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The exchange of the monocarboxylate ligand of the zirconium methacrylate oxocluster Zr(6)O(4)(OH)(4)(OMc)(12) (OMc = CH(2)=CH(CH(3))COO) with dicarboxylic acids (trans,trans muconic acid and terephthalic acid) leads to porous zirconium dicarboxylates exhibiting the UiO-66 architecture; the mild reaction conditions allow the control of their particle size.

A new isomer of the oxozirconium cluster Zr 4 O 2 (methacrylate) 12 was obtained by reaction of zirconium butoxide with an excess of methacrylic acid. Contrary to the known isomer, the structure is centrosymmetric with a planar, rhombic Zr 4 core. Copolymerization with a 56-207-fold excess of methylmethacrylate results in cluster-crosslinked poly(methylmethacrylate) that swells in ethyl acetate but does not dissolve. The solvent uptake during swelling decreases and the thermal stability improves with an increasing portion of the cluster.