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
1. [1]
  Chai, Y.; Guo, T.; Jin, C. M.; Haufler, R. E.; Chibante, L. P. F.; Fure, J.; Wang, L. H.; Alford, J. M.; Smalley, R. E. J. Phys. Chem. 1991, 95, 7564. doi: 10.1021/j100173a002 doi: 10.1021/j100173a002
2. [2]
  Zhang, Y.; Shi, Z. J.; Hao, C.; Xu, J. X.; He, X. R.; Gu, Z. N. Acta Phys. -Chim. Sin. 2004, 20, 573. doi: 10.3866/PKU.WHXB20040604
3. [3]
  Liu, X. S.; Lei, D.; Gan, L. H. Acta Phys. -Chim. Sin. 2016, 32, 929. doi: 10.3866/PKU.WHXB201601221
4. [4]
  Popov, A. A.; Yang, S.; Dunsch, L. Chem. Rev. 2013, 113, 5989. doi: 10.1021/cr300297r doi: 10.1021/cr300297r
5. [5]
  Lu, X.; Akasaka, T.; Nagase, S. Chem. Commun. 2011, 47, 5942. doi: 10.1039/c1cc10123d doi: 10.1039/c1cc10123d
6. [6]
  Ross, R. B.; Cardona, C. M.; Guldi, D. M.; Sankaranarayanan, S. G.; Reese, M. O.; Kopidakis, N.; Peet, J.; Walker, B.; Bazan, G. C.; Van Keuren, E.; et al. Nat. Mater. 2009, 8, 208. doi: 10.1038/NMAT2379 doi: 10.1038/NMAT2379
7. [7]
  Bolskar, R. D. Nanomedicine 2008, 3, 201. doi: 10.2217/17435889.3.2.201 doi: 10.2217/17435889.3.2.201
8. [8]
  Feng, L.; Radhakrishnan, S. G.; Mizorogi, N.; Slanina, Z.; Nikawa, H.; Tsuchiya, T.; Akasaka, T.; Nagase, S.; Martin, N.; Guldi, D. M. J. Am. Chem. Soc. 2011, 133, 7608. doi: 10.1021/ja202331r doi: 10.1021/ja202331r
9. [9]
  Jiang, Y. H.; Wang, D. S.; Xu, D.; Zhang, J. Y.; Wang, Z. Y. ChemPhysChem 2018, 19, 2995. doi: 10.1002/cphc.201800797 doi: 10.1002/cphc.201800797
10. [10]
  Liu, F.; Krylov, D. S.; Spree, L.; Avdoshenko, S. M.; Samoylova, N. A.; Rosenkranz, M.; Kostanyan, A.; Greber, T.; Wolter, A. U. B.; Buchner, B.; et al. Nat. Commun. 2017, 8, 16098. doi: 10.1038/ncomms16098 doi: 10.1038/ncomms16098
11. [11]
  Wang, T. S.; Wang, C. R. Acc. Chem. Res. 2014, 47, 450. doi: 10.1021/ar400156z doi: 10.1021/ar400156z
12. [12]
  Hu, Z. Q.; Dong, B. W.; Liu, Z.; Liu, J. J.; Su, J.; Yu, C.; Xiong, J.; Shi, D. E.; Wang, Y. Y.; Wang, B. W.; et al. J. Am. Chem. Soc. 2018, 140, 1123. doi: 10.1021/jacs.7b12170 doi: 10.1021/jacs.7b12170
13. [13]
  Stevenson, S.; Rice, G.; Glass, T.; Harich, K.; Cromer, F.; Jordan, M.; Craft, J.; Hadju, E.; Bible, R.; Olmstead, M. Nature 1999, 401, 55. doi: 10.1038/43415 doi: 10.1038/43415
14. [14]
  Dunsch, L.; Yang, S. Small 2007, 3, 1298. doi: 10.1002/smll.200700036 doi: 10.1002/smll.200700036
15. [15]
  Zhang, J. Y.; Stevenson, S.; Dorn, H. C. Acc. Chem. Res. 2013, 46, 1548. doi: 10.1021/ar300301v doi: 10.1021/ar300301v
16. [16]
  Campanera, J. M.; Bo, C.; Olmstead, M. M.; Balch, A. L.; Poblet, J. M. J. Phys. Chem. A 2002, 106, 12356. doi: 10.1021/jp021882m doi: 10.1021/jp021882m
17. [17]
  Iiduka, Y.; Wakahara, T.; Nakahodo, T.; Tsuchiya, T.; Sakuraba, A.; Maeda, Y.; Akasaka, T.; Yoza, K.; Horn, E.; Kato, T. J. Am. Chem. Soc. 2005, 127, 12500. doi: 10.1021/ja054209u doi: 10.1021/ja054209u
18. [18]
  Stevenson, S.; Mackey, M. A.; Stuart, M. A.; Phillips, J. P.; Easterling, M. L.; Chancellor, C. J.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 2008, 130, 11844. doi: 10.1021/ja803679u doi: 10.1021/ja803679u
19. [19]
  Mercado, B. Q.; Olmstead, M. M.; Beavers, C. M.; Easterling, M. L.; Stevenson, S.; Mackey, M. A.; Coumbe, C. E.; Phillips, J. D.; Phillips, J. P.; Poblet, J. M.; et al. Chem. Commun. 2010, 46, 279. doi: 10.1039/b918731f doi: 10.1039/b918731f
20. [20]
  Krause, M.; Ziegs, F.; Popov, A. A.; Dunsch, L. ChemPhysChem 2007, 8, 537. doi: 10.1002/cphc.200600363 doi: 10.1002/cphc.200600363
21. [21]
  Wang, T. S.; Feng, L.; Wu, J. Y.; Xu, W.; Xiang, J. F.; Tan, K.; Ma, Y. H.; Zheng, J. P.; Jiang, L.; Lu, X.; et al. J. Am. Chem. Soc. 2010, 132, 16362. doi: 10.1021/ja107843b doi: 10.1021/ja107843b
22. [22]
  Frisch, M.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 09, Revision A.1; Gaussian: Wallingford, CT, USA, 2009.
