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:
-
- 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
- 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
- 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.
- 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)
- 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. https://doi.org/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. https://doi.org/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 = {Mon Feb 05 00:00:00 EST 2018},
month = {Mon Feb 05 00:00:00 EST 2018}
}
Web of Science
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