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A new [Zn2L2] metallocycle bearing two metal centers that can coordinate ancillary ligands and a pocket suitable to host guest molecules is reported. These two features are exploited by reacting the metallocycle with a pyridine ligand to self-assemble in the solid state an extended intertwined system with the rare 1D + 1D → 1D topology. This interpenetrated architecture is supported by π···π stacking between two pyridine units of two different metallocycles in the pocket of a third metallocycle.

A Zn(II) Metallocycle as Platform to Assemble a 1D + 1D → 1D Polyrotaxane via π···π Stacking of an Ancillary Ligand