biostudies-literatureUnknown21Yu WOrthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other cooperative intermolecular forces. Zinc ioBeilstein journal of organic chemistry179-188https://www.ebi.ac.uk/biostudies/studies/S-EPMC11744735biostudies-literatureHydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization.PMC11744735Li XYang ZYu CYuan LYu WfalseHydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization.Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other cooperative intermolecular forces. Zinc io2025-01-01T00:00:00Z20252025-04-05T09:32:50.18Z2025-04-05T09:32:50.18ZS-EPMC117447353983489310.3762/bjoc.21.10