title: Three novel and various isopolymolybdate-based hybrids built from the carboxyl oxygen atoms of in situ ligands: substituent-tuned assembly, architectures and properties.
abstract: By changing the N-donor groups of benzonitrile-based reactants, three novel isopolymolybdate-based compounds, [Cu(DBIBA)3][δ-HMo8O26] (1), [Cu(H2O)(DIBA)(DIBAH)(γ-HMo8O26)]·2H2O (2), and [CuI(DTBA)(Mo2O6)] (3) (HDBIBA = 3,5-di(benzoimidazol-1-yl)benzoic acid, HDIBA = 3,5-di(1H-imidazol-1-yl)benzoic acid and HDTBA = 3,5-di(1,2,4-triazol-1-yl)benzoic acid) were synthesized, in which the benzene carboxylate-based ligands DBIBA, DIBA and DTBA were in situ transformed from the benzonitrile-based ligands under hydrothermal conditions. Selecting benzoimidazol as the N-donor group, compound 1 with a 3D (6, 8)-connected framework is constructed from {Cu3(DBIBA)3} hexagonal ring building units and [δ-Mo8O26]4-polyoxoanions. Replacing the benzoimidazol with the imidazol group, a 3D (3, 4, 6)-connected framework 2 containing two types of {(γ-Mo8O26)(DIBA)2} building blocks was obtained. When the triazol groups are introduced, compound 3 displays a 3D framework, which is constructed from {(Mo4O13)(DTBA)2}nchains bridged by CuIatoms. It is interesting to note that the carboxyl oxygen atoms from the in situ ligands participate in the construction of isopolymolybdates in compounds 2 and 3. In addition, the various N-donor groups of in situ ligands show a great effect on the oxidation state of copper ions, the novel polymolybdate unit and the final architectures of the title compounds. The electrochemical properties and photocatalytic activities of compounds 1-3 were investigated herein.
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Xiu-Li
authors.identifier: http://orcid.org/0000-0002-0308-1403
authors.initials: XL
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Rui
authors.initials: R
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Xiang
authors.initials: X
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Hong-Yan
authors.initials: HY
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Guo-Cheng
authors.initials: GC
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China. wangxiuli@bhu.edu.cn.
authors.forename: Hui-Xiu
authors.initials: HX
authors.lastname: Zhang