Metallosupramolecular Zippers Generated by Self‐Organization of Self‐Complementary Molecular Clefts

Abstract
The binding of Co2+ and Pb2+ ions to the terpyridine and pyridine subunits of the ligand 1 leads to the self-complementary molecular clefts 2–6, which result from the crossover combination of orthogonal-terpyridine and linear-pyridine metal-coordination subprograms and are stabilized by strong π–π stacking interactions. Four different cleft-type entities, [Co2+2(1)2] (3), [Pb2+2(1)2] (4), [Co2+4(1)2] (5), [Pb2+4(1)2] (6), are generated in both solution and the solid state, and may be interconverted as a function of metal/ligand stoichiometry. One- and two-dimensional metallosupramolecular zipper architectures result from self-assembly in the solid state driven by a combination of different π–π stacking subprograms. The U-shaped geometry of the ligand influences the possibility of zipping and thus, in turn, the generation of different zipper architectures. The structures of 2–5 have been confirmed by X-ray crystallography; that of 6 is based on NMR spectral data.

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