Optical Monitoring of Supramolecular Interactions in Polymers.

Many stimuli-responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self-healing, switchable adhesion, or mechan-ical adaptation. Despite extensive research into the structure-property relationships of these materials, direct correlations between molecular-level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen-bonding ureido-4-pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supra-molecular cross-linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross-linker content, processing history, and applied stimuli. We demonstrate that the stimuli-induced dissociation of supra-molecular linkages strongly depends on the initial cross-link density, which also dictates whether the force-induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in-situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.

Folded Perylene Diimide Loops as Mechanoresponsive Motifs.

A supramolecular mechanophore that can be integrated into polymers and indicates deformation by a fluorescence color change is reported. Two perylene diimides (PDIs) were connected by a short spacer and equipped with peripheral atom transfer polymerization initiators. In the idle state, the motif folds into a loop and its emission is excimer dominated. Poly(methyl acrylate) (PMA) chains were grown from the motif and the mechanophore-containing polymer was blended with unmodified PMA to afford materials that display a visually discernible fluorescence color change upon deformation, which causes the loops to unfold. The response is instant, and correlates linearly with the applied strain. Experiments with a reference polymer containing only one PDI moiety show that looped mechanophores that display intramolecular excimer formation offer considerable advantages over intermolecular dye aggregates, including a concentration-independent response, direct signaling of mechanical processes, and a more pronounced optical change.

From Molecules to Polymers-Harnessing Inter- and Intramolecular Interactions to Create Mechanochromic Materials.

The development of mechanophores as building blocks that serve as predefined weak linkages has enabled the creation of mechanoresponsive and mechanochromic polymer materials, which are interesting for a range of applications including the study of biological specimens or advanced security features. In typical mechanophores, covalent bonds are broken when polymers that contain these chemical motifs are exposed to mechanical forces, and changes of the optical properties upon bond scission can be harnessed as a signal that enables the detection of applied mechanical stresses and strains. Similar chromic effects upon mechanical deformation of polymers can also be achieved without relying on the scission of covalent bonds. The dissociation of motifs that feature directional noncovalent interactions, the disruption of aggregated molecules, and conformational changes in molecules or polymers constitute an attractive element for the design of mechanoresponsive and mechanochromic materials. In this article, it is reviewed how such alterations of molecules and polymers can be exploited for the development of mechanochromic materials that signal deformation without breaking covalent bonds. Recent illustrative examples are highlighted that showcase how the use of such mechanoresponsive motifs enables the visual mapping of stresses and damage in a reversible and highly sensitive manner.

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production.

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.