Chemically Induced Mismatch of Rings and Stations in Rotaxanes
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Embargo End Date2022-04-29
Permanent link to this recordhttp://hdl.handle.net/10754/669028
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AbstractThe mechanical interlocking of molecular components can lead to the appearance of novel and unconventional properties and processes, with potential relevance for applications in nanoscience, sensing, catalysis, and materials science. We describe a rotaxane in which the number of recognition sites available on the axle component can be changed by acid-base inputs, encompassing cases in which this number is larger, equal to, or smaller than the number of interlocked macrocycles. These species exhibit very different properties and give rise to a unique network of acid-base reactions that leads to a fine p<i>K</i><sub>a</sub> tuning of chemically equivalent acidic sites. The rotaxane where only one station is available for two rings exhibits a rich coconformational dynamics, unveiled by an integrated experimental and computational approach. In this compound, the two crown ethers compete for the sole recognition site, but can also come together to share it, driven by the need to minimize free energy without evident inter-ring interactions.
CitationCurcio, M., Nicoli, F., Paltrinieri, E., Fois, E., Tabacchi, G., Cavallo, L., … Credi, A. (2021). Chemically Induced Mismatch of Rings and Stations in Rotaxanes. Journal of the American Chemical Society. doi:10.1021/jacs.1c02230
SponsorsThis work was supported by the European Union’s H2020 Research and Innovation Program (ERC Advanced Grant n.692981), the Italian Ministry of University and Research (FARE R16S9XXKX3 and PRIN 20173L7W8K), and FAR2019 Uninsubria, and L.C. and E.F. acknowledge the King Abdullah University of Science and Technology (KAUST) and the KAUST Supercomputing Laboratory (KSL) for support and for providing computational resources on the Shaheen II HPC system (project K1438).
PublisherAmerican Chemical Society (ACS)
Except where otherwise noted, this item's license is described as This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.1c02230.
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