Multicomponent Supramolecular Copolymerization for Controlled Defect Engineering
Project area:
Preparatory and Physical Chemistry of Polymers
Project leader:
Dhiman Shikha, Jun.-Prof. Dr.
Johannes Gutenberg-Universität Mainz
Department of Chemistry
Duesbergweg 10–14, 55128 Mainz
Phone: +49 (0)6131 39-30517
shikha.dhiman[a]uni-mainz.de
Summary
Supramolecular materials that are composed of small building blocks interacting through non-covalent interactions offer promising applications in various fields.P1-P2 The dynamic nature of supramolecular polymers, which contributes to their highly desirable adaptive and responsive behavior, is believed to stem from defects in the monomer packing. Defect engineering is a well-established strategy in hard materials to control properties and achieve emergent characteristics. While extensive research has focused on achieving precise structures in supramolecular polymers,P3-P6 the potential of incorporating defects in the realm of supramolecular polymers has been unexplored. This proposal aims to deviate from the pursuit of precision supramolecular polymers and instead explore precision defect engineering. Preliminary results suggest the existence of intrinsic defects in supramolecular polymers, which can be harnessed by introducing dopants that exhibit optimal misfit penalties,P7-P8 allowing co-assembly while inducing disorder. Innovative experimental methodsP9 will be developed to identify and characterize defects at different lengths and time scales, examining their formation and determining whether they evolve or remain static (Figure 1). Additionally, defect engineering strategies will be devised, utilizing doping defects to manipulate the physical and chemical properties of supramolecular polymers. By systematically varying the proportions of multiple components, the extent of defect formation can be regulated. Furthermore, to understand the relationship between the preparation pathway and defect generation, alternative preparation methods using multicomponent supramolecular copolymerization of monomer and dopant will be explored.P7,P8,P10 The ultimate objective is to learn about the existence of defects, develop methods for defect engineering, and control defects in supramolecular polymers, which will pave the way for programming physical and chemical properties of supramolecular materials.P1 This study will be supported by theoretical modelling in the group of Friederike Schmid, who is a PI of the Project C02 within the SFB1552.
This project addresses a central question in SFB1552, namely: Are there intrinsic defects present in supramolecular polymers? How can we identify defects? Are these defects static or dynamic? How can defects be engineered in supramolecular polymers? It will not only give insight into fundamental aspects of defect and defect engineering in supramolecular polymers but will also provide tools to create new supramolecular materials.
Figure 1. Schematic illustration of this proposal. This proposal aims to O1: identify and understand defects in supramolecular polymers, O2: develop defect engineering strategies using doping defects, and O3: investigate the impact of preparation methods on defects.
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[P1] Temporally Controlled Supramolecular Polymerization, Dhiman, S. J. George, Bull. Chem. Soc. of Jpn., 2018, 91, 687-699. https://doi.org/10.1246/bcsj.20170433 [P2] ATP‐Driven Synthetic Supramolecular Assemblies: From ATP as a Template to Fuel, A. Mishra,ǂ Dhiman,ǂ S. J. George, Angew. Chem. Int. Ed., 2021, 60, 2740-2756. https://doi.org/10.1002/anie.202006614 [P3] Adenosine-Phosphate-Fueled, Temporally Programmed Supramolecular Polymers with Multiple Transient States, S. Dhiman, A. Jain, M. Kumar, S. J. George, Am. Chem. Soc., 2017, 139, 16568-16575. https://doi.org/10.1002/anie.202006614 [P4] Transient Helicity: Fuel‐Driven Temporal Control over Conformational Switching in a Supramolecular Polymer, Dhiman, A. Jain, S. J. George, Angew. Chem. Int. Ed., 2017, 56, 1329-1333. https://doi.org/10.1002/anie.201610946 [P5] Chemical fuel-driven living and transient supramolecular polymerization, A. Jain, S. Dhiman, A. Dhayani, P. K. Vemula, S. J. George, Commun., 2019, 10, 450. https://doi.org/10.1038/s41467-019-08308-9 [P6] Redox-Mediated, Transient Supramolecular Charge-Transfer Gel and Ink, Dhiman, K. Jalani, S. J. George, ACS Appl. Mater. Interfaces, 2020, 12, 5259-5264. https://doi.org/10.1021/acsami.9b17481 [P7] Visualization of Stereoselective Supramolecular Polymers by Chirality‐Controlled Energy Transfer, A. Sarkar, S. Dhiman, A. Chalishazar, S. J. George, Chem. Int. Ed., 2017, 56, 13767-13771. https://doi.org/10.1002/anie.201708267 [P8] Self-Sorted, Random, and Block Supramolecular Copolymers via Sequence Controlled, Multicomponent Self-Assembly, A. Sarkar, R. Sasmal, C. Empereur-mot, D. Bochicchio, S. V. K. Kompella, K. Sharma, S. Dhiman, S. Balasubramanian, S. S. Agasti, G. M. Pavan, S. J. George, Am. Chem. Soc., 2020, 142, 7606–7617. https://doi.org/10.1021/jacs.0c01822 [P9] Can Super-Resolution Microscopy Become a Standard Characterization Technique for Material Chemistry? S. Dhiman, T. Andrian, B. S. Gonzalez, M. Tholen, Y. Wang, L. Albertazzi, Chem. Sci. 2022, 13, 2152-2166. https://doi.org/10.1039/D1SC05506B [P10] Dilution-Induced Gel-Sol-Gel-Sol Transitions by Competitive Supramolecular Pathways in Water, L. Su, J. Mosuqera, M. F. J. Mabesoone, S. M. C. Schoenmakers, C. Muller, M. E. J. Vleugels, S. Dhiman, S. Wijkers, A. R. A. Palmans, E. W. Meijer, Science 2022, 377, 213-218. https://doi.org/10.1126/science.abn3438