Mechanochemistry in Polymeric Materials
Mechanically responsive polymeric materials.
Biological processes, such as cell-cell contacts, cell motility or even haptic perception (touch) all rely on the conversion of mechanical stimuli into chemical energy. Building on our expertise in the field of mechano-responsive polymers, we are exploring a new family of polymeric materials that translate mechanical forces into chemical reactions. These reactions, in turn, are used to bestow polymers with unusual and previously unavailable functionalities, such as mechanical morphing, mechanically induced generation of light, mechanically controlled cell growth, auto-lubricating behavior, and the ability to release small molecules such as drugs, fragrances and antiseptics.
Current research efforts include the design of new mechanically responsive motifs or “mechanophores”, the development of a predictive understanding for the relationships between the connectivity of such mechanophores with a matrix polymer, the morphology and mechanical properties of the system, and the mechanoresponse. Several mechanophores that rely on either homolytic (radical formation) or heterolytic cleavage of covalent bonds are being studied in this context. In parallel, non-covalent mechanophores based on excimer-forming dyes, cavitands, and supramolecular motifs such as metal-ligand complexes are being developed.
Selected research examples
Metal-ligand complexes are particularly promising for mechanochemical active systems as they offer a great opportunity to control the strength of the complex through the metal-ligand interaction. Recent results (J. Am. Chem. Soc. 2014, 136, 10493) showed that these metal-ligand complexes are mechanoresponsive in both solution as well as in the solid state. Currently, the details of these materials are under investigation on different length scales, ranging from the single-molecule level to macroscopic polymer films.
Hydrogen-bonding supramolecular binding motifs can be readily employed to derivatized dyes that display mechanoresponsive luminescent behavior. While hundreds of such dyes are known (Adv. Mater. 2016, 28, 1073), they generally do not display any useful mechanical properties. We have demonstrated that this can be overcome by introducing self-complementary hydrogen-bonding groups to promote the self-assembly of an excimer-forming cyano-substituted oligo(p-phenylene vinylene) derivative into a supramolecular polymer (J. Am. Chem. Soc., 2017, 139, 4302).
Novel covalent mechanophores are explored to prepare polymers that yield a tangible optical response to a mechanical stimulus. In particular, we focus on self-reporting materials that display a mechanically-triggered change of the fluorescence emission properties.
- Related publications
Mechanochemistry with Metallosupramolecular Polymers
Balkenende Diederik W. R., Coulibaly Souleymane, Balog Sandor, Simon Yoan C., Fiore Gina L., Weder Christoph
Journal of the American Chemical Society (2014)Mechanoresponsive Luminescence: Mechanoresponsive Luminescent Molecular Assemblies: An Emerging Class of Materials (Adv. Mater. 6/2016)
Sagara Yoshimitsu, Yamane Shogo, Mitani Masato, Weder Christoph, Kato Takashi
Advanced Materials (2016)Mechano- and Thermoresponsive Photoluminescent Supramolecular Polymer
Lavrenova Anna, Balkenende Diederik W. R., Sagara Yoshimitsu, Schrettl Stephen, Simon Yoan C., Weder Christoph
Journal of the American Chemical Society (2017)Self-Calibrating Mechanochromic Fluorescent Polymers Based on Encapsulated Excimer-Forming Dyes
Calvino Céline, Guha Anirvan, Weder Christoph, Schrettl Stephen
Advanced Materials (2018)Rotaxanes as Mechanochromic Fluorescent Force Transducers in Polymers
Sagara Yoshimitsu, Karman Marc, Verde-Sesto Ester, Matsuo Kazuya, Kim Yuna, Tamaoki Nobuyuki, Weder Christoph
Journal of the American Chemical Society (2018)Mechanochemical Fluorescence Switching in Polymers Containing Dithiomaleimide Moieties
Karman Marc, Verde-Sesto Ester, Weder Christoph, Simon Yoan C.
