Conformational Analysis of the Supramolecular Complexation of Diaryl-Substituted Tetrathiafulvalene Vinylogues with Fullerenes

[Image: see text] Tetrathiafulvalene vinylogues (TTFVs) functionalized with diaryl substituents (aryl = 1-napthyl, 9-anthryl, and 1-pyrenyl) via click chemistry have been previously synthesized and studied as tweezer-type receptors for binding with C(60) and C(70) fullerenes. In particular, dianthryl-TTFV exhibits unique selectivity for C(70) fullerene, giving rise to effective fluorescence turn-on sensing of C(70) in the presence of a large excess of C(60) fullerene. This observation indicated that dianthryl-TTFV has a preferential binding affinity for C(70) over C(60) fullerene, but the reason for such selectivity is unclear. Aiming at addressing this issue, we herein investigated the relative conformational stability of diaryl-substituted TTFVs in complexation with C(70) and C(60) fullerenes. The dispersion-corrected density functional theory approximation (B3LYP-D3) was employed in our computational analysis to determine binding energies and electronic properties of these supramolecular complexes. It was found that the highest binding energies (and the lowest relative conformational energies) are in pairings when fullerenes are placed around the central TTFV moieties (such as the triazole rings). The results of electronic properties show that the dianthryl-TTFV and dipyrenyl-TTFV conformers have lower highest occupied molecular orbital–lowest unoccupied molecular orbital gaps relative to the ones obtained for dinaphthyl-TTFV, indicating that dianthryl-TTFV, and to some extend dipyrenyl-TTFV, could be good candidates for chemical sensing of fullerenes with fluorescence spectroscopy. We also investigated the effect of the solvent on the interactions of the diaryl-TTFVs with fullerenes using the polarizable continuum model. In general, the presence of a solvent decreases the diaryl-TTFV/fullerene binding energies, presumably because of the interactions of the solvent with individual fullerenes and diaryl-TTFVs.