Author, as appears in the article.: Li X; Roselló Y; Yao YR; Zhuang J; Zhang X; Rodríguez-Fortea A; De Graaf C; Echegoyen L; Poblet JM; Chen N

Department: Química Física i Inorgànica

e-ISSN: 2041-6539

URV's Author/s: De Graaf, Cornelis / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio

Abstract: © 2021 The Royal Society of Chemistry. For the first time, an actinide nitride clusterfullerene, U2N@Ih(7)-C80, is synthesized and fully characterized by X-ray single crystallography and multiple spectroscopic methods. U2N@Ih(7)-C80 is by far the first endohedral fullerene that violates the well-established tri-metallic nitride template for nitride clusterfullerenes. The novel UNU cluster features two UN bonds with uneven bond distances of 2.058(3) Å and 1.943(3) Å, leading to a rare unsymmetrical structure for the dinuclear nitride motif. The combined experimental and theoretical investigations suggest that the two uranium ions show different oxidation states of +4 and +5. Quantum-chemical investigation further reveals that the f1/f2 population dominantly induces a distortion of the UNU cluster, which leads to the unsymmetrical structure. A comparative study of U2X@C80 (X = C, N and O) reveals that the U-X interaction in UXU clusters can hardly be seen as being formed by classical multiple bonds, but is more like an anionic central ion Xq- with biased overlaps with the two metal ions, which decrease as the electronegativity of X increases. This study not only demonstrates the unique bonding variety of actinide clusters stabilized by fullerene cages, showing different bonding from that observed for the lanthanide analogs, it also reveals the electronic structure of the UXU clusters (X = C, N and O), which are of fundamental significance to understanding these actinide bonding motifs.

Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 2041-6520

Author's mail: coen.degraaf@urv.cat antonio.rodriguezf@urv.cat josepmaria.poblet@urv.cat

Author identifier: 0000-0001-8114-6658 0000-0001-5884-5629 0000-0002-4533-0623

Record's date: 2023-02-23

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2021/sc/d0sc04677a#!divAbstract

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Chemical Science. 12 (1): 282-292

APA: Li X; Roselló Y; Yao YR; Zhuang J; Zhang X; Rodríguez-Fortea A; De Graaf C; Echegoyen L; Poblet JM; Chen N (2021). U2N@: I h(7)-C80: fullerene cage encapsulating an unsymmetrical U(iv)NU(v) cluster. Chemical Science, 12(1), 282-292. DOI: 10.1039/d0sc04677a

Article's DOI: 10.1039/d0sc04677a

Entity: Universitat Rovira i Virgili

Journal publication year: 2021

Publication Type: Journal Publications