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RESEARCH PRODUCT

ChemInform Abstract: Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

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Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV–vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)]4– (1) consists of a trilacunary [B-α-PW9O34]9– unit which accommodates a cubane-like {CoII4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2]9– (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n– (3), and [Co7(OH)6(H2O)6(P2W15O56)2]15– (4), dicubane-like {CoII6CoIIIO8} cores are encapsulated between two heptadentate [B-α-PW9O34]9– (in 2 and 3) or [α-P2W15O56]15– (in 4) ligands. While 1, 2, and 4 are discrete polyoxometalates, 3 exhibits a polymeric, chain-like structure that results from the condensation of polyoxoanions of type 2. The magnetic properties of these complexes have been fitted according to an anisotropic exchange model in the low-tempe...