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The aim to develop stimuli-responsive supramolecular hyperbranched polymers with tunable morphology transitions in solutions has theoretical and practical significance in wide applications. By a combination of a 1 → 7 branching strategy and supramolecular polymerization, here we demonstrate a simple approach to prepare well-defined POSS-embedded stimuli-responsive supramolecular hyperbranched polymers (POSS-SSHPs) with monomer concentration-dependences, pH- and light-triggered disassembly behaviors and solvent polarity-dependent morphological transitions. Further addition of an appropriate amount of competitive guests in selective solvents can achieve other well-organized morphology transitions by the multiple supramolecular driving forces of host–guest inclusion complexations, hydrophilic–hydrophobic interactions and unique POSS aggregation behaviors. This work may provide a universal strategy to construct novel supramolecular polymers with tailored architectures, desired functionalities and potential biomedical applications.

Graphical abstract: Fabrication of POSS-embedded supramolecular hyperbranched polymers with multi-responsive morphology transitions

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