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Dynamic nuclear polarization (DNP) is an NMR sensitivity enhancementtechnique that mediates polarization transfer from unpaired electrons toNMR-active nuclei. Despite its success in elucidating important structuralinformation on biological and inorganic materials, the detailedpolarization-transfer pathway-from the electrons to the nearby and then thebulk solvent nuclei, and finally to the molecules of interest-remains unclear.In particular, the nuclei in the paramagnetic polarizing agent play significantroles in relaying the enhanced NMR polarizations to more remote nuclei. Despitetheir importance, the direct NMR observation of these nuclei is challengingbecause of poor sensitivity. Here, we show that a combined DNP and electrondecoupling approach can facilitate direct NMR detection of these nuclei. Weachieved an ~80 % improvement in NMR intensity via electron decoupling at 0.35T and 80 K on trityl radicals. Moreover, we recorded a DNP enhancement factorof $\epsilon$ ~ 90 and ~11 % higher NMR intensity using electron decoupling ona paramagnetic metal-organic framework, magnesium hexaoxytriphenylene (MgHOTPMOF).

Observing Nearby Nuclei on Paramagnetic Trityls and MOFs via DNP and Electron Decoupling