordination polymers

溶剂热条件下合成出4个结构新颖的配位聚合物[Zn(NO2)2(H2O)2]n(1),[M(bipy)(NO2)2]n[bipy=4,4'-联吡啶,M=Zn(2);Co(3),Mn(4)],并通过元素分析、红外光谱、紫外光谱、热重分析和单晶X-射线衍射等方式进行了表征.配合物1中2个晶体学独立的Zn(Ⅱ)离子通过μ1,3-NO-2桥连形成3D结构,拓扑分析可简化为6-连单节点mab网格.配合物2~4是同构的,均可简化为6-连单节点jsm网格,其中NO-2配体构象发生明显扭曲,形成双螺旋链.此外,配合物2和3对环己烯的氧化反应具有催化作用.

Four new nitrito-bridged coordination polymers of formulation [ Zn （ NO2 ） 2 （ H2 O） 2 ] n （ 1 ） and [ M （bipy） （ NO2 ）2 }n [ M = Zn （2） ; Co （ 3 ）, Mn（4） ] were synthesized under solvothermal condition using DMF as reducing solvent.All the complexes were characterized by elemental analysis, FT-IR spectroscopy ,UV-vis spectroscopy, TG analysis and single crystal X-ray diffraction methods. For complex 1, two crystallographically independent Zn（ Ⅱ ） ions were bridged by μ1.3-NO2-, resulting in a 3D framework, which can be rationalized as 6-connected uninodal mab net by topological point. Complexes 2-4 are isostructural, and can be simplified as uninodal 6-connected jsm net.The NO2 - ligand in 2--4 presents, significantly twisted conformation, which responsible for the formation of double helical chains in the crystal structure.In addition, this work also describes the preliminary study of catalytic properties of heterogeneous oxidation of cyclohexene by 2 and 3.