Supramolecular Nanocages as Masks for Fullerene Regiofunctionalization and Beyond

Résumé :

The design of a confined cavity dictates the type of guest to be encapsulated, and supramolecular cages are tunable scaffolds that allow the rational design of their cavities. Nowadays, easily accessible C60 and C70 fullerene mono-adducts are mainly used in any application (1) due to the hampered accessibility to pure alternative fullerene poly-adduct derivatives. In general, multi-adduct mixtures with uncontrolled regioselectivity (multi-isomers) are obtained, and chromatographic purification is too costly and time-consuming. Herein, porphyrin-based supramolecular nanocapsules (2,3) are used as supramolecular shadow masks to tame the over-reactivity of Bingel-type cyclopropanation reactions and to have full control over the equatorial regioselectivity
and the number of additions. Furthermore, the regioselectivity control is finely tuned using a three-shell Matryoshka-like assembly towards synthesizing a single trans-3 bis-Bingel-C60 for the first time (4). Also, the mask strategy is extended to C60 and C70 for Bingel and Diels-Alder (5,6). We envision that the described protocol will produce a plethora of derivatives for applications such as solar cells. We will also discuss our recent selective purification of fullertube mixtures and beyond (7,8).

References :
1. E. Castro, L. Echegoyen et al. J. Mater. Chem. C, 2018, 6, 2635.
2. C. García-Simón, X. Ribas, et al. Nat. Commun. 2014, 5:5557.
3. C. Fuertes-Espinosa, X. Ribas, et al, Chem 2020, 6, 169–186.
4. E. Ubasart, X. Ribas, et al, Nat. Chem. 2021, 13, 420-427.
5. V. Iannace, X. Ribas et al, J. Am. Chem. Soc. 2024, 146, 5186−5194.
6. T. Pèlachs, X. Ribas et al, CCS Chem. 2025, 7, 703–715
7. V. Iannace, X. Ribas et al, J. Am. Chem. Soc. 2025, 147, 36079−36084
8. V. Iannace, X. Ribas, Acc. Chem. Res. 2026, 59, 1414−1425

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Contact : noemie.lalaoui@univ-grenoble-alpes.fr