Mechanically bonded macromolecules constitute a class of challenging synthetic targets in polymer science. The controllable intramolecular motions of mechanical bonds, in combination with the processability and useful physical and mechanical properties of macromolecules, ultimately ensure their potential for applications in materials science, nanotechnology and medicine. This tutorial review describes the syntheses and properties of a library of diverse mechanically bonded macromolecules, which covers (i) main-chain, side-chain, bridged, and pendant oligo/polycatenanes, (ii) main-chain oligo/polyrotaxanes, (iii) poly[c2]daisy chains, and finally (iv) mechanically interlocked dendrimers. A variety of highly efficient synthetic protocols—including template-directed assembly, step-growth polymerisation, quantitative conjugation, etc.—were employed in the construction of these mechanically interlocked architectures. Some of these structures, i.e., side-chain polycatenanes and poly[c2]daisy chains, undergo controllable molecular switching in a manner similar to their small molecular counterparts. The challenges posed by the syntheses of polycatenanes and polyrotaxanes with high molecular weights are contemplated.

The contamination of water by per- and polyfluorinated substances (PFAS) is a pressing global issue due to their harmful effects on health and the environment. This study explores a cationic covalent organic framework (COF), TG-PD COF, for the efficient detection and removal of perfluorooctanoic acid (PFOA) from water. Synthesized via a simple sonochemical method, TG-PD COF shows remarkable selectivity and sensitivity to PFOA, with a detection limit as low as 1.8 µg·L⁻¹. It achieves significant PFOA adsorption exceeding 2600 mg·g⁻¹ within seconds over several cycles in batch mode and complete removal at environmentally relevant concentrations in column adsorption. Results reveal unique adsorption behavior characterized by two phases, leveraging PFOA aggregation through hydrophobic interactions. Computer simulations elucidate the mechanisms underlying TG-PD COF’s sensing, adsorption, and charge transfer dynamics. Our findings position this COF design strategy as a promising solution for combating PFAS contamination in water bodies worldwide.