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Title: Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages

Abstract

>Novel actinide cluster fullerenes, U2C2@Ih(7)-C80 and U2C2@D3h(5)-C78, were synthesized and fully characterized by mass spectrometry, single-crystal X-ray crystallography, UV–vis–NIR, nuclear magnetic resonance spectroscopy (NMR), X-ray absorption spectroscopy (XAS), Raman spectroscopy, IR spectroscopy, as well as density functional and multireference wave function calculations. The encapsulated U2C2 is a novel example of a uranium carbide cluster featuring two U centers bridged by a C≡C unit. The U–C bond distances in these U2C2 clusters are in the range between 2.130 and 2.421 Å. While the U2C2 cluster in U2C2@C80 adopts a butterfly-shaped geometry with a U–C2–U dihedral angle of 112.7° and a U–U distance of 3.855 Å, the U–U distance in U2C2@C78 is 4.164 Å and the resulting U–C2–U dihedral angle is increased to 149.1°. The combined experimental and quantum-chemical results suggest that the formal U oxidation state is +4 in the U2C2 cluster, and each U center transfers three electrons to the C2n cage and one electron to C2. Different from the strong U = C covalent bonding reported for U2C2@ C80, the U–C bonds in U2C2 are less covalent and predominantly ionic. The C–C triple bond is somewhat weaker than in HCCH, and the C–C π bonds undergo donation bonding withmore » the U centers. This work shows that the combination of the unique encapsulation effect of fullerene cages and the variable oxidation states of actinide elements can lead to the stabilization of novel actinide clusters, which are not accessible by conventional synthetic methods.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Soochow Univ. (China)
  2. State Univ. of New York (SUNY), Buffalo, NY (United States)
  3. Univ. of Texas at El Paso, TX (United States)
Publication Date:
Research Org.:
Florida State Univ., Tallahassee, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation China (NNSFC); Robert A. Welch Foundation
OSTI Identifier:
1596909
Grant/Contract Number:  
SC0016568; SC0001136
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 51; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; endohedral fullerenes; uranium carbide; cluster; actinides; chemical bonding

Citation Formats

Zhuang, Jiaxin, Abella, Laura, Sergentu, Dumitru-Claudiu, Yao, Yang-Rong, Jin, Meihe, Yang, Wei, Zhang, Xingxing, Li, Xiaomeng, Zhang, Duo, Zhao, Yiming, Li, Xiaohong, Wang, Shuao, Echegoyen, Luis, Autschbach, Jochen, and Chen, Ning. Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages. United States: N. p., 2019. Web. doi:10.1021/jacs.9b10247.
Zhuang, Jiaxin, Abella, Laura, Sergentu, Dumitru-Claudiu, Yao, Yang-Rong, Jin, Meihe, Yang, Wei, Zhang, Xingxing, Li, Xiaomeng, Zhang, Duo, Zhao, Yiming, Li, Xiaohong, Wang, Shuao, Echegoyen, Luis, Autschbach, Jochen, & Chen, Ning. Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages. United States. https://doi.org/10.1021/jacs.9b10247
Zhuang, Jiaxin, Abella, Laura, Sergentu, Dumitru-Claudiu, Yao, Yang-Rong, Jin, Meihe, Yang, Wei, Zhang, Xingxing, Li, Xiaomeng, Zhang, Duo, Zhao, Yiming, Li, Xiaohong, Wang, Shuao, Echegoyen, Luis, Autschbach, Jochen, and Chen, Ning. Mon . "Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages". United States. https://doi.org/10.1021/jacs.9b10247. https://www.osti.gov/servlets/purl/1596909.
@article{osti_1596909,
title = {Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages},
author = {Zhuang, Jiaxin and Abella, Laura and Sergentu, Dumitru-Claudiu and Yao, Yang-Rong and Jin, Meihe and Yang, Wei and Zhang, Xingxing and Li, Xiaomeng and Zhang, Duo and Zhao, Yiming and Li, Xiaohong and Wang, Shuao and Echegoyen, Luis and Autschbach, Jochen and Chen, Ning},
abstractNote = {>Novel actinide cluster fullerenes, U2C2@Ih(7)-C80 and U2C2@D3h(5)-C78, were synthesized and fully characterized by mass spectrometry, single-crystal X-ray crystallography, UV–vis–NIR, nuclear magnetic resonance spectroscopy (NMR), X-ray absorption spectroscopy (XAS), Raman spectroscopy, IR spectroscopy, as well as density functional and multireference wave function calculations. The encapsulated U2C2 is a novel example of a uranium carbide cluster featuring two U centers bridged by a C≡C unit. The U–C bond distances in these U2C2 clusters are in the range between 2.130 and 2.421 Å. While the U2C2 cluster in U2C2@C80 adopts a butterfly-shaped geometry with a U–C2–U dihedral angle of 112.7° and a U–U distance of 3.855 Å, the U–U distance in U2C2@C78 is 4.164 Å and the resulting U–C2–U dihedral angle is increased to 149.1°. The combined experimental and quantum-chemical results suggest that the formal U oxidation state is +4 in the U2C2 cluster, and each U center transfers three electrons to the C2n cage and one electron to C2. Different from the strong U = C covalent bonding reported for U2C2@ C80, the U–C bonds in U2C2 are less covalent and predominantly ionic. The C–C triple bond is somewhat weaker than in HCCH, and the C–C π bonds undergo donation bonding with the U centers. This work shows that the combination of the unique encapsulation effect of fullerene cages and the variable oxidation states of actinide elements can lead to the stabilization of novel actinide clusters, which are not accessible by conventional synthetic methods.},
doi = {10.1021/jacs.9b10247},
journal = {Journal of the American Chemical Society},
number = 51,
volume = 141,
place = {United States},
year = {2019},
month = {12}
}

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