Synthesis and Characterizations of 15N Isotope Labeling Metal Nitride Clusterfullerene

doi:10.6023/A22020087

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (7): 874-878.DOI: 10.6023/A22020087 Previous Articles Next Articles

Article

¹⁵N同位素标记的金属氮化物内嵌富勒烯的合成与表征

邱玲^a, 梁家艺^a, 张竹霞^a^,^b^,^c^,^*(), 王太山^d^,^*()

a 太原理工大学新材料界面科学与工程教育部重点实验室太原 030024
b 太原理工大学化学学院太原 030024
c 山西师范大学磁性分子与磁信息材料教育部重点实验室太原 030000
d 中国科学院化学研究所分子纳米结构与纳米技术重点实验室北京 100190

投稿日期:2022-02-25 发布日期:2022-04-26
通讯作者: 张竹霞, 王太山
基金资助:
国家自然科学基金(51832008); 国家自然科学基金(52022098); 国家自然科学基金(51972309); 中科院青促会(Y201910); 固体表面物理化学国家重点实验室(厦门大学)开放课题(201928); 山西省自然科学基金(201901D111109)

Synthesis and Characterizations of ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene

Ling Qiu^a, Jiayi Liang^a, Zhuxia Zhang^a^,^b^,^c(), Taishan Wang^d()

a Key Laboratory of Interface Science and Engineering in Advanced Materials Ministry of Eduacation, Taiyuan University of Technology, Taiyuan 030024, China
b College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China
c Key Laboratory of Magnetic Molecules and Magnetic Information Materials Ministry of Eduacation, Shanxi Normal University, Taiyuan 030000, China
d CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, China

Received:2022-02-25 Published:2022-04-26
Contact: Zhuxia Zhang, Taishan Wang
Supported by:
National Natural Science Foundation of China(51832008); National Natural Science Foundation of China(52022098); National Natural Science Foundation of China(51972309); Youth Innovation Promotion Association of Chinese Academy of Sciences(Y201910); Opening Project of PCOSS, Xiamen University(201928); Natural Science Foundation of Shanxi Province(201901D111109)

1. .pdf(559KB)

Abstract

In this work, we prepared the ¹⁵N-labeled metal nitride clusterfullerene by arc discharge method. In the synthetic process, scandium metal, graphite powder, and ¹⁵NH₄Cl were atomized by arc discharge method under helium atmosphere with ¹⁵NH₄Cl as solid nitrogen source, and finally Sc₃¹⁵N@C₈₀ and Sc₃¹⁵N@C₇₈ were obtained. Sc₃¹⁵N@C₈₀ was isolated by high-performance liquid chromatography (HPLC) and characterized by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, UV-Vis absorption spectra, and ¹³C NMR. These results demonstrate the successful labeling of ¹⁵N and also illustrate that the prepared Sc₃¹⁵N@C₈₀ has an I_h-C₈₀ cage. The prepared ¹⁵N-labeled metal nitride clusterfullerenes contain more than 98% of the ¹⁵N isotope, which will expand the application fields of metallofullerene materials such as isotope tracing. In detail, clusterfullerenes were separated from hollow fullerenes by multistage HPLC. And then pure samples of Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ were obtained. Mass spectrometry was used to characterize the molecular weight of Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈. According to the isotopic distributions of Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ in mass spectra, their molecular weight values have increased by 1 compared to those of unlabeled Sc₃N@C₈₀-I_h and Sc₃N@C₇₈, revealing the successful labeling of isotope ¹⁵N on the Sc₃N cluster. At the same time, we added Y₃N@C₈₀ as an internal standard into Sc₃¹⁵N@C₈₀-I_h and Sc₃¹⁵N@C₇₈ samples to further confirm the labeling of ¹⁵N atom on the Sc₃N cluster. Moreover, the UV-Vis absorption spectrum showed that the absorption of Sc₃¹⁵N@C₈₀ begins at 820 nm, and the lowest energy transition was observed at 735 nm. Based on the absorption onset, the optical energy gap of Sc₃¹⁵N@C₈₀ can be calculated, which is about 1.51 eV. According to the reported UV-Vis absorption spectra in literature, the carbon cage of the isolated Sc₃¹⁵N@C₈₀ can be characterized as I_h-symmetry. The carbon nuclear magnetic resonance spectroscopy (¹³C NMR) was executed by dissolving Sc₃¹⁵N@C₈₀ in 1,2-dichlorobenzene-d₄ at 293 K. The ¹³C NMR spectrum consists of only two NMR lines of chemical shifts of 143.60 and 136.37 with an intensity ratio of 3:1. This is a characteristic ¹³C NMR spectrum of the I_h-symmetric C₈₀ carbon cage.

