For the past two years we have been involved in the synthesis and characterization of new Uranium-based endohedral fullerenes and have obtained X-Ray crystal structures for several of these compounds. Some are mono-uranium species, U@C2n, while some are di-uranium compounds (see structure at the left), U2@C2n.1 Very recently we isolated two new mono-uranium compounds that violate the Isolated Pentagon Rule (IPR) with a C76 and a C80 cage possessing fused five-membered rings (pentalenes) on their surfaces.2 Still other endohedral structures are much more interesting and totally unanticipated, with formula U2X@C2n, where X= C, O, S or N and 2n= 72, 78 or 80, which reveal interesting metal-cage interactions and totally unprecedented clusters trapped inside. Some of the carbide compounds have been crystallized and the encapsulated U2C cluster (in U=C=U@C80) exhibits unprecedented bonding with totally unanticipated properties (see structure to the right).3
Finally, we have found that bis-porphyrin capsules exhibit exquisitely selective supramolecular binding for several of these uranium-based endohedral fullerene compounds.4
The synthesis, purification and characterization of these interesting endohedral fullerenes will be presented and discussed, along with very recent results about uranium-based endohedrals.
References
1. Zhang, X.; Wang, Y.; Morales Martínez, R.; Zhong, J.; de Graaf, C.; Rodríguez Fortea, A.; Poblet, J. M.; Echegoyen, L.; Feng , L.; Chen, N., J Am Chem Soc 2018, 140 (11), 3907-3915.
2. Cai, W.; Abella, L.; Zhuang, J.; Zhang, X.; Feng, L.; Wang, Y.; Morales Martínez, R.; Esper, R.; Boero, M.; Metta Magaña, A.; Rodríguez Fortea, A.; Poblet, J. M.; Echegoyen, L.; Chen, N., J A m Chem Soc 2018, 140 (51), 18039 18050.
3. Zhang, X.; Li, W.; Feng, L.; Chen, X.; Hansen, A.; Grimme, S.; Fortier, S.; Sergentu, D. C.; Duignan, T. J.; Autschbach, J.; Wang, S.; Wang, Y.; Velkos, G.; Popov, A. A.; Aghdassi, N.; Duhm, S.; Li, X.; Li, J.; Echegoyen, L.; Schwarz, W. H. E.; Chen, N., Nature Comm 2018, 9 (1), 2753
4. Fuertes Espinosa, C.; Gómez Torres, A.; Morales Martínez, R.; Rodríguez Fortea, A.; García Simón, C.; Gándara, F.; Imaz, I.; Juanhuix, J.; Maspoch, D.; Poblet, J. M.; Echegoyen , L.; Ribas, X., Angew Chem Int Ed 2018, 57 (35), 11294 11299.