title: Two tetra-Cd(II)-substituted vanadogermanate frameworks.
abstract: Two new tetra-Cd(II)-substituted vanadogermanate frameworks {(CdX)4Ge8V(IV)10O46(H2O)[V(III)(H2O)2]4(GeO2)4}·8H2O (X = ethylenediamine (en, 1) and 1,2-diaminopropane (dap, 2)) were hydrothermally prepared and characterized by IR spectra, elemental analysis, powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Both are isomorphic, and their 3-D frameworks are made up of tetra-Cd(II)-substituted {(CdX)4Ge8V(IV)10O46(H2O)}(12-) fundamental building units interconnected through planar tetra-V(III) [V(III)4O2(H2O)8](8-) clusters and tetrahedral GeO4 bridges. In the unique {(CdX)4Ge8V(IV)10O46(H2O)}(12-) cage, four [Ge2O7] dimers and four CdO4N2 trigonal prisms are alternately concatenated by μ3-O bridges to create a round {Ge8Cd4O28(X)4}(16-) fragment, five VO5 groups are linked by sharing edges to generate a pentanuclear [V5O17] subunit, and then the {Ge8Cd4O28(X)4}(16-) fragment is sandwiched by two V5O17 subunits via sharing O-atoms producing a D4h-symmetric {(CdX)4Ge8V(IV)10O46(H2O)}(12-) cage with a free water molecule located at the center. As we know, both display unprecedented 3-D organic-inorganic hybrid frameworks built up from the largest number of transition-metal-substituted vanadogermanate {(CdX)4Ge8V(IV)10O46}(12-) cluster shells linked by both GeO4 tetrahedra and rare [V(III)4O2(H2O)8](8-) clusters. Magnetic measurements reveal the antiferromagnetic couplings within the magnetic vanadium centers.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, China.
authors.forename: Jian
authors.initials: J
authors.lastname: Zhou
authors.forename: Jun-Wei
authors.initials: JW
authors.lastname: Zhao
authors.forename: Qi
authors.initials: Q
authors.lastname: Wei
authors.forename: Jie
authors.initials: J
authors.lastname: Zhang
authors.forename: Guo-Yu
authors.initials: GY
authors.lastname: Yang
mesh_terms: D002104:Cadmium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003959:Diamines / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry; D005857:Germanium / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D013052:Spectrometry, X-Ray Emission; D013055:Spectrophotometry, Infrared; D014639:Vanadium / Q000737:chemistry*
chemical_list: D003959:Diamines; D005029:Ethylenediamines; D009942:Organometallic Compounds; D005857:Germanium; D002104:Cadmium; D014639:Vanadium; C031234:ethylenediamine; C070006:1,2-diaminopropane