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The disassembly and reassembly of giant molecules are essential processes in controlling the structure and function of biological and artificial systems. In this work, the disassembly and reassembly of a giant ring-shaped polyoxometalate (POM) without isomerization of the monomeric units is reported. The reaction of a hexavacant lacunary POM that is soluble in organic solvents, P2 W12 O48 (14-), with manganese cations gave the giant ring-shaped POM γ-P2 W12 O48 Mn4 (C5 H7 O2) 2 (CH3 CO2) 6 (42-). This POM is a hexamer of manganese-substituted P2 W12 O48 Mn4 units, and its inner cavity was larger than any of those previously reported for ring-shaped polyoxotungstates. It was disassembled into monomeric units in acetonitrile, and the removal of the capping organic ligands on the manganese cations led to reassembly into a tetrameric ring-shaped POM, γ-P2 W12 O48 Mn4 (H2 O) 6 4 (H2 O) 4 (24-).
Minato et al. (2016) studied this question.