The inherently low sensitivity of nuclear magnetic resonance (NMR) spectroscopy is the major limiting factor for its application to elucidate structure and dynamics in solids. In the solid state, nuclear spin hyperpolarization methods based on microwave-induced dynamic nuclear polarization (DNP) provide a versatile platform to enhance the bulk NMR signal of many different sample formulations, leading to significant sensitivity improvements. Here we show that H NMR hyperpolarization can also be generated in solids at high magnetic fields by optical irradiation of the sample. We achieved this by exploiting a donor-chromophore-acceptor molecule with an excited state electron-electron interaction similar to the nuclear Larmor frequency, enabling solid-state H photochemically induced DNP (photo-CIDNP) at high magnetic fields. Through hyperpolarization relay, we obtained bulk NMR signal enhancements ε by factors of ∼100 at both 9.4 and 21.1 T for the H signal of -terphenyl in magic angle spinning (MAS) NMR experiments at 100 K. These findings open a pathway toward a general light-induced hyperpolarization approach for dye-sensitized high-field NMR in solids.
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| http://dx.doi.org/10.1021/jacs.4c06151 | DOI Listing |
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