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Title: Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection

Abstract

Many transition metals commonly encountered in inorganic materials and organometallic compounds possess NMR-active nuclei with very low gyromagnetic ratios (γ) such as 89Y, 103Rh, 109Ag, and 183W. A low-γ leads to poor NMR sensitivity and other experimental challenges. Consequently, nuclei with low-γ are often impossible to study with conventional solid-state NMR methods. In this paper, we combine fast magic angle spinning (MAS) and proton detection to enhance the sensitivity of solid-state NMR experiments with very low-γ nuclei by 1–2 orders of magnitude. Coherence transfer between 1H and low-γ nuclei was performed with low-power double quantum (DQ) or zero quantum (ZQ) cross-polarization (CP) or dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT). Comparison of the absolute sensitivity of CP NMR experiments performed with proton detection with 1.3 mm rotors and direct detection with 4 mm rotors shows that proton detection with a 1.3 mm rotor provides a significant boost in absolute sensitivity, while requiring approximately 1/40 th of the material required to fill a 4 mm rotor. Fast MAS and proton detection were applied to obtain 89Y and 103Rh solid-state NMR spectra of organometallic complexes. Finally, these results demonstrate that proton detection and fast MAS represents a general approach tomore » enable and accelerate solid-state NMR experiments with very low-γ nuclei.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  2. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Lab. and Iowa State Univ., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1459536
Report Number(s):
IS-J 9683
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 25; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., and Rossini, Aaron J. Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b05107.
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., & Rossini, Aaron J. Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection. United States. doi:10.1021/acs.jpca.8b05107.
Venkatesh, Amrit, Ryan, Matthew J., Biswas, Abhranil, Boteju, Kasuni C., Sadow, Aaron D., and Rossini, Aaron J. Mon . "Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection". United States. doi:10.1021/acs.jpca.8b05107. https://www.osti.gov/servlets/purl/1459536.
@article{osti_1459536,
title = {Enhancing the Sensitivity of Solid-State NMR Experiments with Very Low Gyromagnetic Ratio Nuclei with Fast Magic Angle Spinning and Proton Detection},
author = {Venkatesh, Amrit and Ryan, Matthew J. and Biswas, Abhranil and Boteju, Kasuni C. and Sadow, Aaron D. and Rossini, Aaron J.},
abstractNote = {Many transition metals commonly encountered in inorganic materials and organometallic compounds possess NMR-active nuclei with very low gyromagnetic ratios (γ) such as 89Y, 103Rh, 109Ag, and 183W. A low-γ leads to poor NMR sensitivity and other experimental challenges. Consequently, nuclei with low-γ are often impossible to study with conventional solid-state NMR methods. In this paper, we combine fast magic angle spinning (MAS) and proton detection to enhance the sensitivity of solid-state NMR experiments with very low-γ nuclei by 1–2 orders of magnitude. Coherence transfer between 1H and low-γ nuclei was performed with low-power double quantum (DQ) or zero quantum (ZQ) cross-polarization (CP) or dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT). Comparison of the absolute sensitivity of CP NMR experiments performed with proton detection with 1.3 mm rotors and direct detection with 4 mm rotors shows that proton detection with a 1.3 mm rotor provides a significant boost in absolute sensitivity, while requiring approximately 1/40th of the material required to fill a 4 mm rotor. Fast MAS and proton detection were applied to obtain 89Y and 103Rh solid-state NMR spectra of organometallic complexes. Finally, these results demonstrate that proton detection and fast MAS represents a general approach to enable and accelerate solid-state NMR experiments with very low-γ nuclei.},
doi = {10.1021/acs.jpca.8b05107},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 25,
volume = 122,
place = {United States},
year = {2018},
month = {6}
}

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