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- Title
Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate.
- Authors
Liu, Fu ‐ Ling; Kozlevčar, Bojan; Strauch, Peter; Zhuang, Gui ‐ Lin; Guo, Ling ‐ Yu; Wang, Zhi; Sun, Di
- 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 CuII as the polyatom, CO32- as the heteroanion, and OH- and suc2- or glu2- (H2suc=succinic acid; H2glu=glutaric acid) as the terminal ligands, which suggests a conceptual similarity to classical polyoxometalates. Even in the presence of competitive SO42- in the assembly system, the CO32- anion is still captured as a template to direct the formation of the Cu20 nanocluster, which indicates the stronger templation ability of CO32- compared with SO42-. When other aliphatic dicarboxylates, such as glutaric acid, were used as ligands, the CO32--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.
- Subjects
COPPER clusters; CARBONATES; ENCAPSULATION (Catalysis); CARBON dioxide; POLYOXOMETALATES
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 51, p18847
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201502834