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Title: Ultrastable actinide endohedral borospherenes

Abstract

Since the discovery of the first all-boron fullerenes B40-/0, metal-doped borospherenes have received extensive attention. So far, in spite of theoretical efforts on metalloborospherenes, the feasibility of actinide analogues remains minimally explored. Here we report a series of actinide borospherenes AnBn(An=U, Th; n=36, 38, 40) from extensive first-principles theory calculations. All the AnBn complexes are found to possess endohedral structures (An@Bn) as the global minima. In particular, U@B36 (C2h, 3Ag) and Th@B38 (C2h, 3Bu) exhibit nearly ideal endohedral borospherene structures. The C2h U@B36 and Th@B38 complexes are predicted to be highly robust both thermodynamically and dynamically. In addition to the actinide size match to the cage, the covalent character of the metal-cage bonding in U@B36 and Th@B38 affords further stabilization. Bonding analysis indicates that the C2h Th@B38 exhibits 3D aromaticity with σ plus π double delocalization bonding. IN conclusion, the results demonstrate that doping with appropriate actinide atoms is promising to stabilize diverse borospherenes, and may provide routes for borospherene modification and functionalization.

Authors:
 [1];  [2];  [2]; ORCiD logo [2];  [3];  [4]; ORCiD logo [2]
  1. Chinese Academy of Sciences (CAS), Beijing (China). Lab. of Nuclear Energy Chemistry and Key Lab. for Biomedical Effects of Nanomaterials and Nanosafety Inst. of High Energy Physics
  2. Chinese Academy of Sciences (CAS), Beijing (China). Lab. of Nuclear Energy Chemistry and Key Lab. for Biomedical Effects of Nanomaterials and Nanosafety Inst. of High Energy Physics
  3. Chinese Academy of Sciences (CAS), Beijing (China). Lab. of Nuclear Energy Chemistry and Key Lab. for Biomedical Effects of Nanomaterials and Nanosafety Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School for Radiological and interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Inst.
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1461131
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 54; Journal Issue: 18; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinides; aromaticity; borospherenes; Density functional calculations; metalloborospherenes

Citation Formats

Wang, Cong -Zhi, Bo, Tao, Lan, Jian -Hui, Wu, Qun -Yan, Chai, Zhi -Fang, Gibson, John K., and Shi, Wei -Qun. Ultrastable actinide endohedral borospherenes. United States: N. p., 2018. Web. doi:10.1039/c7cc09837e.
Wang, Cong -Zhi, Bo, Tao, Lan, Jian -Hui, Wu, Qun -Yan, Chai, Zhi -Fang, Gibson, John K., & Shi, Wei -Qun. Ultrastable actinide endohedral borospherenes. United States. doi:10.1039/c7cc09837e.
Wang, Cong -Zhi, Bo, Tao, Lan, Jian -Hui, Wu, Qun -Yan, Chai, Zhi -Fang, Gibson, John K., and Shi, Wei -Qun. Mon . "Ultrastable actinide endohedral borospherenes". United States. doi:10.1039/c7cc09837e. https://www.osti.gov/servlets/purl/1461131.
@article{osti_1461131,
title = {Ultrastable actinide endohedral borospherenes},
author = {Wang, Cong -Zhi and Bo, Tao and Lan, Jian -Hui and Wu, Qun -Yan and Chai, Zhi -Fang and Gibson, John K. and Shi, Wei -Qun},
abstractNote = {Since the discovery of the first all-boron fullerenes B40-/0, metal-doped borospherenes have received extensive attention. So far, in spite of theoretical efforts on metalloborospherenes, the feasibility of actinide analogues remains minimally explored. Here we report a series of actinide borospherenes AnBn(An=U, Th; n=36, 38, 40) from extensive first-principles theory calculations. All the AnBn complexes are found to possess endohedral structures (An@Bn) as the global minima. In particular, U@B36 (C2h, 3Ag) and Th@B38 (C2h, 3Bu) exhibit nearly ideal endohedral borospherene structures. The C2h U@B36 and Th@B38 complexes are predicted to be highly robust both thermodynamically and dynamically. In addition to the actinide size match to the cage, the covalent character of the metal-cage bonding in U@B36 and Th@B38 affords further stabilization. Bonding analysis indicates that the C2h Th@B38 exhibits 3D aromaticity with σ plus π double delocalization bonding. IN conclusion, the results demonstrate that doping with appropriate actinide atoms is promising to stabilize diverse borospherenes, and may provide routes for borospherene modification and functionalization.},
doi = {10.1039/c7cc09837e},
journal = {ChemComm},
number = 18,
volume = 54,
place = {United States},
year = {2018},
month = {2}
}

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