Weak Intermolecular CH···N Hydrogen Bonding: Determination of ¹³CH-¹⁵N Hydrogen-Bond Mediated J Couplings by...

Weak hydrogen bonds are increasingly hypothesized to play key roles in a wide range of chemistry from catalysis to gelation to polymer structure. Here, ¹⁵N/¹³C spin-echo magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) experiments are applied to "view" intermolecular CH···N hydrogen bonding in two selectively labeled organic compounds, 4-[¹⁵N] cyano-4'-[¹³C₂] ethynylbiphenyl (1) and [¹⁵N₃,¹³C₆]-2,4,6-triethynyl-1,3,5-triazine (2). The synthesis of 2-N,C is reported here for the first time via a multistep procedure, where the key element is the reaction of [¹⁵N₃]-2,4,6-trichloro-1,3,5-triazine (5) with [¹³C₂]-[(trimethylsilyl)ethynyl]zinc chloride (8) to afford its immediate precursor [¹⁵N₃,¹³C₆]-2,4,6-tris[(trimethylsilyl)ethynyl]-1,3,5-triazine (9). Experimentally determined hydrogen-bond-mediated ^2hJ_CN couplings (4.7 ± 0.4 Hz (1) and 4.1 ± 0.3 Hz (2)) are compared with density functional theory (DFT) gauge-including projector augmented wave (GIPAW) calculations, whereby species-independent coupling values ^2hK_CN (29.0 × 10¹⁹ kg m^-2 s^-2 A^-2 (1) and 27.9 × 10¹⁹ kg m^-2 s^-2 A^-2 (2)) quantitatively demonstrate the J couplings for these "weak" CH···N hydrogen bonds to be of a similar magnitude to those for conventionally observed NH···O hydrogen-bonding interactions in uracil (^2hK_NO: 28.1 and 36.8 × 10¹⁹ kg m^-2 s^-2 A^-2). Moreover, the GIPAW calculations show a clear correlation between increasing ^2hJ_CN (and ^3hJ_CN) coupling and reducing C(H)···N and H···N hydrogen-bonding distances, with the Fermi contact term accounting for at least 98% of the isotropic ^2hJ_CN coupling.