Four Hybrid Materials Based on Preyssler P sub(5)W sub(30) Polyoxometalate and First-Row Transition-Metal Complex

• Published in: Inorganic chemistry 2015-08, Vol.54 (15), p.7415-7423
• Main Authors: Hu, Tuo-Ping, Zhao, Ya-Qin, Jaglicic, Zvonko, Yu, Kai, Wang, Xing-Po, Sun, Di
• Format: Article
• Language: English
• Subjects: Acetal resins; Aldehydes; Clusters; Construction; Networks; Polyoxometallates; Reduction; Three dimensional
• ISSN: 0020-1669
• DOI: 10.1021/acs.inorgchem.5b00962

Four Preyssler P sub(5)W sub(30) based inorganic-organic hybrids, formulated as {[Cu sub(12)(pbtz) sub(2)(Hpbtz) sub(2)(OH) sub(4)(H sub(2)O) sub(16)][Na(H sub(2 )O) P sub(5)W sub(30)O sub(110)]} times 16H sub(2)O (1; H sub(2)pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu sub(10)(ttbz) sub(2)(Httbz) sub(4)(OH) sub(6)(H sub(2)O) sub(8)][K(H sub(2)O )H sub(2)P sub(5)W sub(30)O sub(110)]} times 30H sub(2)O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni sub(6)(bpz) sub(6)(H sub(2)O) sub(16)] [Na(H sub(2)O)H sub(2)P sub(5)W sub(30)O sub(110)] } times 36H sub(2)O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co sub(4)(bpz) sub(6)(H sub(2)O) sub(9)][K(H sub(2)O)H sub(6)P sub(5)W sub(3 0)O sub(110)]} times 46H sub(2)O (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 P sub(5)W sub(30) polyoxometalate (POM) clusters and discrete [Cu sub(6)(pbtz) (Hpbtz)(OH) sub(2)(H sub(2)O) sub(8)] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu sub(5)(ttbz)(Httbz) sub(2)(OH ) sub(3)(H sub(2)O) sub(4)] sheets pillared by individual P sub(5)W sub(30) clusters. Compound 3 contains octa-supporting P sub(5)W sub(30) POM clusters and novel [Ni sub(6)(bpz) sub(6)] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4 super(5) times 6 super(4) times 8}{4 super(5) times 6 super(5)} network built by pentasupporting P sub(5)W sub(30) POM clusters and discrete [Co sub(4)(bpz) sub(6)(H sub(2)O) sub(9)] subunits. In 1-4, the unified features are the Preyssler-type [P sub(5)W sub(30)O sub(110 )] 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.