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

Venkatesh, Amrit; Ryan, Matthew J.; Biswas, Abhranil; Boteju, Kasuni C.; Sadow, Aaron D.; Rossini, Aaron J.

doi:10.1021/acs.jpca.8b05107

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

Journal Article · Mon Jun 04 04:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b05107· OSTI ID:1459536

^[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

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 to enable and accelerate solid-state NMR experiments with very low-γ nuclei.

View Accepted Manuscript (DOE)

Research Organization:: Ames Lab. and Iowa State Univ., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1459536

Report Number(s):: IS--J 9683

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 25 Vol. 122; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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