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.
Two novel lanthanide-organic polymers [Er2（pdc）2（o-bdc）（H2O）2]·H2O（1,H2pdc = 2,6-pyridinedicarboxylic acid,o-H2bdc = 1,2-benzenedicarboxylic acid） and Er（Himdc）（mbdc）0.5（H2O）（2,H3imdc = 4,5-imidazoledicarboxylic acid,m-H2bdc = 1,3-benzenedicarboxylic acid） have been synthesized and characterized by elemental analysis,IR,thermogravimetric analysis and X-ray single-crystal diffraction studies.1 crystallizes in monoclinic,space group P21/c,while 2 in the orthorhombic space group Pbcn.Both compounds 1 and 2 display two-dimensional network structures. For 1, the tetranuclear parallelogram {Era} cluster as a building block is further assembled into a wonderful 2D grid, and the layers are interconnected via hydrogen bonds and π-π stacking interactions to yield a 3D supramolecular architecture; for 2, its configuration is a rare double-decker structure. These two complexes represent good examples for using mixcarboxylate-containing ligands to construct diverse 2D lanthanide coordination polymers.
One new arsenic-vanadium cluster, [Zn（dien）（Hdien）]2[As6V15O42（H2O）]·4H2O （1, dien = diethylenetriamine）, has been hydrothermally synthesized and characterized by IR, elemental analysis, TGA, magnetic property and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group P21/n, a = 13.959（3）, b = 22.428（5）, c = 22.831（5） A^°, β = 90.733（4）°, Z = 4. X-ray crystallographic study showed that compound 1 is constructed from [As6V15O42（H2O）]^6- polyoxoanions linked together by novel [Zn（dien）（Hdien）]^3＋ complex fragments via hydrogen bonds into a three-dimensional network. Variable temperature susceptibility measurement demonstrates the presence of antiferromagnetic interaction between V^IV cations in 1.
A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.