ACS Macro Letters (2018)Mechanoresponsive, Luminescent Polymer Blends Based on an Excimer-Forming Telechelic Macromolecule
Calvino Céline, Sagara Yoshimitsu, Buclin Véronique, Haehnel Alexander P., del Prado Anselmo, Aeby Christian, Simon Yoan C., Schrettl Stephen, Weder Christoph
Macromolecular Rapid Communications (2018)Rotaxane-Based Mechanophores Enable Polymers with Mechanically Switchable White Photoluminescence
Sagara Yoshimitsu, Karman Marc, Seki Atsushi, Pannipara Mehboobali, Tamaoki Nobuyuki, Weder Christoph
ACS Central Science (2019)Preparation of metallosupramolecular single-chain polymeric nanoparticles and their characterization by Taylor dispersion
Neumann Laura N., Urban Dominic A., Lemal Philipp, Ramani Sushila, Petri-Fink Alke, Balog Sandor, Weder Christoph, Schrettl Stephen
Polymer Chemistry (2020)Mechanochromic Polymers Based on Microencapsulated Solvatochromic Dyes
Calvino Céline, Henriet Emma, Muff Livius F., Schrettl Stephen, Weder Christoph
Macromolecular Rapid Communications (2020)Structure–Property Relationships of Microphase-Separated Metallosupramolecular Polymers
Neumann Laura N., Gunkel Ilja, Barron Amber, Oveisi Emad, Petzold Albrecht, Thurn-Albrecht Thomas, Schrettl Stephen, Weder Christoph
Macromolecules (2020)From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials
Traeger Hanna, Kiebala Derek J., Weder Christoph, Schrettl Stephen
Macromolecular Rapid Communications (2020)Mechanochromism in Structurally Colored Polymeric Materials
Clough Jess M., Weder Christoph, Schrettl Stephen
Macromolecular Rapid Communications (2020)Mechanoresponsive Elastomers Made with Excimer-Forming Telechelics
Kiebala Derek J., Fan Zhiyuan, Calvino Celine, Fehlmann Lauren, Schrettl Stephen, Weder Christoph
Organic Materials (2020)Tuning the Properties of Shape‐Memory Polyurethanes via the Nature of the Polyester Switching Segment
Karasu Feyza, Weder Christoph
Macromolecular Materials and Engineering (2021)Mechanically Responsive Luminescent Polymers Based on Supramolecular Cyclophane Mechanophores
Sagara Yoshimitsu, Traeger Hanna, Li Jie, Okado Yuji, Schrettl Stephen, Tamaoki Nobuyuki, Weder Christoph
Journal of the American Chemical Society (2021)Dynamics and healing behavior of metallosupramolecular polymers
Neumann Laura N., Oveisi Emad, Petzold Albrecht, Style Robert W., Thurn-Albrecht Thomas, Weder Christoph, Schrettl Stephen
Science Advances (2021)Folded Perylene Diimide Loops as Mechanoresponsive Motifs
Traeger Hanna, Sagara Yoshimitsu, Kiebala Derek J., Schrettl Stephen, Weder Christoph
Angewandte Chemie International Edition (2021)Tough Bioinspired Composites That Self-Report Damage
Magrini Tommaso, Kiebala Derek, Grimm Dominique, Nelson Anna, Schrettl Stephen, Bouville Florian, Weder Christoph, Studart André R.
ACS Applied Materials & Interfaces (2021)Folded Perylene Diimide Loops as Mechanoresponsive Motifs
Traeger Hanna, Sagara Yoshimitsu, Kiebala Derek J., Schrettl Stephen, Weder Christoph
Angewandte Chemie (2021)Rotaxane-Based Dual Function Mechanophores Exhibiting Reversible and Irreversible Responses
Muramatsu Tatsuya, Okado Yuji, Traeger Hanna, Schrettl Stephen, Tamaoki Nobuyuki, Weder Christoph, Sagara Yoshimitsu
Journal of the American Chemical Society (2021)Modeling ultrasound-induced molecular weight decrease of polymers with multiple scissile azo-mechanophores
Ayer Mathieu A., Verde-Sesto Ester, Liu Cheyenne H., Weder Christoph, Lattuada Marco, Simon Yoan C.
Polymer Chemistry (2021)Heterolytic Bond Cleavage in a Scissile Triarylmethane Mechanophore
Hemmer James R., Rader Chris, Wilts Bodo D., Weder Christoph, Berrocal José Augusto
Journal of the American Chemical Society (2021)Mechanically robust supramolecular polymer co-assemblies
Sautaux Julien, Marx Franziska, Gunkel Ilja, Weder Christoph, Schrettl Stephen
Nature Communications (2022)Metallosupramolecular polymers as precursors for platinum nanocomposites
Cappelletti Claudio, Olaechea Luis M., Ianiro Alessandro, Prado-Martínez Cristina, Oveisi Emad, Weder Christoph, Schrettl Stephen
Polymer Chemistry (2022)Strain-correlated mechanochromism in different polyurethanes featuring a supramolecular mechanophore
Traeger Hanna, Sagara Yoshimitsu, Berrocal José Augusto, Schrettl Stephen, Weder Christoph
Polymer Chemistry (2022)A perspective on the force-induced heterolytic bond cleavage in triarylmethane mechanophores
Berrocal José Augusto, Hemmer James Robert
Synlett (2022)Excited State Charge‐Transfer Complexes Enable Fluorescence Color Changes in a Supramolecular Cyclophane Mechanophore
Thazhathethil Shakkeeb, Muramatsu Tatsuya, Tamaoki Nobuyuki, Weder Christoph, Sagara Yoshimitsu
Angewandte Chemie International Edition (2022)
- Related projects
Projects of SCHRETTL Stephen
Projects of WEDER Christoph