Solvation Entropy as a Lever for Steering the Macroscopic Properties of a Functional Supramolecular Helical Polymer
Abstract
Abstract Solvent‐solute interactions are utterly important in supramolecular polymers (SPs), yet the high responsivity of SPs to solvent polarity makes it challenging to play on other solvation effects to tune their macroscopic properties in a rational manner. Herein, we report the characterization at various scales of the assembly properties of a C 2 ‐symmetric benzene‐1,3,5‐tricarboxamide monomer with two (1 S )‐methylheptyl moieties and one diphenylphosphino group as lateral chains. Our investigation reveals a highly cooperative structural transition between two SP states, which can exquisitely be tuned by solvents of similar polarities, leading to variation of the transition temperature (T*) over a range of 85 K. The structural transition was detected in 4 pure solvents and 13 toluene/cosolvent mixtures; a fair relationship is determined between T* and the solvent molar volume. The transition is only weakly favored by enthalpy (by ca. 2 kJ.mol −1 at 286 K). However, minimization of the entropic cost leads to a notable increase in the T*. This allows a fine tuning of the thermothickening and catalytic properties of the resulting SPs auguring that solvation, and notably solvation entropy, may constitute an important lever for steering SPs structure and properties.
Article Details
Authors (13)
Huanjun Kong
Sorbonne Université CNRS Institut Parisien de Chimie Moléculaire 4 Place Jussieu Paris 75005 France
Mayte A. Martínez‐Aguirre
Sorbonne Université CNRS Institut Parisien de Chimie Moléculaire 4 Place Jussieu Paris 75005 France
Yan Li
Tomoyuki Ikai
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering
Eiji Yashima
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering
Gangamallaiah Velpula
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven 3001, Belgium
Steven De Feyter
Division of Molecular Imaging and Photonics, Department of Chemistry
Pierre‐Antoine Albouy
Laboratoire de Physique des Solides CNRS Université Paris‐Sud Université Paris‐Saclay Orsay 91400 France
Komivi Akpo
Service de Chimie des Matériaux Nouveaux Institut de Recherche sur les Matériaux Université de Mons Place du Parc, 20 Mons B‐7000 Belgium
Patrick Brocorens
Service de Chimie des Matériaux Nouveaux Institut de Recherche sur les Matériaux Université de Mons Place du Parc, 20 Mons B‐7000 Belgium
Roberto Lazzaroni
Laboratory for Chemistry of Novel Materials, Materials Research Institute, University of Mons, Place du Parc 20, Mons 7000, Belgium
Laurent Bouteiller
Sorbonne Université CNRS Institut Parisien de Chimie Moléculaire 4 Place Jussieu Paris 75005 France
Matthieu Raynal
Sorbonne Université CNRS Institut Parisien de Chimie Moléculaire 4 Place Jussieu Paris 75005 France