Multilayer mesoporous vesosomes of block copolymer.

Multilayer mesoporous vesosomes uniquely combine hollow multilayer shells with ordered mesopores, providing a basis for multilevel gating, controlled release, and programmed reaction cascades, yet robust construction remains challenging. Herein, we report a molecular engineering strategy based on 3D-confined self-assembly to produce multilayer vesosomes with nearly hexagonally ordered shell perforations. Selective association of pentadecylphenol (PDP) and 1,5-dibromopentane (DBP) with the poly(4-vinylpyridine) block precisely tunes block-copolymer volume fraction to stabilize an unconventional perforated lamellar morphology, while reversible hydrogen bonding enables region-selective pore generation. Experiments and simulations reveal cooperative roles of confinement and hydrogen bonding in directing morphological evolution, with DBP further refining assembly through electrostatic and cross-linking interactions. The resulting multilayer mesoporous vesosomes feature a pyridine-rich corona and show iodine capture (1.26 g g-1), good recyclability, and faster uptake than nonporous multilayer analogues. This work offers a versatile route to complex hollow architectures and clarifies key determinants governing their formation.