Accuracy in Homonuclear Distance Determinations by Solid-State NMR Spectroscopy: The Benefits of Fast Magic-Angle Spinning up to 100 kHz
7 affiliations
- 1Max Planck Institute for Chemical Energy Conversion
- 2Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, Aachen, Germany, 52074
- 3Laboratory of Inorganic Chemistry, ETH Zürich, Vladimir-Prelog-Weg 2, Zürich, Switzerland, 8049
- 4Institute of Organic Chemistry
- 5Leipzig University
- 6Institute for a Sustainable Hydrogen Economy, Forschungszentrum Jülich, Wilhelm-Johnen-Straße, Jülich, Germany, 52428
- 7Bundesanstalt für Materialforschung und -Prüfung, Richard Willstätter-Strasse 11, Berlin, Germany, 12489
Abstract
Homonuclear distance measurements by solid-state nuclear magnetic resonance (NMR) spectroscopy under magic-angle spinning (MAS) conditions are key to structural analysis in complex materials. While a wide variety of dipolar recoupling techniques involving the excitation of double quantum (DQ) coherences is available, the excitation efficiency is critically affected by the chemical-shift anisotropy (CSA) and the (often unknown) relative orientations between chemical-shift and dipolar-coupling tensors of the involved nuclei. Here, we demonstrate that a previously reported DQ-based sequence, Constant-Time Dipolar Recoupling Effects Nuclear Alignment Reduction (CT-DRENAR), enables robust and highly accurate homonuclear distance determinations for 19F and 31P nuclei under fast MAS conditions up to 100 kHz. We establish a numerical simulation approach to investigate the uncertainties in such distance measurements arising from the orientational effects and show that they become negligible when the MAS frequency exceeds approximately twice the spectral dispersion due to the CSA. Using this numerical simulation approach for data analysis, 31P–31P and 19F–19F effective distances in crystalline model systems with shortest internuclear contacts of 3–5 Å and CSA magnitudes exceeding 100 ppm are determined with accuracies of 0.1–0.5 Å. The experiment is applied to probe the conformational change of a phosphine ligand upon ruthenium coordination in a heterogeneous solid molecular ruthenium-polyphosphine catalyst. These results demonstrate the suitability of CT-DRENAR as a reliable strategy for precise homonuclear distance measurements in complex functional materials.
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BibTeX
@misc{wu2026accuracy,
title = {{Accuracy in Homonuclear Distance Determinations by Solid-State NMR Spectroscopy: The Benefits of Fast Magic-Angle Spinning up to 100 kHz}},
author = {Yufei Wu and Julius Schlüter and Felix J. Byn and Janine C. Baums and Jonas Koppe and Tom Gabler and Kirsten Zeitler and Peter J. C. Hausoul and Regina Palkovits and Hellmut Eckert and Thomas Wiegand},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009842/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009842/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Accuracy in Homonuclear Distance Determinations by Solid-State NMR Spectroscopy: The Benefits of Fast Magic-Angle Spinning up to 100 kHz
AU - Yufei Wu
AU - Julius Schlüter
AU - Felix J. Byn
AU - Janine C. Baums
AU - Jonas Koppe
AU - Tom Gabler
AU - Kirsten Zeitler
AU - Peter J. C. Hausoul
AU - Regina Palkovits
AU - Hellmut Eckert
AU - Thomas Wiegand
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009842/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009842/v1
AB - Homonuclear distance measurements by solid-state nuclear magnetic resonance (NMR) spectroscopy under magic-angle spinning (MAS) conditions are key to structural analysis in complex materials. While a wide variety of dipolar recoupling techniques involving the excitation of double quantum (DQ) coherences is available, the excitation efficiency is critically affected by the chemical-shift anisotropy (CSA) and the (often unknown) relative orientations between chemical-shift and dipolar-coupling tensors of the involved nuclei. Here, we demonstrate that a previously reported DQ-based sequence, Constant-Time Dipolar Recoupling Effects Nuclear Alignment Reduction (CT-DRENAR), enables robust and highly accurate homonuclear distance determinations for 19F and 31P nuclei under fast MAS conditions up to 100 kHz. We establish a numerical simulation approach to investigate the uncertainties in such distance measurements arising from the orientational effects and show that they become negligible when the MAS frequency exceeds approximately twice the spectral dispersion due to the CSA. Using this numerical simulation approach for data analysis, 31P–31P and 19F–19F effective distances in crystalline model systems with shortest internuclear contacts of 3–5 Å and CSA magnitudes exceeding 100 ppm are determined with accuracies of 0.1–0.5 Å. The experiment is applied to probe the conformational change of a phosphine ligand upon ruthenium coordination in a heterogeneous solid molecular ruthenium-polyphosphine catalyst. These results demonstrate the suitability of CT-DRENAR as a reliable strategy for precise homonuclear distance measurements in complex functional materials.
ER -