Two new organic-inorganic hybrid mono-transition-metal-substituted polyoxometalates [Ni（2,2′-bipy）3]3[Ni（H2O）SiW11O39]·11H2O 1 and [Cu（dien）（H2O）][Cu（dien）（H2O）2]2- [CuSiW11O39]·5.5H2O 2 （2,2′-bipy = 2,2′-bipyridine, dien = diethylenetriamine） have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, magnetic properties, and IR spectrum. Crystal data for 1： monoclinic, space group P21/n, a = 17.492（3）, b = 33.481（5）, c = 20.493（3）A^°, β = 101.894（3）°, Dc = 2.563 mg/A^°^3, F（000） = 8440, μ = 11.454 mm^-1 and Z = 4; and those for 2：monoclinic, space group P21/n, a = 11.114（3）, b = 22.803（7）, c = 22.468（7） A^°, β = 97.896（6）°, Dc = 4.036 mg/A^°^3, F（000） = 6140, μ = 23.942 mm^-1 and Z = 4. The study on the magnetic susceptibility of 2 demonstrates the presence of ferromagnetic interaction.
A chiral salency complex,[Mn（Salency）（H2O）2]（PF6）·2H2O 1（Salency =（R,R）-N,N＇-bis（salicylidene）-1,2-cyclohexanediamine）,has been prepared by the reaction of Mn（CH3COO）3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299（8）,b=10.012（8）,c=13.461（11）,α=92.037（15）,β=92.974（12）,γ=93.530（18）°,V=1248.3（18）3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F（000）=608,μ=0.676 mm–1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I 2σ（I）.
Two one-dimensional chain-like cyanide-bridged compounds, [Fe（Phen）2（CN）2Ni（Cyclam）]（ClO4）2·DMF-2H2O 1 （Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenanthroline, and DMF = N,N-dimethylformamide） and [Fe（Phen）2（CN）2Zn（Cyclam）]（PF6）2·CH3CN 2, were prepared by the reaction of [Fe（Phen）2（CN）2]·2H2O with M（Cyclam）^2＋ （M = Ni, Zn）. In complexes 1 and 2, the metal atoms are connected alternatively with CN groups. X-ray structure and IR analyses for 1 and 2 were performed. Structure analysis revealed that both complexes are centrosymmetric and the geometry around each metal atom is an octahedron. The two complexes crystallize in triclinic with space group of P^1-. For 1, a = 10.439（4）, b = 14.976（7）, c = 15.914（8）A,α = 83.168（15）, β = 74.338（15）, γ = 78.023（15）°, V = 2338.3（18）A^3, Z = 2, Mr = 1035.37, Dc = 1.471 g/cm^3, F（000） = 1076,μ = 0.895 mm^-1, the final R = 0.0616 and wR = 0.1414 for 5849 observed reflections （1 〉 2σ（I））. For 2, a = 9.656（6）, b = 15.404（9）, c = 15.822（10）A, α = 78.68（2）, β= 78.917（19）, γ = 77.15（2）°, V = 2223（2）A^3, Z = 2, Mr = 1064.87, Dc = 1.587 g/cm^3, F（000） = 1078,μ = 1.032 mm^-1, the final R = 0.0672 and wR = 0.1595 for 6819 observed reflections （I 〉 2σ（I））.
A novel sodium holmium carboxylate compound,namely Na 4 Ho 4 （μ 3-OH） 4 （1,4BDC） 6 ·6.25H 2 O （1,1,4-BDC=1,4-benzenedicarboxylate）,has been solvothermally synthesized and structurally characterized.The structure features a two-fold interpenetrated three-dimensional open-framework constructed by the [Ho 4 （μ 3-OH） 4 ] 8＋ clusters bridged by 1,4-BDC ligands.The Na ＋ ions and lattice water molecules are located in the channels.The structure is further stabilized by hydrogen-bonding and π-π stacking interactions.The thermal stability of the compound has been investigated via thermogravimetric analysis.
Two isostructural inorganic-organic hybrid M（II）–Nb（V） oxyfluorides, namely, M（H2O）2（pyz）NbOF5 （M=Co 1, Cu 2; pyz=pyrazine） have been hydrothermally synthesized and structurally characterized. Both compounds possess two-dimensional layer structure constructed by neutral M（H2O）2NbOF5 chains inter-connected via bridging pyrazine ligands. The structure is further extended into three-dimensional supramolecular architecture through inter-layer H-bonding interactions between the coordinated water molecules and fluorine ions. The luminescent properties and thermal stability of both compounds have been investigated.
