A diuranium carbide cluster stabilized inside a C80 fullerene cage

Xingxing Zhang; Wanlu Li; Lai Feng; Xin Chen; Andreas Hansen; Stefan Grimme; Skye Fortier; Dumitru-Claudiu Sergentu; Thomas J Duignan; Jochen Autschbach; Shuao Wang; Yaofeng Wang; Giorgios Velkos; Alexey A Popov; Nabi Aghdassi; Steffen Duhm; Xiaohong Li; Jun Li; Luis Echegoyen; W H Eugen Schwarz; Ning Chen

doi:10.1038/s41467-018-05210-8

A diuranium carbide cluster stabilized inside a C₈₀ fullerene cage

Nat Commun. 2018 Jul 16;9(1):2753. doi: 10.1038/s41467-018-05210-8.

Authors

Xingxing Zhang¹, Wanlu Li², Lai Feng³, Xin Chen², Andreas Hansen⁴, Stefan Grimme⁴, Skye Fortier⁵, Dumitru-Claudiu Sergentu⁶, Thomas J Duignan⁶, Jochen Autschbach⁶, Shuao Wang⁷, Yaofeng Wang¹, Giorgios Velkos⁸, Alexey A Popov⁸, Nabi Aghdassi⁹, Steffen Duhm⁹, Xiaohong Li¹, Jun Li¹⁰, Luis Echegoyen¹¹, W H Eugen Schwarz^{2

12}, Ning Chen¹³

Affiliations

¹ Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, 215123, China.
² Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, 100084, China.
³ Soochow Institute for Energy and Materials InnovationS (SIEMIS), College of Physics, Optoelectronics and Energy & Collaborative, Soochow University, Suzhou, Jiangsu, 215006, China.
⁴ Mulliken Center for Theoretical Chemistry, Universität Bonn, 53115, Bonn, Germany.
⁵ Department of Chemistry, University of Texas at El Paso, 500 West University Avenue, El Paso, TX, 79968, USA.
⁶ Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY, 14260-3000, USA.
⁷ School of Radiological and Interdisciplinary Sciences & Collaborative Innovation Center of Radiation Medicine of Jiangsu, Higher Education Institutions, Soochow University, Suzhou, Jiangsu, 215123, China.
⁸ Nanoscale Chemistry, Leibniz Institute for Solid State and Materials Research, 01069, Dresden, Germany.
⁹ Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, Jiangsu, 215123, China.
¹⁰ Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, 100084, China. [email protected].
¹¹ Mulliken Center for Theoretical Chemistry, Universität Bonn, 53115, Bonn, Germany. [email protected].
¹² Physikalische und Theoretische Chemie, Universität Siegen, 57068, Siegen, Germany.
¹³ Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, 215123, China. [email protected].

Abstract

Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I_h(7)-C₈₀ fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I_h(7)-C₈₀. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (Ni^II-OEP) to produce UCU@I_h(7)-C₈₀·[Ni^II-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I_h(7)-C₈₀ and the covalent nature of the U(f¹)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Abstract

Publication types

Grants and funding