J. Am. Chem. Soc., 130 (38), 12663–12670, 2008.

Density Functional Theory Calculations of Hydrogen-Bond-Mediated NMR J Coupling in the Solid State
Siân A. Joyce,† Jonathan R. Yates,*‡ Chris J. Pickard,§ and Steven P. Brown∥

Abstract:
A recently developed method for calculating NMR J coupling in solid-state systems is applied to calculate hydrogen-bond-mediated 2hJNN couplings across intra- or intermolecular N−H···N hydrogen bonds in two 6-aminofulvene-1-aldimine derivatives and the ribbon structure formed by a deoxyguanosine derivative. Excellent quantitative agreement is observed between the calculated solid-state J couplings and those previously determined experimentally in two recent spin-echo magic-angle-spinning NMR studies (Brown, S. P.; et al. Chem. Commun.2002, 1852−1853 and Pham, T. N.; et al. Phys. Chem. Chem. Phys. 2007, 9, 3416−3423). For the 6-aminofulvene-1-aldimines, the differences in 2hJNN couplings in pyrrole and triazole derivatives are reproduced, while for the guanosine ribbons, an increase in 2hJNN is correlated with a decrease in the N−H···N hydrogen-bond distance. J couplings are additionally calculated for isolated molecules of the 6-aminofulevene-1-aldimines extracted from the crystal with and without further geometry optimization. Importantly, it is shown that experimentally observed differences between J couplings determined by solution- and solid-state NMR are not solely due to differences in geometry; long-range electrostatic effects of the crystal lattice are shown to be significant also. J couplings that are yet to be experimentally measured are calculated. Notably, 2hJNO couplings across N−H···O hydrogen bonds are found to be of a similar magnitude to 2hJNN couplings, suggesting that their utilization and quantitative determination should be experimentally feasible.