Unprecedented Application of Flexible Bis(pyridyl-tetrazole) Ligands To Construct Helix/Loop Subunits To Modify Polyoxometalate Anions

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• 作者：Xiu-Li Wang ; Na Li ; Ai-Xiang Tian ; Jun Ying ; Tian-Jiao Li ; Xiao-Ling Lin ; Jian Luan ; Yang Yang
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 21, 2014
• 年：2014
• 卷：53
• 期：14
• 页码：7118-7129
• 全文大小：702K
• ISSN：1520-510X

文摘

By introducing the unprecedented and flexible isomeric bis(pyridyl-tetrazole) ligands into a polyoxometalates (POMs) system, three POM-based compounds, {Ag₂(4-bptzb)₂(H₂O)₂[H₂PMo₁₂O₄₀]₂}路4-bptzb路5H₂O (1), [Ag₄(3-bptzb)₂(PMo^VMo^VI₁₁O₄₀)]路2H₂O (2), and Ag₃(3-bptzb)_2.5(H₂O)₂[H₃P₂W₁₈O₆₂] (3) [4-bptzb = 1,4-bis(5-(4-pyridyl)tetrazolyl)butane and 3-bptzb =1,4-bis(5-(3-pyridyl)tetrazolyl)butane], were synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses. Compound 1 exhibits a dimeric structure constructed from two Keggin [PMo₁₂O₄₀]^{3鈥?/sup> anions and a binuclear [Ag₂(trans-4-bptzb)₂]2+ subunit in which the trans-4-bptzb acts as a bidentate bridging ligand with one tetrazolyl group. In 2, the 3-bptzb acts as a tetradentate bridging ligand with the tetrazolyl and pyridyl groups linking AgI ions to generate a 3D metal鈥搊rganic framework (MOF), which contains charming meso-helix chains. The Keggin anions acting as bidentate inorganic ligands reside in the distorted tetragonal channels of the MOF. In compound 3, the 3-bptzb adopts versatile coordination modes linking AgI ions to first construct loop connecting loop 1D chains, which are linked by {Ag[P₂W₁₈O₆₂]}_n zigzag chains to form a scarce hamburger-style 2D sheet. These adjacent sheets are further fused by 3-bptzb ligands to construct a 3D framework. The influences of isomeric bptzb ligands and POMs on the construction of Ag-bptzb subunits and the whole structures of the title compounds are discussed. The electrochemical behaviors and electrocatalytic activities of compounds 2 and 3 and their corresponding parent POMs as well as the fluorescent properties of the title compounds have been studied in detail. In addition, the photocatalytic activities of compounds 2 and 3 and their corresponding parent POMs for decomposition of methylene blue, rhodamine B, and methyl orange under UV irradiation have also been investigated.}