Kinetically Controlled Supramolecular Block Copolymer Self-Assembly:Multicolor Photonic Crystal Patterns from a Single Formulation

Photonic crystal(PC)patterns with tunable and changeable nonvolatile structural colors printed from a single ink are of great interest for optical products but have rarely been reported because most inks can only output one respective structural color.Herein,we propose a facile yet effective kinetically controlled self-assembly strategy to address this challenge.An ink formulation containing supramolecular block copolymers(SBCPs)is developed.SBCP patterns were printed by direct-ink-writing followed by solvent annealing to generate different structural colors by simply controlling the annealing time.The self-assembly kinetic regime suggests that different colors result from various kinetically trapped metastable states.In turn,the variation in structural color enables“visualization”of the self-assembly dynamics.Furthermore,we demonstrate that these kinetically trapped structures exhibit different responsive color-change behaviors.In addition,this kinetic control strategy can be synergistic with thermodynamic control to extend the color range.This study provides a facile yet effective solution for well-designed PC patterns with tunable,responsive,and unfading colors printed from the simplest single-nozzle printer with a single colorless ink,presenting great potential in broad applications,including information storage,encryption,and anti-fake.

Hierarchical Microphase Behaviors of Chiral Block Copolymers under Kinetic and Thermodynamic Control

Chiral superstructures in confined spaces are subtly affected by the complex interplay among various noncovalent interactions,details of which are still in adequately understood.Herein,we report the threedimensional confined assembly of the chiral block copolymers of polystyrene-block-poly(D-lactide)andits enantiomer in emulsion droplets and demonstrate unprecedented successive microphase transformations from single helices to double helices with inverted helicity,and then to twisted cylinders in the constructedcolloidal particles.Theabovehierarchical structural transformations of chiral microphases are kinetically dependent and can further transform into thermodynamically stable achiral cylinders with saddle-shaped topology upon solvent annealing.The formation and subsequent structural transformations as well as thefinal degeneration of chiral architectures provide guidance to understand the chiral evolution at different length scales within spherical confined space and to fabricate biomimetic systems.