Thermally Induced Macromolecular Sequence Inversion in Triblock Copolymers and Terpolymers

Dynamic control over polymer sequences remains a major challenge in synthetic macromolecules, limiting their adaptability relative to biomacromolecules. Herein, we introduce an intra‐macromolecular sequence inversion in triblock copolymers and terpolymers using a furan–maleimide–anthracene Diels–Alder system, enabling thermal reconfiguration at 120°C without altering composition or molecular weight. Bifunctional initiators bearing reversible Diels–Alder linkages allow the synthesis of symmetric (ABA) and asymmetric (ABC) triblock co/terpolymers. Upon heating, retro‐Diels–Alder dissociation followed by anthracene–maleimide (Anth–Mal) cycloaddition induces sequence inversion, yielding BAB or BAC architectures. Comprehensive experimental characterization confirms preservation of chain integrity, while revealing altered diffusion coefficients and distinct microphase‐separated morphologies, highlighting the pronounced influence of sequence on polymer properties. This strategy establishes a paradigm for programmable polymer metamorphosis, opening new avenues toward stimuli–responsive materials with tunable self‐assembly, crystallinity, and mechanical properties.