Molecular Basis for the Recognition of Higher Fullerenes into Ureidopyrimidinone-Cyclotriveratrylene Self-Assembled Capsules
E. Huerta, S. A. Serapian, E. Santos, E. Cequier, C. Bo, J. de Mendoza
Chem. Eur. J., 2016, DOI: 10.1002/chem.201601690

Fullerenes C₆₀, C₇₀, and C₈₄ may be readily encaged within a hydrogen-bonded dimeric capsule, based on two concave cyclotriveratrylene (CTV) scaffolds, each containing three self-complementary 2-ureido-4-[1H]-pyrimidinone (UPy) subunits. NMR spectroscopy and circular dichroism studies, complemented by dispersion-corrected DFT calculations, are reported with the aim of characterizing such capsule–fullerene complexes both structurally and energetically. Six fullerenes are considered: in agreement with experiments, calculations find that encapsulation is most favorable for C₈₄(on a par with C₉₀), and follows the trend C₆₀<C₇₀<C₇₆<C₇₈<C₈₄≈C₉₀. As also found by NMR spectroscopy, the most stable capsules are formed by monomers of identical stereochemistry with UPy and the OMe groups of CTV in a mutualanti orientation and UPy–CTV ethylene linkers within the capsular surface plane. Up to C₇₈, encapsulation is favored by increasing host–guest contacts, but the trend is thereafter increasingly inhibited by growing capsule strain.