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Title: Ultrastable actinide endohedral borospherenes

Journal Article · · ChemComm
DOI:https://doi.org/10.1039/c7cc09837e· OSTI ID:1461131
 [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
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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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1461131
Journal Information:
ChemComm, Vol. 54, Issue 18; ISSN 1359-7345
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (5)

The Reliability of the Density‐Functional Theory in Actinide Endohedral Systems journal July 2019
Aggregation behavior and non‐covalent functionalization of borofullerenes B 28 , B 38 , and B 40 : A density functional theory investigation journal March 2019
Low-dimensional functional networks of cage-like B 40 with effective transition-metal intercalations journal January 2019
Double aromaticity of the B 40 fullerene: induced magnetic field analysis of π and σ delocalization in the boron cavernous structure journal January 2019
Lanthanide and actinide doped B 12 H 12 2− and Al 12 H 12 2− clusters: new magnetic superatoms with f-block elements journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
aromaticity
borospherenes
Density functional calculations
metalloborospherenes