Key words: metal nitride clusterfullerenes, isotope labeling, solid nitrogen source, arc-discharge method, rare earth scandium

Cite this article

Ling Qiu, Jiayi Liang, Zhuxia Zhang, Taishan Wang. Synthesis and Characterizations of ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene[J]. Acta Chimica Sinica, 2022, 80(7): 874-878.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

Figure 1. Based on the dc-arc discharge method, 15NH4Cl was used as an inorganic solid nitrogen source to synthesize Sc-based metal nitride clusterfullerenes. Sc315N@C2n and C2n represent the isotope-labeled Sc-based metal nitride clusterfullerenes (Sc315N@C80, Sc315N@C78) and hollow fullerenes (C60, C70, C76, C78, C84, etc.), respectively

Figure 2. (a) MALDI-TOF mass spectrum of pure Sc315N@C80. (b) Isotope distribution map of Sc315N@C80. (c) MALDI-TOF mass spectrum of Y3N@C80 and Sc315N@C80 mixture. The insets show their respective molecular structures. In the carbon cage, C is gray; in the encaged cluster, 15N is cyan, Sc is magenta, 14N is blue, and Y is green

样品	实验同位素峰质荷比	模拟同位素峰质荷比
Sc₃¹⁵N@C₈₀	1110.00, 1111.00, 1112.02, 1113.02, 1114.02	1109.89, 1110.89, 1111.89, 1112.89, 1113.89
Sc₃¹⁵N@C₇₈	1086.00, 1087.00, 1088.02, 1089.02, 1090.02	1085.89, 1086.89, 1087.89, 1088.89, 1089.89
Y₃N@C₈₀	1241.84, 1242.84, 1243.86, 1244.86, 1245.86	1241.73, 1242.73, 1243.73, 1244.73, 1245.73

Table 1. The experimental and simulated isotope peak mass-to-charge ratio of Sc315N@C80, Sc315N@C78 and Y3N@C80

Figure 3. (a) MALDI-TOF mass spectrum of pure Sc315N@C78. (b) Isotope distribution map of Sc315N@C78. (c) The MALDI-TOF mass spectrum of Y3N@C80 and Sc315N@C78 mixture. The insets show their respective molecular structures. In the carbon cage, C is gray; in the encaged cluster, 15N is cyan, Sc is magenta, 14N is blue, and Y is green

Figure 4. (a) The UV-Vis absorption spectrum of Sc315N@C80. (b) Carbon NMR spectrum of Sc315N@C80. The inset is the integral area of the two spectral lines. The area integrals of the left and right spectral lines are 68279.89 and 22795.17. The spectral line displacement intensity ratio is 3∶1

