Probing a Hydrogen-π Interaction Involving a Trapped Water Molecule in the Solid State

Ettore Bartalucci; Alexander A Malär; Anne Mehnert; Julius B Kleine Büning; Lennart Günzel; Maik Icker; Martin Börner; Christian Wiebeler; Beat H Meier; Stefan Grimme; Berthold Kersting; Thomas Wiegand

doi:10.1002/anie.202217725

Probing a Hydrogen-π Interaction Involving a Trapped Water Molecule in the Solid State

Angew Chem Int Ed Engl. 2023 Mar 27;62(14):e202217725. doi: 10.1002/anie.202217725. Epub 2023 Feb 21.

Authors

Ettore Bartalucci^{1

2}, Alexander A Malär³, Anne Mehnert⁴, Julius B Kleine Büning⁵, Lennart Günzel⁴, Maik Icker⁶, Martin Börner⁴, Christian Wiebeler^{7

8}, Beat H Meier³, Stefan Grimme⁵, Berthold Kersting⁴, Thomas Wiegand^{1

2

9}

Affiliations

¹ Max-Planck-Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
² Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074, Aachen, Germany.
³ Physical Chemistry, ETH Zurich, 8093, Zurich, Switzerland.
⁴ Institute of Inorganic Chemistry, Leipzig University, Johannisallee 29, 04103, Leipzig, Germany.
⁵ Mulliken Center for Theoretical Chemistry, Clausius Institute of Physical and Theoretical Chemistry, University of Bonn, Beringstraße 4, 53115, Bonn, Germany.
⁶ Institute of Organic Chemistry, Leipzig University Linnéstraße 3, 04103, Leipzig, Germany.
⁷ Institute of Analytic Chemistry, Leipzig University, Linnéstraße 3, 04103, Leipzig, Germany.
⁸ Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Leipzig University, Linnéstraße 2, 04103, Leipzig, Germany.
⁹ previous address: Physical Chemistry, ETH Zurich, 8093, Zurich, Switzerland.

PMID: 36630178
DOI: 10.1002/anie.202217725

Abstract

The detection and characterization of trapped water molecules in chemical entities and biomacromolecules remains a challenging task for solid materials. We herein present proton-detected solid-state Nuclear Magnetic Resonance (NMR) experiments at 100 kHz magic-angle spinning and at high static magnetic-field strengths (28.2 T) enabling the detection of a single water molecule fixed in the calix[4]arene cavity of a lanthanide complex by a combination of three types of non-covalent interactions. The water proton resonances are detected at a chemical-shift value close to zero ppm, which we further confirm by quantum-chemical calculations. Density Functional Theory calculations pinpoint to the sensitivity of the proton chemical-shift value for hydrogen-π interactions. Our study highlights how proton-detected solid-state NMR is turning into the method-of-choice in probing weak non-covalent interactions driving a whole branch of molecular-recognition events in chemistry and biology.

Keywords: Calixarene; DFT; Hydrogen-π Interaction; Lanthanide; Solid-State NMR.

Abstract

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