The ability to control the thermodynamic driving forces of self-assembly is key to the development of functional and in particular thermoresponsive materials. This is especially challenging in water due to the solvophobic effects which dictate association. Herein, we present naphthalene and perylene bisimides whose aggregation is observed either upon heating or cooling depending on the connection of solubilising side chains to the π-cores. Rylene bisimides, where phenyl substituent with three oligoethylene glycol (OEG) chains are attached directly to the hydrophobic π-cores undergo association at elevated temperatures with a favorable entropy as revealed by UV-vis spectroscopy and calorimetric measurements. In contrast, rylene bisimides where the phenyl substituent with three OEG chains are attached via a methylene spacer unit self-assemble upon cooling. This surprisingly different thermodynamic signature for quite similar molecules will be explained by the different hydration of the hydrophobic cores and the OEG side chains as well as by structural peculiarities.

Aggregation of amphiphilic naphthalene and perylene bisimides in water: Thermodynamic analysis

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.