Author, as appears in the article.: Cai, Wenting; Abella, Laura; Zhuang, Jiaxin; Zhang, Xingxing; Feng, Lai; Wang, Yaofeng; Morales-Martinez, Roser; Esper, Ronda; Boero, Mauro; Metta-Magana, Alejandro; Rodriguez-Fortea, Antonio; Poblet, Josep M; Echegoyen, Luis; Chen, Ning
Department: Química Física i Inorgànica
URV's Author/s: Abella Guzman, Laura / Morales Martínez, Roser / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Keywords: Structural-characterization Relative stabilities Nitride cluster Metal atoms Isomers Ipr Fullerene cage Family Density Crystal-structures
Abstract: © 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.
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 00027863
Author's mail: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
Record's date: 2024-10-12
Papper version: info:eu-repo/semantics/acceptedVersion
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 140 (51): 18039-18050
APA: Cai, Wenting; Abella, Laura; Zhuang, Jiaxin; Zhang, Xingxing; Feng, Lai; Wang, Yaofeng; Morales-Martinez, Roser; Esper, Ronda; Boero, Mauro; Metta-Mag (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
Entity: Universitat Rovira i Virgili
Journal publication year: 2018
Publication Type: Journal Publications
Repositori URV