Citation: Junjie Shi, Ziqi Hu, Yihao Yang, Yuxiang Bu, Zujin Shi. Stability and Formation Mechanism of Endohedral Metal Carbonitride Clusterfullerenes[J]. Acta Physico-Chimica Sinica, ;2021, 37(10): 190707. doi: 10.3866/PKU.WHXB201907077 shu

Stability and Formation Mechanism of Endohedral Metal Carbonitride Clusterfullerenes

Junjie Shi ¹ ,
Ziqi Hu ² ,
Yihao Yang ² ,
Yuxiang Bu ^1,, ,
Zujin Shi ^2,,

1.
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
2.
National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Yuxiang Bu, byx@sdu.edu.cn Zujin Shi, zjshi@pku.edu.cn
Received Date: 25 July 2019
Revised Date: 9 August 2019
Accepted Date: 9 August 2019
Available Online: 14 August 2019
Fund Project: the National Natural Science Foundation of China 21875002the National Natural Science Foundation of China 21873056National Basic Research Program of China 2017YFA024901

Fullerene molecules have nano-scale cavities in which various metal or metal clusters of different sizes can be embedded to form metallofullerenes with unique core-shell structures. The physical and chemical properties of metallofullerenes can be modified through the interaction between the encapsulated metals and the fullerene cages. As such, the investigation of metallofullerenes with novel structures has been a principal research focus in the field of fullerenes. In this study, we investigated the size matching effect between encapsulated clusters and fullerene cages for the endohedral metal carbonitride clusterfullerenes in order to discover new metallofullerenes. The stability and electronic structure of the metallofullerenes formed by encapsulating M₃NC clusters (M = Y, La, Gd) into D₂(186)-C₉₆ and D₂(35)-C₈₈ fullerenes were studied using quantum chemical calculations. It was found that the fullerene cages formed stable structures by accepting six electrons transferred from the encapsulated clusters. The change in configuration of the encapsulated clusters was clarified by a comparison with the corresponding M₃N@C_2n metal nitride clusterfullerenes; the size matching effect between M₃NC cluster and fullerene cage was elucidated on the basis of the calculated results and previous studies on Sc₃NC@I_h(7)-C₈₀. For the D₂(186)-C₉₆ fullerene, the Gd₃NC cluster was found to have smaller changes in the configuration as compared with the La₃NC cluster, proving that Gd₃NC is more suitable than La₃NC for encapsulation in the D₂(186)-C₉₆ fullerene cage. In addition, it was determined that the La₃NC cluster requires a large structural change to maintain its planar configuration. For the D₂(35)-C₈₈ fullerene cage, the Y₃NC cluster is more suitable than Gd₃NC for encapsulation owing to the smaller size of the Y₃NC cluster. The spatial distribution of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of Gd₃NC@D₂(186)-C₉₆ were found to be similar to those of Gd₃N@D₂(186)-C₉₆. However, a unique endohedral cluster-based occupied molecular orbital was found for Gd₃NC@D₂(186)-C₉₆. This orbital is derived from the interaction between the NC unit and the Gd atoms. The spatial distribution of the HOMO of Y₃NC@D₂(35)-C₈₈ is similar to that of Y₃N@D₂(35)-C₈₈, while the LUMO of Y₃NC@D₂(35)-C₈₈ has a much larger contribution from the endohedral cluster as compared to Y₃N@D₂(35)-C₈₈. Thus, the addition of a carbon atom in the cluster has a remarkable impact on the electronic structure of the metallofullerenes. With respect to structural characteristics, we found that the three fullerene cages, D₂(186)-C₉₆, D₂(35)-C₈₈, and I_h(7)-C₈₀, have a uniform distribution of five-membered carbon atom rings; these fullerenes can be greatly stabilized in the form of C_2n^6- anions. However, the formation mechanism of fullerenes and metallofullerenes, at present, is poorly understood. Based on the structural analysis, we propose a direct mechanism for the formation of fullerenes without the Stone-Wales isomerization, i.e., the rearrangement of five-membered rings through the addition of carbon atoms and the transformation into larger carbon cages while maintaining stable structural units.
- Fullerene,
- Metallofullerene,
- Density functional theory,
- Electronic structure,
- Rare-earth element
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