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

doi:10.1021/acs.jpca.8b05107

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

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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 »« less

Authors:

^[1]; Ryan, Matthew J. ^[2]; Biswas, Abhranil ^[2]; Boteju, Kasuni C. ^[2];

^[1];

^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

Publication Date:: 2018-06-04

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.

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                    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.

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                    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.

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@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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DOI: 10.1021/acs.jpca.8b05107

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