23. [23]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913 doi: 10.1063/1.464913
24. [24]
  Chaur, M. N.; Melin, F.; Ashby, J.; Elliott, B.; Kumbhar, A.; Rao, A. M.; Echegoyen, L. Chem. -Eur. J. 2008, 14, 8213. doi: 10.1002/chem.200800881 doi: 10.1002/chem.200800881
25. [25]
  Xu, W.; Wang, T. S.; Wu, J. Y.; Ma, Y. H.; Zheng, J. P.; Li, H.; Wang, B.; Jiang, L.; Shu, C. Y.; Wang, C. R. J. Phys. Chem. C 2011, 115, 402. doi: 10.1021/jp1087459 doi: 10.1021/jp1087459
26. [26]
  Jin. P; Zhou, Z.; Hao, C.; Gao, Z. X.; Tan, K.; Lu, X.; Chen, Z. F. Phys. Chem. Chem. Phys. 2010, 12, 12442. doi: 10.1039/b923106d doi: 10.1039/b923106d
27. [27]
  Zhang, J.; Bowles, F. L.; Bearden, D. W.; Ray, W. K.; Fuhrer, T.; Ye, Y.; Dixon, C.; Harich, K.; Helm, R. F.; Olmstead, M. M.; et al. Nat. Chem. 2013, 5, 880. doi: 10.1038/NCHEM.1748 doi: 10.1038/NCHEM.1748
28. [28]
  Dunk, P. W.; Kaiser, N. K.; Hendrickson, C. L.; Quinn, J. P.; Ewels, C. P.; Nakanishi, Y.; Sasaki, Y.; Shinohara, H.; Marshall, A. G.; Kroto, H. W. Nat. Commun. 2012, 3, 855. doi: 10.1038/ncomms1853 doi: 10.1038/ncomms1853
29. [29]
  Dang, J.; Wang, W.; Zheng, J.; Zhao, X.; Osawa, E.; Nagase, S. J. Phys. Chem. C 2012, 116, 16233. doi: 10.1021/jp302881u doi: 10.1021/jp302881u
30. [30]
  Wang, W.; Dang, J.; Zheng, J.; Zhao, X.; Nagase, S. J. Phys. Chem. C 2013, 117, 2349. doi: 10.1021/jp3100766 doi: 10.1021/jp3100766
31. [31]
  Mulet-Gas, M.; Abella, L.; Ceron, M. R.; Castro, E.; Marshall, A. G.; Rodriguez-Fortea, A.; Echegoyen, L.; Poblet, J. M.; Dunk, P. W. Nat. Commun. 2017, 8, 1222. doi: 10.1038/s41467-017-01295-9 doi: 10.1038/s41467-017-01295-9
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Wenjiang LI , Pingli GUAN , Rui YU , Yuansheng CHENG , Xianwen WEI . C₆₀-MoP-C nanoflowers van der Waals heterojunctions and its electrocatalytic hydrogen evolution performance. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 771-781. doi: 10.11862/CJIC.20230289
3. [3]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
4. [4]
  Zian Fang , Qianqian Wen , Yidi Wang , Hongxia Ouyang , Qi Wang , Qiuping Li . The Test Paper for Metal Ion: A Popular Science Experiment Based on Color Aesthetics. University Chemistry, 2024, 39(5): 108-115. doi: 10.3866/PKU.DXHX202310032
5. [5]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
6. [6]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
7. [7]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
8. [8]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
9. [9]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
10. [10]
  Yunting Shang , Yue Dai , Jianxin Zhang , Nan Zhu , Yan Su . Something about RGO (Reduced Graphene Oxide). University Chemistry, 2024, 39(9): 273-278. doi: 10.3866/PKU.DXHX202306050
11. [11]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
12. [12]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
13. [13]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
14. [14]
  Zhenlin Zhou , Siyuan Chen , Yi Liu , Chengguo Hu , Faqiong Zhao . A New Program of Voltammetry Experiment Teaching Based on Laser-Scribed Graphene Electrode. University Chemistry, 2024, 39(2): 358-370. doi: 10.3866/PKU.DXHX202308049
15. [15]
  Rui Gao , Ying Zhou , Yifan Hu , Siyuan Chen , Shouhong Xu , Qianfu Luo , Wenqing Zhang . Design, Synthesis and Performance Experiment of Novel Photoswitchable Hybrid Tetraarylethenes. University Chemistry, 2024, 39(5): 125-133. doi: 10.3866/PKU.DXHX202310050
16. [16]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
17. [17]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
18. [18]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
19. [19]
  Hao BAI , Weizhi JI , Jinyan CHEN , Hongji LI , Mingji LI . Preparation of Cu₂O/Cu-vertical graphene microelectrode and detection of uric acid/electroencephalogram. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1309-1319. doi: 10.11862/CJIC.20240001
20. [20]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(300)
HTML views(52)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142