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A new inverted cucurbituril, namely inverted hexamethylcucurbit[3,3]uril (iMe6Q[3,3]), has been isolated and characterized. It incorporates a single inverted un‐substituted glycoluril unit oriented towards the interior of the cavity, shows good solubility in water and organic solvents (DMSO), and exhibits different selectivity for guests to those of iQ[6] and other known Q[6]s.
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