A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages

Qingyu Meng; Laura Abella; Yang-Rong Yao; Dumitru-Claudiu Sergentu; Wei Yang; Xinye Liu; Jiaxin Zhuang; Luis Echegoyen; Jochen Autschbach; Ning Chen

doi:10.1038/s41467-022-34651-5

A charged diatomic triple-bonded U≡N species trapped in C₈₂ fullerene cages

Nat Commun. 2022 Nov 23;13(1):7192. doi: 10.1038/s41467-022-34651-5.

Authors

Affiliations

¹ College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China.
² Department of Chemistry, University at Buffalo, State University of New York. Natural Sciences Complex, Buffalo, NY, 14260-3000, USA.
³ Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, P. R. China.
⁴ A.I. Cuza University of Iași, RA-03 Laboratory (RECENT AIR), Iași, 700506, Romania.
⁵ Department of Chemistry, University of Texas at El Paso, 500 W University Avenue, El Paso, Texas, 79968, USA.
⁶ Department of Chemistry, University at Buffalo, State University of New York. Natural Sciences Complex, Buffalo, NY, 14260-3000, USA. jochena@buffalo.edu.
⁷ College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China. chenning@suda.edu.cn.

^# Contributed equally.

Abstract

Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@C_s(6)-C₈₂ and UN@C₂(5)-C₈₂, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@C_s(6)-C₈₂ and UN@C₂(5)-C₈₂. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)²⁺@(C₈₂)^2- electronic structure with formal +5 oxidation state (f¹) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species.

Grants and funding

S10 OD024973/OD/NIH HHS/United States