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While a single pillar[6]arene ring, nestling between two cucurbit[6]uril rings in a series of three hetero[4]rotaxanes, is conformationally mobile in solution, it adopts the energetically most favourable conformation with local C3V symmetry in the solid state.

Graphical abstract: Efficient syntheses of pillar[6]arene-based hetero[4]rotaxanes using a cooperative capture strategy

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