title: Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate.
abstract: The encapsulation of carbonate derived from atmospheric CO2 has resulted in an icosanuclear heteropolyoxocopperate, isolated as a metal-organic 1D chain, 2D sheet, or 3D framework, in which the Cu20 nanocluster represents the first eight-capped α-Keggin polyoxometalate with the late-transition-metal Cu(II) as the polyatom, CO3(2-) as the heteroanion, and OH(-) and suc(2-) or glu(2-) (H2suc=succinic acid; H2glu=glutaric acid) as the terminal ligands, which suggests a conceptual similarity to classical polyoxometalates. Even in the presence of competitive SO4(2-) in the assembly system, the CO3(2-) anion is still captured as a template to direct the formation of the Cu20 nanocluster, which indicates the stronger templation ability of CO3(2-) compared with SO4(2-). When other aliphatic dicarboxylates, such as glutaric acid, were used as ligands, the CO3(2-)-templated Cu20 nanocluster was maintained and acted as a cluster building unit (CBU) to be linked by two glutarate bridges to generate a distinct 1D metal-organic chain. This report presents not only a rare example of a huge anion-templated transition-metal cluster, but also its use as a robust CBU to construct novel coordination architectures. Variable-temperature magnetic susceptibility studies revealed that an antiferromagnetic interaction exists within the Cu20 nanocluster. The correlation between the coordination structure and the electron paramagnetic resonance spectra recorded of both powder and single-crystal samples are discussed in detail.
authors.affiliation: Key Lab for Colloid and Interface Chemistry of the Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100 (P. R. China).
authors.forename: Fu-Ling
authors.initials: FL
authors.lastname: Liu
authors.affiliation: Faculty of Chemistry and Chemical Technology, University of Ljubljana, Vecna pot 113, 1000 Ljubljana (Slovenia).
authors.forename: Bojan
authors.initials: B
authors.lastname: Kozlevčar
authors.affiliation: Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam-Golm (Germany).
authors.forename: Peter
authors.initials: P
authors.lastname: Strauch
authors.affiliation: Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou, 310032 (P. R. China).
authors.forename: Gui-Lin
authors.initials: GL
authors.lastname: Zhuang
authors.affiliation: Key Lab for Colloid and Interface Chemistry of the Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100 (P. R. China).
authors.forename: Ling-Yu
authors.initials: LY
authors.lastname: Guo
authors.affiliation: Key Lab for Colloid and Interface Chemistry of the Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100 (P. R. China).
authors.forename: Zhi
authors.initials: Z
authors.lastname: Wang
authors.affiliation: Key Lab for Colloid and Interface Chemistry of the Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100 (P. R. China). dsun@sdu.edu.cn.
authors.forename: Di
authors.initials: D
authors.lastname: Sun
keywords: carbon dioxide fixation; cluster compounds; copper; magnetic properties; polyoxometalates