Inorganic-organic hybrid compounds based on octamolybdates and metal-organic fragments with flexible multidentate ligand: syntheses, structures and characterization.
Six polyoxometalate-based (POM) hybrid materials based on octamolybdate building blocks and metal-organic fragments with flexible multidentate ligand, namely [Cu(II)(2)(ttb)(2)(β-Mo(8)O(26))(H(2)O)(2)]·2H(2)O (1), Cu(I)(4)(ttb)(2)(β-Mo(8)O(26))(H(2)O) (2), [Cu(I)(4)(ttb)(3)(β-Mo(8)O(26))] (3), [Ni(2)(ttb)(2)(β-Mo(8)O(26))(H(2)O)(6)]·2H(2)O (4), [Zn(2)(ttb)(2)(α-Mo(8)O(26))(H(2)O)(2)] (5), and [Ag(4)(ttb)(2)(β-Mo(8)O(26))] (6), where ttb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethyl benzene, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, TGA, IR spectra, and electrochemistry. Compounds 1 and 2 exhibit three-dimensional (3D) 2-fold interpenetrating frameworks with (3,6)-connected (4(1)·6(2))(4(2)·6(10)·10(3)) and (3,4)-connected (6(2)·8(1))(2)(6(2)·8(4)) topologies, respectively. We are not aware of any other examples of interpenetrating (3,6)- and (3,4)-connected frameworks which involves the octamolybdates. Compound 3 shows a rare two-dimensional (2D) 2-fold interpenetrating network structure. In compound 4, a 3D supramolecular framework with the channels is constructed by the hydrogen-bonding interactions between (β-Mo(8)O(26))(4-) polyanions and the Ni-ttb double layers, in which the guest (β-Mo(8)O(26))(4-) anions are included. If ZnO interactions are considered, the structure of 5 is a 3D (3,4)-connected framework with (4·8(2))(4·8(2)·10(3)) topology. In 6, the ttb ligand as a tetradentate ligand links the Ag atoms to yield a 2D POM-based network. By careful inspection of the structures of 1-6, it can be seen that the ttb ligand, the metal ion and the coordination mode of the octamolybdate anion play important roles in the formation of the POM-based MOFs.
Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun, 130024, People's Republic of China.
Hai-Yan
HY
Liu
Hua
H
Wu
Jian-Fang
JF
Ma
Ying-Ying
YY
Liu
Jin
J
Yang
Ji-Cheng
JC
Ma
D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D008024:Ligands; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D017973:Tungsten Compounds / Q000737:chemistry; D000099294:Polyoxometalates
D056831:Coordination Complexes; D003300:Copper; D008024:Ligands; D008982:Molybdenum; D010087:Oxides; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates