Structural Elucidation of Amorphous Photocatalytic Polymers from Dynamic Nuclear Polarization Enhanced Solid State NMR #DNPNMR
Brownbill, Nick J., Reiner Sebastian Sprick, Baltasar Bonillo, Shane Pawsey, Fabien Aussenac, Alistair J. Fielding, Andrew I. Cooper, and Frédéric Blanc. “Structural Elucidation of Amorphous Photocatalytic Polymers from Dynamic Nuclear Polarization Enhanced Solid State NMR.” Macromolecules 51, no. 8 (April 24, 2018): 3088–96.
Dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) oﬀers a recent approach to dramatically enhance NMR signals and has enabled detailed structural information to be obtained in a series of amorphous photocatalytic copolymers of alternating pyrene and benzene monomer units, the structures of which cannot be reliably established by other spectroscopic or analytical techniques. Large 13C cross-polarization (CP) magic angle spinning (MAS) signal enhancements were obtained at high magnetic ﬁelds (9.4− 14.1 T) and low temperature (110−120 K), permitting the acquisition of a 13C INADEQUATE spectrum at natural abundance and facilitating complete spectral assignments, including when small amounts of speciﬁc monomers are present. The high 13C signal-to-noise ratios obtained are harnessed to record quantitative multiple contact CP NMR data, used to determine the polymers’ composition. This correlates well with the putative pyrene:benzene stoichiometry from the monomer feed ratio, enabling their structures to be understood.