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

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

Chemistry

Soochow University
Tsinghua University
University of Bonn
University of Texas at El Paso
SUNY Buffalo
Leibniz Institute for Solid State and Materials Research Dresden
University of Siegen

Research output: Contribution to journal › Article › peer-review

85 Scopus citations

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.

Original language	English
Article number	2753
Journal	Nature Communications
Volume	9
Issue number	1
DOIs	https://doi.org/10.1038/s41467-018-05210-8
State	Published - Dec 1 2018

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Zhang, X., Li, W., Feng, L., Chen, X., Hansen, A., Grimme, S., Fortier, S., Sergentu, D. C., Duignan, T. J., Autschbach, J., Wang, S., Wang, Y., Velkos, G., Popov, A. A., Aghdassi, N., Duhm, S., Li, X., Li, J., Echegoyen, L., ... Chen, N. (2018). A diuranium carbide cluster stabilized inside a C₈₀ fullerene cage. Nature Communications, 9(1), Article 2753. https://doi.org/10.1038/s41467-018-05210-8

@article{aec830248ed04011b82fdfe92bad90fa,

title = "A diuranium carbide cluster stabilized inside a C80 fullerene cage",

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 Kr{\"a}tschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@I h(7)-C80·[NiII-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 {\AA}) 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.",

author = "Xingxing Zhang and Wanlu Li and Lai Feng and Xin Chen and Andreas Hansen and Stefan Grimme and Skye Fortier and Sergentu, \{Dumitru Claudiu\} and Duignan, \{Thomas J.\} and Jochen Autschbach and Shuao Wang and Yaofeng Wang and Giorgios Velkos and Popov, \{Alexey A.\} and Nabi Aghdassi and Steffen Duhm and Xiaohong Li and Jun Li and Luis Echegoyen and Schwarz, \{W. H.Eugen\} and Ning Chen",

note = "Publisher Copyright: {\textcopyright} 2018 The Author(s).",

year = "2018",

month = dec,

day = "1",

doi = "10.1038/s41467-018-05210-8",

language = "English",

volume = "9",

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issn = "2041-1723",

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Zhang, X, Li, W, Feng, L, Chen, X, Hansen, A, Grimme, S, Fortier, S, Sergentu, DC, Duignan, TJ, Autschbach, J, Wang, S, Wang, Y, Velkos, G, Popov, AA, Aghdassi, N, Duhm, S, Li, X, Li, J, Echegoyen, L, Schwarz, WHE & Chen, N 2018, 'A diuranium carbide cluster stabilized inside a C₈₀ fullerene cage', Nature Communications, vol. 9, no. 1, 2753. https://doi.org/10.1038/s41467-018-05210-8

TY - JOUR

T1 - A diuranium carbide cluster stabilized inside a C80 fullerene cage

AU - Zhang, Xingxing

AU - Li, Wanlu

AU - Feng, Lai

AU - Chen, Xin

AU - Hansen, Andreas

AU - Grimme, Stefan

AU - Fortier, Skye

AU - Sergentu, Dumitru Claudiu

AU - Duignan, Thomas J.

AU - Autschbach, Jochen

AU - Wang, Shuao

AU - Wang, Yaofeng

AU - Velkos, Giorgios

AU - Popov, Alexey A.

AU - Aghdassi, Nabi

AU - Duhm, Steffen

AU - Li, Xiaohong

AU - Li, Jun

AU - Echegoyen, Luis

AU - Schwarz, W. H.Eugen

AU - Chen, Ning

PY - 2018/12/1

Y1 - 2018/12/1

N2 - 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 (NiII-OEP) to produce UCU@I h(7)-C80·[NiII-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.

AB - 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 (NiII-OEP) to produce UCU@I h(7)-C80·[NiII-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.

UR - https://www.scopus.com/pages/publications/85050384003

U2 - 10.1038/s41467-018-05210-8

DO - 10.1038/s41467-018-05210-8

M3 - Article

C2 - 30013067

AN - SCOPUS:85050384003

SN - 2041-1723

VL - 9

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 2753

ER -

A diuranium carbide cluster stabilized inside a C₈₀ fullerene cage

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