Solid-State ¹⁷ O NMR Reveals Hydrogen-Bonding Energetics: Not All Low-Barrier Hydrogen Bonds Are Strong

While NMR and IR spectroscopic signatures and structural characteristics of low-barrier hydrogen bond (LBHB) formation are well documented in the literature, direct measurement of the LBHB energy is difficult. Here, we show that solid-state ¹⁷ O NMR spectroscopy can provide unique information about the energy required to break a LBHB. Our solid-state ¹⁷ O NMR data show that the HB enthalpy of the O⋅⋅⋅H⋅⋅⋅N LBHB formed in crystalline nicotinic acid is only 7.7±0.5 kcal mol^-1 , suggesting that not all LBHBs are particularly strong.