In Honor of Nobel Laureate Prof. M Stanley Whittingham
| ACTINIDE ENDOHEDRAL METALLOFULLERENES Josep Maria Poblet1; 1UNIVERSITAT ROVIRA I VIRGILI, Tarragona, Spain; PAPER: 28/Nanomaterials/Regular (Oral) OS SCHEDULED: 11:55/Wed. 29 Nov. 2023/Dreams 3 ABSTRACT: For almost two decades, intensive work from experimental and theoretical groups has made it possible to advance in the understanding of structural and electronic properties of endohedral metallofullerenes and cluster metal fullerenes. Hence, several groups have proposed diverse rules related with the relative stability of fullerene cages.[1] All of them considered the potential energy when they predict the stability of IPR and non-IPR isomers based on the ionic model, in which the guest transfers usually between three and six electrons to the hosting carbon cage. Those guidelines have explained why the highly symmetric C80(Ih) cage is the preferred fullerene when there is a transfer of six electrons, like in the well-known Sc3N@C80,[2] or in many other examples, such as Lu3N@C80, La2@C80, Y3@C80, etc.[3] In endohedral fullerenes with four or less electron transfer between host and guest, there is not a prevalent structure, like C80(Ih), and the diversity of captured carbon cages is larger, the theoretical prediction of the most abundant species to be formed in a K-H reactor being much more difficult. In addition to the relative potential energy, it is also necessary to consider the enthalpic and entropic contributions to the stability of the endohedral fullerenes. A systematic theoretical analysis for a series of A@C2n fullerenes with A = Th and U, in combination with accurate experimental characterization, have allowed us to show that the structures of A4+@C2n4- species are different from those of cluster fullerenes, such as Sc2O4+@C2n4-, Sc2S4+@C2n4-or Sc2C24+@C2n4-.[4] Here, we will present some of the most recent studies carried out in collaboration with Prof. Luis Echegoyen concerning to stabilization of non-IPR, formation of strong covalent actinide-actinide bons and electrochemical reactions in endofullerenes.[5] References: [1] Campanera, J. M.; Bo, C.; Poblet, J. M., Angew. Chem., Int. Ed. 2005, 44, 7230-7233; Rodríguez-Fortea, A.; Alegret, N.; Balch, A. L.; Poblet, J. M., Nature Chem. 2010, 2, 955; Garcia-Borràs M., Osuna S., Swart M., Luis J.M., Solà M. Angew. Chem. Int.. Ed. 2013, 52, 9275-9278; Wang, Y.; Díaz-Tendero, S.; Martín, F. and Alcamí, M. J. Am. Chem. Soc., 2016, 138, 1551–1560 [2] Stevenson, S.; Rice, G.; Glass, T.; Harich, K.; Cromer, F.; Jordan, M. R.; Craft, J.; Hadju, E.; Bible, R.; Olmstead, M. M.; Maitra, K.; Fisher, A. J.; Balch, A. L.; Dorn, H. C., Nature 1999, 401, 55. [3] Popov, A. A.; Yang, S.; Dunsch, L., Chem. Rev. 2013, 113, 5989-6113. [4] W. Cai, L. Abella, J. Zhuang, X. Zhang, L. Feng, Y. Wang, R. Morales-Martínez, R. Esper, M. Boero, A. Metta-Magaña, A. Rodríguez-Fortea, J. M Poblet, L. Echegoyen, N. Chen J. Am. Chem. Soc. 2018, 140, 18039-18050. [5] X. Zhang, Y. Wang, R. Morales-Martínez, J. Zhong, C. de Graaf, A. Rodríguez-Fortea, J. M Poblet, L. Echegoyen, L. Feng, N. Chen J. Am. Chem. Soc. 2018, 140, 3907-3915; A. Moreno-Vicente, Y. Roselló, N. Chen, L. Echegoyen, P.W. Dunk, A. Rodríguez-Fortea, C. de Graaf, J. M Poblet, J. Am. Chem. Soc. 2023, 145, 6710-6718. |
