Terminal Diazirines Enable Reverse Polarization Transfer from ¹⁵ N₂ Singlets

Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The ¹⁵ N₂ labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long-lived lifetimes. The (-CH¹⁵ N₂ ) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (-CH¹⁵ N₂ ) moiety to ¹ H, thus combining the advantages of long lifetimes of ¹⁵ N polarization with superior sensitivity of ¹ H detection. Despite the proximity of ¹ H to ¹⁵ N nuclei in the diazirine moiety, ¹⁵ N T₁ times of up to (4.6±0.4) min and singlet lifetimes T_s of up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized ¹ H₂ singlet states in CH₂ groups of chiral molecules. The singlet lifetime of ¹ H singlets is up to (9.2±1.8) min, thus exceeding ¹ H T₁ relaxation time (at 8.45 T) by a factor of ≈100.