Controlled\nSupramolecular Self-Assembly of Large Nanoparticles\nin Amphiphilic Brush Block Copolymers

Abstract

To date the self-assembly\nof ordered metal nanoparticle (NP)/block\ncopolymer hybrid materials has been limited to NPs with core diameters\n(<i>D</i>_core) of less than 10 nm, which represents\nonly a very small fraction of NPs with attractive size-dependent physical\nproperties. Here this limitation has been circumvented using amphiphilic\nbrush block copolymers as templates for the self-assembly of ordered,\nperiodic hybrid materials containing large NPs beyond 10 nm. Gold\nNPs (<i>D</i>_core = 15.8 ± 1.3 nm) bearing\npoly­(4-vinylphenol) ligands were selectively incorporated within the\nhydrophilic domains of a phase-separated (polynorbornene-<i>g</i>-polystyrene)-<i>b</i>-(polynorbornene-<i>g</i>-poly­(ethylene oxide)) copolymer via hydrogen bonding between the\nphenol groups on gold and the PEO side chains of the brush block copolymer.\nWell-ordered NP arrays with an inverse cylindrical morphology were\nreadily generated through an NP-driven order–order transition\nof the brush block copolymer.