Impact of intramolecular hydrogen bonding of gallic acid conformers on chemical shift through NMR spectroscopy

Abstract

Intramolecular hydrogen bonding of gallic acid conformers was probed as a function of their dihedral angles using 13C nuclear magnetic resonance (NMR) chemical shift (δC). The quantum mechanically calculated 13C NMR chemical shift based on the most stable conformer (GA-I) in dimethylsulfoxide (DMSO) solution agrees to available measurement in the same solvent (RMSD = 0.95 ppm), better than to the measurement in solid phase (RMSD = 1.93 ppm). The accuracy of the calculated NMR chemical shift of the nominal but non-equivalent phenyl carbons C(3)/C(7) and C(4)/C(6) (ortho and meta to the acid –C(1)OOH group) of GA may not be evaluated using the experimental measurements at room temperature. The splitting in chemical shift of the nominal phenyl carbons is able to be experimentally measured only in low temperature NMR and using quantum mechanical calculations. We further recognised that the C NMR chemical shifts of the nominal phenyl carbons (C(3)/C(7) and C(4)/C(6)) encode information for intramolecular hydrogen bonding network formed by GA conformers. The ability to obtain accurate splitting of NMR chemical shifts for nominal carbons, therefore, determines the usefulness of the NMR technique as a probe for conformation of GA.