Are there reliable DFT approaches for 13C NMR chemical shift predictions of fullerene C60 derivatives?

Abstract

AbstractThe relationships between experimental and theoretical 13C NMR chemical shifts of a pristine fullerene C60, monoadducts from [2 + n] cycloaddition (n = 1–3), and one [2 + 1] bis‐adduct are systematically analyzed for the first time by using diverse quantum‐chemical levels of theory. These levels involved B3LYP, B3PW91, B97‐2, mPW1PW91, PBE1PBE, and X3LYP hybrid functionals combined with 3‐21G, 6‐31G, 6‐31G(d), 6‐31G(d,p), 6‐31G(d,2p), LanL2DZ, and SDDAll basis sets. X3LYP/6‐31G approach is determined to have the lowest deviations from the 13C NMR experimental data compared to the other methods for all the fullerene compounds (mean absolute error value is 0.856 ppm and root mean squared error value is 1.197 ppm). The highest deviations are characteristic for α (sp2 C2/C5/C8/C10) and β (sp2 C6/C7/C11/C12) carbon atoms relative to a functionalization site and for those (sp3 C1/C9) directly attached with a side fragment in the [2 + n] monoadducts (n = 1–3). A probable reason of such deviation is that the approaches do not take into account a contribution of paramagnetic ring currents to 13C NMR chemical shifts. The results will be useful in design of novel fullerene derivatives and in performing unambiguous 13C NMR chemical shift assignments with modern quantum chemistry calculations.