Effect of annealing on self-assembly kinetics and structural colors of supramolecular polymer patterns

Block copolymer (BCP) photonic crystals (PCs) have great potential in color decoration, optical encryption, and smart sensing because of their excellent flexibility and stimuli-responses. Supramolecular BCPs (SBCPs) provide a versatile platform for engineering structural colors through reversible non-covalent interactions, yet their precise dynamic modulation under confined environments remains underexplored. Here, we develop an integrated real-time monitoring system to elucidate the temperature-solvent synergistic annealing strategy to regulate the disorder-to-order transition of hydrogen-bonded comb-like SBCPs and homopolymers binary co-assembly system, which can yield a lamellar structure and exhibit structural color. Systematic investigation revealed that increasing solvent content accelerates ordering kinetics and induces a red-shift of structural color in their swollen states, while the equilibrium structural color remains solvent-independent upon solvent removal. Unexpectedly, elevating the temperature decelerates ordering kinetics and induces a blue-shift in both swollen and dry states. This counterintuitive phenomenon can be attributed to thermally reduced solvent uptake (by SBCPs) and partial hydrogen-bond dissociation, diminishing the molecular weight and rigidity of SBCPs. These findings elucidate the critical role of swelling and dynamic hydrogen-bond interactions in governing assembly pathways, structure and optical properties of SBCPs, providing a versatile platform for designing stimuli-responsive PC materials with on-demand colors and color switching.