Molecular Necklaces Formed Through Zn2+‐Templated Binding of Macrocycles with Dynamically Formed Imines as Guest Recognition Sites.

Herein we demonstrate an "in‐ring establishing" strategy for assembling interlocked molecules through dynamic imine formation, "establishing" the host recognition sites in situ. Using Zn2+ ions to template the assembly of a pyridine‐containing macrocycle with semidumbbell‐shaped triazole‐containing aldehyde and amine derivatives, we obtained the corresponding [2]rotaxane in high yield (85 %) after subsequent imine reduction (NaBH4) and amine protonation (NH4PF6). We performed the same three steps (assembly, reduction, protonation) to prepare a stable and highly symmetrical [5]molecular necklace ([5]MN) from 12 components (two almost‐90°‐oriented dialdehydes, two almost‐90°‐oriented diamines, four macrocycles, four Zn2+ ions) in an overall yield of 69 %. [ABSTRACT FROM AUTHOR]