Abstract
AbstractRecent investigations of supramolecular polymers based on chiral triphenylene‐2,6,10‐tricarboxamides (TTAs) showed how temperature‐induced changes in solvation can greatly influence the preferred helical conformation of the supramolecular polymers formed. Here, we combine chiral TTA with achiral copolymerization partners to further investigate temperature‐dependent solvation effects. Systematic variation of the system's composition shows clear impacts on the temperature window where the conformational change occurs. Further, simple chain length variations in the achiral comonomer greatly affect the ability to influence the conformational change in the copolymer, while the differences in the properties of the individual homopolymers are rather small. We herein highlight how subtle changes in the monomers can impact the observed copolymer properties drastically; an effect arising from the emerging complexity of multicomponent interactions in supramolecular copolymers with solvent‐solute interactions being more important than typically thought.
Highlights
Detailed understanding of association thermodynamics in catalysis, biochemistry, medicinal chemistry, and supramolecular chemistry is of great importance to successfully design functional molecular systems
We highlight how subtle changes in the monomers can impact the observed copolymer properties drastically; an effect arising from the emerging complexity of multicomponent interactions in supramolecular copolymers with solvent-solute interactions being more important than typically thought
R displays two temperature-dependent helical conformations as shown by VT-electronic circular dichroism (ECD) measurements, in the following described as less solvated high-temperature (HT) and more solvated low-temperature (LT) state
Summary
Detailed understanding of association thermodynamics in catalysis, biochemistry, medicinal chemistry, and supramolecular chemistry is of great importance to successfully design functional molecular systems. As discussed in an excellent review by George Whitesides on protein-ligand interactions, proteinligand complex formation in solution is always accompanied by changes in the solvation sphere of the protein, the ligand, and the forming protein-ligand complex. These solvation effects are influencing the thermodynamic landscape of intermolecular interactions.[3] The principles of monomermonomer associations and the role of solvation are closely related to those discussed for protein-ligand interactions, and the aforementioned points are conferrable to supramolecular polymerization processes by translating protein into polymer and ligand into monomer
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