Sc@B28−, Ti@B28, V@B28+, and V@B292−: Spherically Aromatic Endohedral Seashell-like Metallo-Borospherenes
Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28−/0 and Cs B29− as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-met...
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| Published in | Molecules (Basel, Switzerland) Vol. 28; no. 9; p. 3892 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
Basel
MDPI AG
05.05.2023
MDPI |
| Subjects | |
| Online Access | Get full text |
| ISSN | 1420-3049 1420-3049 |
| DOI | 10.3390/molecules28093892 |
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| Abstract | Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28−/0 and Cs B29− as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C2 Sc@B28− (1), C2 Ti@B28 (2), C2 V@B28+ (3), and Cs V@B292− (4) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D6h Cr(C6H6)2 with two B12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal “pearl” sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso−chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C6H6)2, these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S21P61D10), rendering spherical aromaticity and extra stability to the systems. |
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| AbstractList | Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28−/0 and Cs B29− as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C2 Sc@B28− (1), C2 Ti@B28 (2), C2 V@B28+ (3), and Cs V@B292− (4) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D6h Cr(C6H6)2 with two B12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal “pearl” sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso−chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C6H6)2, these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S21P61D10), rendering spherical aromaticity and extra stability to the systems. Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28-/0 and Cs B29- as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C2 Sc@B28- (1), C2 Ti@B28 (2), C2 V@B28+ (3), and Cs V@B292- (4) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D6h Cr(C6H6)2 with two B12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal "pearl" sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso-chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C6H6)2, these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S21P61D10), rendering spherical aromaticity and extra stability to the systems.Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28-/0 and Cs B29- as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C2 Sc@B28- (1), C2 Ti@B28 (2), C2 V@B28+ (3), and Cs V@B292- (4) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D6h Cr(C6H6)2 with two B12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal "pearl" sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso-chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C6H6)2, these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S21P61D10), rendering spherical aromaticity and extra stability to the systems. Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C 2 B 28 −/0 and C s B 29 − as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C 2 Sc@B 28 − ( 1 ), C 2 Ti@B 28 ( 2 ), C 2 V@B 28 + ( 3 ), and C s V@B 29 2− ( 4 ) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D 6h Cr(C 6 H 6 ) 2 with two B 12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal “pearl” sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso−chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C 6 H 6 ) 2 , these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S 2 1P 6 1D 10 ), rendering spherical aromaticity and extra stability to the systems. |
| Author | Lu, Xiao-Qin Yan, Qiao-Qiao Li, Si-Dian Zhang, Ting Zhao, Xiao-Ni Zhang, Min |
| AuthorAffiliation | 3 Shanxi Center for Testing of Functional Agro-Products, Shanxi Agricultural University, Taiyuan 030031, China; luxiaoqin@sxu.edu.cn 2 Department of Chemistry, Xinzhou Teachers’ University, Xinzhou 034000, China 1 Institute of Molecular Science, Shanxi University, Taiyuan 030006, China; zhangting0913@sxu.edu.cn (T.Z.); zhangm22@sxu.edu.cn (M.Z.); yanqiaoqiao@sxu.edu.cn (Q.-Q.Y.); zhaoxiaoni@sxu.edu.cn (X.-N.Z.) |
| AuthorAffiliation_xml | – name: 3 Shanxi Center for Testing of Functional Agro-Products, Shanxi Agricultural University, Taiyuan 030031, China; luxiaoqin@sxu.edu.cn – name: 2 Department of Chemistry, Xinzhou Teachers’ University, Xinzhou 034000, China – name: 1 Institute of Molecular Science, Shanxi University, Taiyuan 030006, China; zhangting0913@sxu.edu.cn (T.Z.); zhangm22@sxu.edu.cn (M.Z.); yanqiaoqiao@sxu.edu.cn (Q.-Q.Y.); zhaoxiaoni@sxu.edu.cn (X.-N.Z.) |
| Author_xml | – sequence: 1 givenname: Ting surname: Zhang fullname: Zhang, Ting – sequence: 2 givenname: Min surname: Zhang fullname: Zhang, Min – sequence: 3 givenname: Xiao-Qin surname: Lu fullname: Lu, Xiao-Qin – sequence: 4 givenname: Qiao-Qiao surname: Yan fullname: Yan, Qiao-Qiao – sequence: 5 givenname: Xiao-Ni surname: Zhao fullname: Zhao, Xiao-Ni – sequence: 6 givenname: Si-Dian surname: Li fullname: Li, Si-Dian |
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| Snippet | Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2... Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C 2... |
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| Title | Sc@B28−, Ti@B28, V@B28+, and V@B292−: Spherically Aromatic Endohedral Seashell-like Metallo-Borospherenes |
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