期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 13, 期 18, 页码 4000-4006出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c00748
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资金
- U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences through a DOE Early Career Project
- DOE [DE-AC02-07CH11358]
- University of Michigan-Dearborn
- Pacific Northwest National Laboratory
The Overhauser effect, which requires the modulation of electron-nuclear hyperfine interactions, dominates dynamic nuclear polarization (DNP) in liquids and metals. This effect can also occur in insulating solids through rapid structural modulations linked to a modulation in hyperfine coupling. In this study, the addition of a methyl group to Blatter's radical was found to trigger Overhauser DNP. The rotation of the methyl group leads to a modulation of the hyperfine coupling to its protons, facilitating electron-nuclear cross-relaxation. The findings suggest the possibility of designing tailor-made Overhauser DNP polarizing agents for high-field MAS-DNP.
The Overhauser effect is unique among DNP mechanisms in that it requiresthe modulation of the electron-nuclear hyperfine interactions. While it dominates DNP inliquids and metals, where unpaired electrons are highly mobile, Overhauser DNP is possiblein insulating solids if rapid structural modulations are linked to a modulation in hyperfinecoupling. Herein, we report that Overhauser DNP can be triggered by the strategic additionof a methyl group, demonstrated here in a Blatter's radical. The rotation of the methyl groupleads to a modulation of the hyperfine coupling to its protons, which in turn facilitateselectron-nuclear cross-relaxation. Removal of the methyl protons, through deuteration,quenches the process, as does the reduction of the hyperfine coupling strength. This resultsuggests the possibility for the design of tailor-made Overhauser DNP polarizing agents forhigh-field MAS-DNP
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