Autor según el artículo: Moreno-Vicente, Antonio; Rosello, Yannick; Chen, Ning; Echegoyen, Luis; Dunk, Paul W; Rodriguez-Fortea, Antonio; de Graaf, Coen; Poblet, Josep M
Departamento: Química Física i Inorgànica
Autor/es de la URV: De Graaf, Cornelis / Moreno Vicente, Antonio / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio / Rosello Marin, Yannick
Palabras clave: Space Pseudopotentials Metal multiple bonds Electronic-structure Chemistry Atoms
Resumen: Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th2@C80 and U2@C80 have shown that although the two Th3+ ions form a strong covalent bond within the carbon cage, the interaction between the U3+ ions is weaker and described as an "unwilling" bond. To evaluate the feasibility of covalent U-U bonds, which are neglected in classical actinide chemistry, we have first investigated the formation of smaller diuranium EMFs by laser ablation using mass spectrometric detection of dimetallic U2@C2n species with 2n >= 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f3)-U(5f3) triple bonds, two U3+ ions can be incarcerated inside the fullerene. The formation of U-U bonds competes with U-cage interactions that tend to separate the U ions, hindering the observation of short U-U distances in the crystalline structures of diuranium endofullerenes as in U2@C80. Smaller cages like C60 exhibit the two interactions, and a strong triple U-U bond with an effective bond order higher than 2 is observed. Although 5f-5f interactions are responsible for the covalent interactions at distances close to 2.5 angstrom, overlap between 7s6d orbitals is still detected above 4 angstrom. In general, metal ions within fullerenes should be regarded as templates in cage formation, not as statistically confined units that have little chance of being observed.
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/
Direcció de correo del autor: coen.degraaf@urv.cat yannick.rosello@estudiants.urv.cat josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Identificador del autor: 0000-0001-8114-6658 0000-0002-4533-0623 0000-0001-5884-5629
Fecha de alta del registro: 2024-10-12
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jacs.2c12346
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Journal Of The American Chemical Society. 145 (12): 6710-6718
Referencia de l'ítem segons les normes APA: Moreno-Vicente, Antonio; Rosello, Yannick; Chen, Ning; Echegoyen, Luis; Dunk, Paul W; Rodriguez-Fortea, Antonio; de Graaf, Coen; Poblet, Josep M (2023). Are U-U Bonds Inside Fullerenes Really Unwilling Bonds?. Journal Of The American Chemical Society, 145(12), 6710-6718. DOI: 10.1021/jacs.2c12346
DOI del artículo: 10.1021/jacs.2c12346
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2023
Tipo de publicación: Journal Publications