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 C60 and C70 fullerenes. In particular, dianthryl-TTFV exhibits unique selectivity for C70 fullerene, giving rise to effective fluorescence turn-on sensing of C70 in the presence of a large excess of C60 fullerene. This observation indicated that dianthryl-TTFV has a preferential binding affinity for C70 over C60 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 C70 and C60 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 propertiesshow that the dianthryl-TTFV and dipyrenyl-TTFV conformers have lowerhighest occupied molecular orbital–lowest unoccupied molecularorbital gaps relative to the ones obtained for dinaphthyl-TTFV, indicatingthat dianthryl-TTFV, and to some extend dipyrenyl-TTFV, could be goodcandidates for chemical sensing of fullerenes with fluorescence spectroscopy.We also investigated the effect of the solvent on the interactionsof the diaryl-TTFVs with fullerenes using the polarizable continuummodel. In general, the presence of a solvent decreases the diaryl-TTFV/fullerenebinding energies, presumably because of the interactions of the solventwith individual fullerenes and diaryl-TTFVs.
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