Spatially Defined Chemical Functionalization of Ordered Block Copolymer Materials

Abstract The independent manipulation of chemical functionality over the equilibrium morphology in conventional block copolymer (BCP) self-assembly is intrinsically hindered due to the tight composition–structure coupling. Here, we report a synthesis strategy that breaks this constraint by employing self-assembled ABC triblock terpolymer base materials with a gyroid nanoarchitecture and one cross-linked end block as robust 3D templates for the spatially defined in-gel functionalization of the tethered non-cross-linked blocks. We demonstrate this generalizable concept with selective amine attachment in the C end block for selective metal ion coordination, uptake, and nanostructure-directed metal nanoparticle synthesis. Additionally, phase-confined sulfonation is achieved selectively on both the middle B and end C blocks, respectively, producing, to the best of our knowledge, the first monolithic gyroidal hydrogels exhibiting tunable swelling up to 600 vol % and nanoconfined hydration while maintaining structural integrity. Combined sequential and block-selective functionalization generates a nanostructured, pH-responsive polyampholyte material bearing blocked cationic and anionic polymer chains tethered to the continuous and cross-linked gyroidal network. The achieved decoupling of structural and chemical versatility in these cross-linked BCP gels provides a modular platform and design paradigm for studying nanoconfined synthesis, nanoarchitected ion-exchange membranes, and stimuli-responsive smart materials.