Controlling the Guanidinium Cation Rotation by Cation–π Interactions
Angewandte Chemie International Edition, vol. 65, pp. e3934559
Abstract
ABSTRACT Guanidinium plays an essential role in many disciplines of biology and chemistry, particularly due to its unique role of being engaged in a variety of molecular‐recognition events that are facilitated by the ability to participate in a broad range of noncovalent interactions. Guanidinium cations in salts or perovskite materials are known to rotate along their local symmetry axes rather fast in the order of ps , even in the solid state. We herein employ a π‐container to trap a guanidinium cation inside the aromatic cavity by cation–π interactions. X‐ray crystallography and solid‐state nuclear magnetic resonance (NMR) spectroscopy at fast magic‐angle spinning (MAS) frequencies have been utilized to probe the underlying host–guest interactions. The guanidinium motion has been fully characterized by temperature‐dependent MAS‐NMR experiments down to 100 K, as well as by a variety of further solid‐state NMR experiments, and supplemented by quantum‐chemical calculations and molecular dynamics (MD) simulations. Our data point to a restriction of the guanidinium cation rotation about the local C 3 ‐axis with correlation times in the order of ns . Our study, therefore, showcases that using the calixarene framework as a bearing for trapping a guanidinium cation, we are getting closer to the chemist's dream of controlling molecular rotations.
Authors 13
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Max Planck Institute for Chemical Energy Conversion · RWTH Aachen University
Affiliation as printed
Institute of Technical and Macromolecular Chemistry RWTH Aachen University Aachen Germany
Max Planck Institute For Chemical Energy Conversion Mülheim a. d. Ruhr Germany
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Affiliation as printed
Institute of Inorganic Chemistry and Crystallography Leipzig University Leipzig Germany
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Max Planck Institute for Chemical Energy Conversion · École Polytechnique Fédérale de Lausanne · RWTH Aachen University
Affiliation as printed
Institute of Technical and Macromolecular Chemistry RWTH Aachen University Aachen Germany
Max Planck Institute For Chemical Energy Conversion Mülheim a. d. Ruhr Germany
Present address: Laboratory of Computational Chemistry and Biochemistry EPFL Lausanne Switzerland
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Affiliation as printed
Institute of Inorganic Chemistry and Crystallography Leipzig University Leipzig Germany
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Affiliation as printed
Institute of Inorganic Chemistry and Crystallography Leipzig University Leipzig Germany
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Affiliation as printed
Institute of Inorganic Chemistry and Crystallography Leipzig University Leipzig Germany
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Affiliation as printed
Center For Computational Life Sciences RWTH Aachen University Aachen Germany
Computational Biotechnology RWTH Aachen University Aachen Germany
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Affiliation as printed
Institute of Chemistry and Department of Life, Light & Matter University of Rostock Rostock Germany
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Affiliation as printed
Institute of Chemistry and Department of Life, Light & Matter University of Rostock Rostock Germany
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Affiliation as printed
Center For Computational Life Sciences RWTH Aachen University Aachen Germany
Computational Biotechnology RWTH Aachen University Aachen Germany
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ETH Zurich · Institute of Molecular Physical Science
Affiliation as printed
Institute For Molecular Physical Sciences, ETH Zürich Zürich Switzerland
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Berthold Kersting corresponding
Affiliation as printed
Institute of Inorganic Chemistry and Crystallography Leipzig University Leipzig Germany
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Max Planck Institute for Chemical Energy Conversion · RWTH Aachen University
Affiliation as printed
Institute of Technical and Macromolecular Chemistry RWTH Aachen University Aachen Germany
Max Planck Institute For Chemical Energy Conversion Mülheim a. d. Ruhr Germany
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