Thermally Controlled Morphologies in a Block Copolymer Supramolecule via Nonreversible Order–Order Transitions

Block copolymer (BCP)-based supramolecules represent a versatile platform to generate functional nanostructures without the need for complex synthesis. The noncovalent bonding between the BCP and small molecules further opens opportunities to access thermal responsive assemblies. A BCP supramolecule containing cholesteric liquid crystal (LC) small molecules is observed to undergo thermally induced, nonreversible order–order transitions (OOTs), resulting in several well-defined morphologies readily tunable by annealing temperature. The nonreversible OOTs highlight the importance of small molecule phase transitions and intermolecular interactions on the overall phase behavior of the supramolecule. The present system also provides a route to manipulate local nanostructures via heating.