Stacked homodimers of substituted contorted hexabenzocoronenes and their complexes with C₆₀ fullerene

Stacking interactions involving substituted contorted hexabenzocoronene (c-HBC) with C₆₀ were studied at the B97-D3M(BJ)/TZVPP//B97-D/TZV(2d,2p) level of theory. First, we showed that substituent effects in benzeneC₆₀ complexes are uncorrelated with those in the benzene sandwich dimer, underscoring the importance of local, direct interactions in substituent effects in stacking interactions. Second, we showed that c-HBC preferentially forms stacked homodimers over complexes with C₆₀; however, if the bowl depth of c-HBC is increased beyond 1.25 Å, the c-HBCC₆₀ complex becomes preferred over the c-HBC homodimer. Ultimately, we showed that the perfluorination of c-HBC leads to sufficient curvature to allow the c-HBCC₆₀ heterodimers to form preferentially over c-HBC homodimers, suggesting the possibility of the development of c-HBC derivatives that assemble into alternating stacks with C₆₀.