title: Organic-Inorganic Hybrid Materials Based on Basket-like {Ca⊂P6Mo18O73} Cages.
abstract: Four basket-like organic-inorganic hybrids, formulated as [{Cu(II)(H2O)2}{Ca4(H2O)4(HO0.5)3(en)2}{Ca⊂P6Mo4(V)Mo14(VI)O73}]·7H2O (1), (H4bth)[{Fe(II)(H2O)}{Ca⊂P6Mo18(VI)O73}]·4H2O (2), (H2bih)3[{Cu(II)(H2O)2}{Ca⊂P6Mo2(V)Mo16(VI)O73}]·2H2O (3), (H2bib)3[{Fe(II)(H2O)2}{Ca⊂P6Mo2(V) Mo16(VI)O73}]·4H2O (4), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bib = 1,4-bis(imidazole)butane) have been hydrothermally synthesized and fully characterized. Compounds 1-4 contain polyoxoanion [Ca⊂P6Mon(V)Mo18-n(VI)O73]((6+n)-) (n = 0, 2, or 4) (abbreviated as {P6Mo18O73}) as a basic building block, which is composed of a "basket body" {P2Mo14} unit and a "handle"-liked {P4Mo4} fragment encasing an alkaline-earth metal Ca(2+) cation in the cage. Compound 1 exhibits an infrequent 2D layer structure linked by the Cu(H2O)2 linker and an uncommon tetranuclear calcium complex, while compound 2 is 8-connected 2-D layers connected by binuclear {Fe2(H2O)3} segaments, which are observed for the first time as 2-D basket-like assemblies. Compounds 3 and 4 are similar 1D Z-typed chains bonded by M(H2O)2 units (M = Cu for 3 and Fe for 4). The optical band gaps of 1-4 reveal their semiconductive natures. They exhibit universal highly efficient degradation ability for typical dyes such as methylene blue, methyl orange, and rhodamine B under UV light. The lifetime and catalysis mechanism of the catalysts have been investigated. The compounds also show good bifunctional electrocatalytic behavior for oxidation of amino acids and reduction of NO2(-).
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: He
authors.initials: H
authors.lastname: Zhang
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Kai
authors.initials: K
authors.lastname: Yu
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Jing-hua
authors.initials: JH
authors.lastname: Lv
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Li-hong
authors.initials: LH
authors.lastname: Gong
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Chun-mei
authors.initials: CM
authors.lastname: Wang
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Chun-xiao
authors.initials: CX
authors.lastname: Wang
authors.affiliation: §School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
authors.forename: Di
authors.initials: D
authors.lastname: Sun
authors.affiliation: †Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, P. R. China.|‡Key Laboratory of Synthesis of Functional Materials and Green Catalysis, College of Heilongjiang Province, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, P. R. China.
authors.forename: Bai-Bin
authors.initials: BB
authors.lastname: Zhou
mesh_terms: D002073:Butanes / Q000737:chemistry; D002118:Calcium / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry; D006586:Hexanes / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry; D010782:Photolysis; D014230:Triazoles / Q000737:chemistry*
chemical_list: D002073:Butanes; D005296:Ferrous Compounds; D006586:Hexanes; D007093:Imidazoles; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D014230:Triazoles; D003300:Copper; D008982:Molybdenum; D002118:Calcium