title: Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate and First-Row Transition-Metal Complex.
abstract: Four Preyssler P5W30 based inorganic-organic hybrids, formulated as {[Cu12(pbtz)2(Hpbtz)2(OH)4(H2O)16][Na(H2O)P5W30O110]}·16H2O (1; H2pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu10(ttbz)2(Httbz)4(OH)6(H2O)8][K(H2O)H2P5W30O110]}·30H2O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni6(bpz)6(H2O)16][Na(H2O)H2P5W30O110]}·36H2O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co4(bpz)6(H2O)9][K(H2O)H6P5W30O110]}·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 {4(5)·6(4)·8}{4(5)·6(5)} network built by pentasupporting P5W30 POM clusters and discrete [Co4(bpz)6(H2O)9] subunits. In 1-4, 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.
authors.affiliation: †Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.|‡Department of Chemistry, North University of China, Taiyuan, 030051, P. R. China.
authors.forename: Tuo-Ping
authors.initials: TP
authors.lastname: Hu
authors.affiliation: †Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Ya-Qin
authors.initials: YQ
authors.lastname: Zhao
authors.forename: Zvonko
authors.initials: Z
authors.lastname: Jagličić
authors.affiliation: ∥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 Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Xing-Po
authors.initials: XP
authors.lastname: Wang
authors.affiliation: †Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Di
authors.initials: D
authors.lastname: Sun