Polymerisation within a well-defined nanocavity leads to the precise control of the rate of polymerisation and the molecular weight of the resultant polymer. We prepared a highly cationic spherical complex that was self-assembled from 12 palladium(II) ions and 24 quaternary ammonium-attached bidentate ligands. NMR experiments confirmed that this spherical complex encapsulates multivalent anions within the cavity. When the free radical polymerisation of an anionic monomer, sodium p-styrenesulphonate, was carried out in the presence of the cationic sphere as a template, acceleration of the polymerisation and control of the molecular weight of the resultant polymer were observed. The molecular weight of the polymer depends on the number of the positive charges on the template.
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