Thermoreversible Polymorph Transitions in Supramolecular Polymers of Hydrogen-Bonded Squaramides
Sergi Bujosa1, Azahara Doncel-Giménez2, Nils Bäumer3
1Department of Chemistry, Universitat de les Illes Balears, Cra. Valldemossa, Km. 7.5, 07122, Palma de Mallorca, Spain.
Abstract:
Hydrogen-bonded squaramide (SQ) supramolecular polymers exhibit uncommon thermoreversible polymorph transitions between particle- and fiber-like nanostructures. SQs 1-3, with different steric bulk, self-assemble in solution into particles (AggI) upon cooling to 298 K, and SQs 1 and 2, with only one dendronic group, show a reversible transformation into fibers (AggII) by further decreasing the temperature to 288 K. Nano-DSC and UV/Vis studies on SQ 1 reveal a concentration-dependent transition temperature and ΔH for the AggI-to-AggII conversion, while the kinetic studies on SQ 2 indicate the on-pathway nature of the polymorph transition. Spectroscopic and theoretical studies reveal that these transitions are triggered by the molecular reorganization of the SQ units changing from slipped to head-to-tail hydrogen bonding patterns. This work unveils the thermodynamic and kinetic aspects of reversible polymorph transitions that are of interest to develop stimuli-responsive systems.
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