Structure assignment in the solid state by the coupling of quantum chemical calculations with NMR experiments: a...

We present a quantum chemical ab initio study which demonstrates a new combined experimental and theoretical approach, whereby a comparison of calculated and experimental (1)H NMR chemical shifts allows the elucidation of structural arrangements in solid-state molecular ensembles, taking advantage of the marked sensitivity of the (1)H chemical shift to intermolecular interactions. Recently, Brown et al. have shown that, under fast magic-angle spinning (MAS) at 35 kHz, the resolution in a (1)H NMR spectrum of the solid phase of an alkyl-substituted hexabenzocoronene (HBC) derivative is sufficient to observe the hitherto unexpected resolution of three distinct aromatic resonances ( J. Am. Chem. Soc. 1999, 121, 6712). Exploiting the additional information about proton proximities provided by (1)H double-quantum (DQ) MAS NMR spectroscopy, it was shown that the results are qualitatively consistent with the aromatic cores packing in a manner similar to that in unsubstituted HBC. Using the HBC-C(12) molecule as an example, we show here that the new combined experimental and theoretical approach allows the observed (1)H chemical shifts to be related in a quantitative manner to the intermolecular structure. In the quantum chemical calculations, a series of model systems of stacked HBC oligomers are used. On account of the marked dependence of the (1)H chemical shift to ring currents arising from nearby aromatic rings, the calculated (1)H chemical shifts are found to be very sensitive to the stacking arrangement of the HBC molecules. Moreover, the ring current effect is found to be particularly long range, with a considerable influence of the second neighbor, at a distance of 700 pm, being observed.