Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate and First-Row Transition-Metal Complex

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• 作者：Tuo-Ping Hu ; Ya-Qin Zhao ; Zvonko Jagli膷i膰 ; Kai Yu ; Xing-Po Wang ; Di Sun
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 3, 2015
• 年：2015
• 卷：54
• 期：15
• 页码：7415-7423
• 全文大小：691K
• ISSN：1520-510X

文摘

Four Preyssler P₅W₃₀ based inorganic鈥搊rganic hybrids, formulated as {[Cu₁₂(pbtz)₂(Hpbtz)₂(OH)₄(H₂O)₁₆][Na(H₂O)P₅W₃₀O₁₁₀]}路16H₂O (1; H₂pbtz = 5鈥?(pyridin-2-yl)-1H,2鈥?i>H-3,3鈥?bi(1,2,4-triazole)), {[Cu₁₀(ttbz)₂(Httbz)₄(OH)₆(H₂O)₈][K(H₂O)H₂P₅W₃₀O₁₁₀]}路30H₂O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni₆(bpz)₆(H₂O)₁₆][Na(H₂O)H₂P₅W₃₀O₁₁₀]}路36H₂O (3; bpz = 3,3鈥?5,5鈥?tetramethyl-4,4-bipyrazole), {[Co₄(bpz)₆(H₂O)₉][K(H₂O)H₆P₅W₃₀O₁₁₀]}路46H₂O (4), have been isolated and structurally identified via microanalysis, thermogravimetry (TG), infrared (IR) spectroscopy, and X-ray single-crystal diffraction. Compound 1 exhibits a 3D binodal (3,6)-connected ant framework composed of dodeca-supported P₅W₃₀ polyoxometalate (POM) clusters and discrete [Cu₆(pbtz)(Hpbtz)(OH)₂(H₂O)₈] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu₅(ttbz)(Httbz)₂(OH)₃(H₂O)₄] sheets pillared by individual P₅W₃₀ clusters. Compound 3 contains octa-supporting P₅W₃₀ POM clusters and novel [Ni₆(bpz)₆] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4⁵路6⁴路8}{4⁵路6⁵} network built by pentasupporting P₅W₃₀ POM clusters and discrete [Co₄(bpz)₆(H₂O)₉] subunits. In 1鈥?b>4, the unified features are the Preyssler-type [P₅W₃₀O₁₁₀] POM as the fundamental building block, which supports the transition-metal compounds with different modes to give the resultant diverse networks. The magnetism studies indicated antiferromagnetically coupled systems for the hexa- and pentanuclear Cu(II) units in 1 and 2, respectively. The electrochemical properties demonstrate that all compounds have electrocatalytic abilities toward the reduction of hydrogen peroxide. Furthermore, the catalytic activities of 1 in the cyanosilylation of aldehydes reaction have been investigated.