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Supramolecular systems in water are of paramount importance and those based on hydrogen bonds are both intriguing and scarce. Here, after studying the peculiar host–guest complexes formed between per‐dimethylamino‐pillar[5]arene (1) and the bis‐sulfonates 2 a–c, we describe the formation of the first hydrogen‐bond‐based supramolecular pentagonal boxes (SPBs), which are stable in water. These pH‐responsive...
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