(1)H/(13)C chemical shift calculations for biaryls: DFT approaches to geometry optimization

Twelve common density functional methods and seven basis sets for geometry optimization were evaluated on the accuracy of (1)H/(13)C NMR chemical shift calculations for biaryls. For these functionals, (1)H shifts calculations for gas phase optimized geometries were significantly less accurate than those for in-solution optimized structures, while (13)C results were not strongly influenced by geometry optimization methods and solvent effects. B3LYP, B3PW91, mPW1PW91 and ωB97XD were the best-performing functionals with lowest errors; among seven basis sets, DGDZVP2 and 6-31G(d,p) outperformed the others. The combination of these functionals and basis sets resulted in high accuracy with CMAE(min) = 0.0327 ppm (0.76%) and 0.888 ppm (0.58%) for (1)H and (13)C, respectively. The selected functionals and basis set were validated when consistently producing optimized structures with high accuracy results for (1)H and (13)C chemical shift calculations of two other biaryls. This study highly recommends the IEFPCM/B3LYP, B3PW91, mPW1PW91 or ωB97XD/DGDZVP2 or 6-31G(d,p) level of theory for the geometry optimization step, especially the solvent incorporation, which would lead to high accuracy (1)H/(13)C calculation. This work would assist in the fully structural assignments of biaryls and provide insights into in-solution biaryl conformations.