Polymeric Multimaterials Enabled by Aza-Michael Addition

Materials with spatially organized domains of distinct properties typically outperform their homogeneous counterparts in achieving sophisticated functionalities. The ability to integrate diverse chemical architectures into a programmable, yet continuous molecular framework has enabled exceptional property synergies. While crystallization plays a critical role in the construction of natural structural architectures, deliberate establishment of heterogeneous crystallizability in synthetic polymers remains in its infancy. Herein, we report a facile chemical strategy for fabricating polymeric multimaterials with spatially tunable crystallizability. These multimaterials are capable of integrating various regions of tunable crystallinity through orthogonal reactions of UV-triggered radical chain-growth and thermally driven aza-Michael step-growth polymerization. While radical-mediated homopolymerization yields high-resolution patterns of densely cross-linked domains, concurrent aza-Michael addition establishes a loose network in shaded regions. This pronounced contrast in cross-linking density further directs the divergent crystallization behaviors of semicrystalline polyesters, thereby enabling programmable mechanical performance and versatile shape morphing. Critically, the spatial programming of condensed-phase organization in synthetic polymers establishes a generalizable strategy for encoding information within programmed heterogeneous architectures, particularly through the selective incorporation of aggregation-responsive dyes.