Science Advances

Supplementary Materials

This PDF file includes:

  • Synthesis of 15N2-diazirine and iridium precatalyst
  • Theoretical derivation of resonance conditions for hyperpolarization transfer
  • Spin dynamics during low- to high-field sample transfer
  • MD simulations of possible transitions states for hyperpolarization transfer
  • Sample preparation and setup to obtain well-controlled milligauss fields
  • Hyperpolarization buildup dynamics, lifetimes, and enhancements in detail
  • Appendix
  • Fig. S1. Synthesis of 2-cyano-3-(3′-(methyl-d3)-3′H-diazirine-3′-yl-1′,2′-15N2) propanoic acid using modified literature procedures.
  • Fig. S2. Spin system for polarization transfer.
  • Fig. S3. Eigenstates of a J-coupled two-spin system as a function of magnetic field.
  • Fig. S4. Simulated spectra for magnetization and singlet order.
  • Fig. S5. Three candidate conformations of 2-cyano-3-(D3-methyl-15N2-diazirine)-propanoic acid as identified by DFT PBE + TS calculations, as used to construct likely catalytically active structures producing hyperpolarization attached to the SABRE catalyst.
  • Fig. S6. First-principles derived candidate conformations of catalytic species that drive hyperpolarization transfer.
  • Fig. S7. Experimental SABRE-SHEATH setup.
  • Fig. S8. Decay time constants, buildup constants, and enhancements as function of magnetic field and concentrations.
  • Fig. S9. The effect of continued singlet-polarization buildup after stopping p-H2 bubbling.
  • Table S1. Relative energies of the diazirine attachment modes tested in this work for the case of two different ligands that are simultaneously present: two equatorial hydrides, axial IMes, axial pyridine, one equatorial pyridine, and diazirine in an equatorial position.
  • Table S2. Relative energies of the diazirine attachment modes tested in this work for the case of two diazirine molecules that are simultaneously present.
  • Table S3. Magnetization lifetimes, T1, under varying catalyst concentrations and holding fields.
  • Table S4. Singlet lifetimes, TS, under varying catalyst concentrations and holding fields.
  • Table S5. Magnetization buildup times, Tb1, at 6 mG under varying catalyst concentrations.
  • Table S6. Singlet buildup times, TbS, under varying catalyst concentrations and magnetic fields.
  • Table S7. Enhancements, ε, under varying concentrations of catalyst IrCl(COD)(IMes) (1a), Ir(COD)(IMes)(Py)PF6 (1b), diazirine substrate (2), pyridine (3), and D2O (4).
  • References (55–69)

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