Autor según el artículo: 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; Echegoyen L; Chen N

Departamento: Química Física i Inorgànica

Autor/es de la URV: Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio

Palabras clave: Structural-characterization Relative stabilities Nitride cluster Metal atoms Isomers Ipr Fullerene cage Family Density Crystal-structures

Resumen: © 2018 American Chemical Society. For the first time, actinide endohedral metallofullerenes (EMFs) with non-isolated-pentagon-rule (non-IPR) carbon cages, U@C 80 , Th@C 80 , and U@C 76 , have been successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray diffractometry, UV-vis-NIR and Raman spectroscopy, and cyclic voltammetry. Crystallographic analysis revealed that the U@C 80 and Th@C 80 share the same non-IPR cage of C 1 (28324)-C 80 , and U@C 76 was assigned to non-IPR U@C 1 (17418)-C 76 . All of these cages are chiral and have never been reported before. Further structural analyses show that enantiomers of C 1 (17418)-C 76 and C 1 (28324)-C 80 share a significant continuous portion of the cage and are topologically connected by only two C 2 insertions. DFT calculations show that the stabilization of these unique non-IPR fullerenes originates from a four-electron transfer, a significant degree of covalency, and the resulting strong host-guest interactions between the actinide ions and the fullerene cages. Moreover, because the actinide ion displays high mobility within the fullerene, both the symmetry of the carbon cage and the possibility of forming chiral fullerenes play important roles to determine the isomer abundances at temperatures of fullerene formation. This study provides what is probably one of the most complete examples in which carbon cage selection occurs through thermodynamic control at high temperatures, so the selected cages do not necessarily coincide with the most stable ones at room temperature. This work also demonstrated that the metal-cage interactions in actinide EMFs show remarkable differences from those previously known for lanthanide EMFs. These unique interactions not only could stabilize new carbon cage structures, but more importantly, they lead to a new family of metallofullerenes for which the cage selection pattern is different to that observed so far for nonactinide EMFs. For this new family, the simple ionic A q+ @C 2nq- model makes predictions less reliable, and in general, unambiguously discerning the isolated structures requires the combination of accurate computational and experimental data.

Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 00027863

Direcció de correo del autor: antonio.rodriguezf@urv.cat josepmaria.poblet@urv.cat

Identificador del autor: 0000-0001-5884-5629 0000-0002-4533-0623

Fecha de alta del registro: 2023-02-18

Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion

Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jacs.8b10435

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Journal Of The American Chemical Society. 140 (51): 18039-18050

Referencia de l'ítem segons les normes APA: 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; Echegoyen L; C (2018). Synthesis and Characterization of Non-Isolated-Pentagon-Rule Actinide Endohedral Metallofullerenes U@ C 1 (17418)-C 76 , U@ C 1 (28324)-C 80 , and Th@ C 1 (28324)-C 80 : Low-Symmetry Cage Selection Directed by a Tetravalent Ion. Journal Of The American Chemical Society, 140(51), 18039-18050. DOI: 10.1021/jacs.8b10435

DOI del artículo: 10.1021/jacs.8b10435

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2018

Tipo de publicación: Journal Publications