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© 2020 The Royal Entomological Society.Polyimidazolium-based cages are considered promising materials based on their fascinating properties and potential applications. These three-dimensional functional structures are highly desirable for the recognition of particular guest molecules, however, their synthesis remains challenging. In this work, we have designed and synthesizes a pure [n]-imidazolium (n = 16) cage, the hexadecakisimidazolium salt H16-2(PF6)16, from tetragonal octakisimidazolium salt H8-1(PF6)8. The synthetic method involves