| 摘要: 向MoO3, H3PO4和bpy(4,4′-bipyridine)组成的反应体系中分别引入Cd(OAc)2·2H2O 和MnCl2·4H2O, 在水热条件下合成了两种基于还原型钼磷酸盐[P4Mo6O28(OH)3]9-(简称{P4Mo6})为建筑单元构筑的新型多维延展型无机-有机杂化材料(H2bpy)2[Cd(H2O)]3[Cd(HPO4)6(PO4)2(OH)6(MoO2)12]·5H2O(1)和 (H2bpy)3[Mn(H2O)2]2 [Mn(HPO4)6(PO4)2(OH)6(MoO2)12]·10H2O(2), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其进行了表征。结果表明, 化合物1和2均属于三斜晶系, P1 空间群。化合物1的阴离子[Cd(H2O)]3[Cd(HPO4)6(PO4)2(OH)6(MoO2)12]2-是由二聚体 Cd[P4Mo6]2通过{Cd3}簇依次连接形成的一维无机链状结构; 化合物2的阴离子[Mn(H2O)2]2[Mn(HPO4)6(PO4)2(OH)6(MoO2)12]3-则是由二聚体Mn[P4Mo6]2通过Mn2+离子连接形成的二维无机层状结构。这2种无机延展结构均同质子化的bpy通过氢键作用形成不同的三维超分子网络。同时还探讨了化合物2的电化学性质。 |
| Abstract: Cd(OAc)2·2H2O and MnCl2·4H2O were separately introduced to the mixture of MoO3, H3PO4 and bpy. Two new reduced molybdenum phosphate [P4Mo6O28(OH)3]9-({P4Mo6}) extended inorganic-organic hybrid supramol-ecular networks (H2bpy)2[Cd(H2O)]3[Cd(HPO4)6(PO4)2(OH)6(MoO2)12]·5H2O(1) and (H2bpy)3[Mn(H2O)2]2[Mn (HPO4)6(PO4)2(OH)6(MoO2)12]·10H2O(2) have been synthesized under hydrothermal techniques. Here, compounds 1 and 2 have been characterized by elementary analyses, IR, TG, and single crystal X-ray diffraction. Compound 1 crystallized in the triclinic, space group P1, a=1.187 7(2) nm, b=1.348 5(3) nm, c=1.410 8(3) nm, α=106.87(3)°, β =108.09(3)°, γ = 107.92(3)°, V = 1.848 3(6) nm3, Z = 1; Compound 2 crystallized in the triclinic, space group P1,a= 1.196 8(2) nm, b= 1.335 4(3) nm, c= 1.462 0(3) nm, α = 77.58(3)°, β = 67.97(3)°, γ = 76.12(3)°, V = 2.082 2(7) nm3, Z = 1. The polyanion of compound 1 [Cd(H2O)]3[Cd(HPO4)6(PO4)2(OH)6(MoO2)12]2- is composed of Cd[P4Mo6]2 dimer and tri-nuclear {Cd3} linkers, which are connected together to form inorganic chains. The polyanion [Mn(H2O)2]2[Mn(HPO4)6(PO4)2(OH)6(MoO2)12]3- of compound 2 exhibits a 2D inorganic layer, consisting of Mn[P4Mo6]2 units linked by the Mn2+ ions. These two kinds of inorganic extended structures are further linked with Hydrogen bonds of protonated bpy to construct different 3D supramolecular networks. Simultaneously, the electrochemical property of compound 2 has been explored. CCDC: 661669, 1; 661670, 2. |
