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Out with the old, in with the new: Can the transmetalation of metal–organic supramolecular assemblies lead to new structure types? A series of Bi, Sb, and As‐containing cryptands is reported that can be transmetalated to give a novel P2L3 cryptand (see scheme). The PS bonds behave reversibly, like traditional metal–ligand bonds, suggesting a possible new motif for dynamic covalent chemistry.
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