References 22

[1]	Yang, S. F.; Liu, F. P.; Chen, C. B.; Jiao, M. Z.; Wei, T. Chem. Commun. 2011, 47, 11822. doi: 10.1039/c1cc12318a
[2]	Dong, W.; Nie, M. S.; Lian, Y. F. Acta. Chim. Sinica 2017, 75, 453. (in Chinese) doi: 10.6023/A17030090
	(董薇, 聂梦思, 廉永福, 化学学报, 2017, 75, 453.) doi: 10.6023/A17030090
[3]	Shi, J. J.; Hu, Z. Q.; Yang, Y. H.; Bu, Y. X.; Shi, Z. J. Acta Phys. -Chim. Sin. 2019, 37, 1907077. (in Chinese)
	(施俊杰, 胡子琦, 杨逸豪, 步宇翔, 施祖进, 物理化学学报, 2019, 37, 1907077.)
[4]	Chaur, M. N.; Melin, F.; Ortiz, A. L.; Echegoyen, L. Angew. Chem. Int. Ed. 2009, 48, 7514. doi: 10.1002/anie.200901746
[5]	Dunsch, L.; Yang, S. F. Small 2007, 3, 1298. doi: 10.1002/smll.200700036
[6]	Dunsch, L.; Yang, S. F. Phys. Chem. Chem. Phys. 2007, 9, 3067. doi: 10.1039/B704143H
[7]	Lu, X.; Feng, L.; Akasaka, T.; Nagase, S. Chem. Soc. Rev. 2012, 41, 7723. doi: 10.1039/c2cs35214a
[8]	Rodriguez-Fortea, A.; Balch, A. L.; Poblet, J. M. Chem. Soc. Rev. 2011, 40, 3551. doi: 10.1039/c0cs00225a
[9]	Liu, T. T.; Wang, H. S.; Zhang, M. X.; Wang, M.; Chen, X. Polym. Bull. 2019, (4), 1. (in Chinese)
	(刘婷婷, 王华山, 张明秀, 王美, 陈醒, 高分子通报, 2019, (4), 1.)
[10]	Ruan, L. F.; Chang, X. L.; Sun, B. Y.; Guo, C. B.; Dong, J. Q.; Yang, S. T.; Gao, X. F.; Zhao, Y. L.; Yang, M. Chin. Sci. Bull. 2014, 59, 905. (in Chinese) doi: 10.1360/972013-1101
	(阮龙飞, 常雪灵, 孙宝云, 郭翠彬, 董金泉, 杨胜韬, 高兴发, 赵宇亮, 杨敏, 科学通报, 2014, 59, 905.)
[11]	Bhate, M. P.; Wylie, B. J.; Thompson, A.; Tian, L.; Nimigean, C.; McDermott, A. E. Protein. Expres. Purif. 2013, 91, 119. doi: 10.1016/j.pep.2013.07.013
[12]	Ruhland, K.; Frenzel, R.; Horny, R.; Nizamutdinova, A.; van Wüllen, L.; Moosburger-Will, J.; Horn, S. Polym. Degrad. Stab. 2017, 146, 298. doi: 10.1016/j.polymdegradstab.2017.10.018
[13]	Stevenson, S.; Rice, G.; Glass, T.; Harich, K.; Cromer, F.; Jordan, M. R.; Craft, J.; Hadju, E.; Bible, R.; Olmstead, M. M.; Maitra, K.; Fisher, A. J.; Balch, A. L.; Dorn, H. C. Nature 1999, 401, 55. doi: 10.1038/43415
[14]	Dunsch, L.; Krause, M.; Noack, J.; Georgi, P. J. Phys. Chem. Solids 2004, 65, 309. doi: 10.1016/j.jpcs.2003.03.002
[15]	Jiao, M. Z.; Zhang, W. F.; Xu, Y.; Wei, T.; Chen, C. B.; Liu, F. P.; Yang, S. F. Chem. Eur. J. 2012, 18, 2666. doi: 10.1002/chem.201101040
[16]	Liu, F. P.; Guan, J.; Wei, T.; Wang, S.; Jiao, M. Z.; Yang, S. F. Inorg. Chem. 2013, 52, 3814. doi: 10.1021/ic302436k
[17]	Lu, Y. X.; Zhang, J.; Zhao, C.; Nie, M. Z.; Wang, C. R.; Wang, T. S. Sci. China. Chem. 2020, 64, 29. doi: 10.1007/s11426-020-9843-2
[18]	Popov, A. A.; Yang, S. F.; Dunsch, L. Chem. Rev. 2013, 113, 5989. doi: 10.1021/cr300297r
[19]	Popov, A. A.; Avdoshenko, S. M.; Pendás, A. M.; Dunsch, L. Chem. Commun. 2012, 48, 8031. doi: 10.1039/c2cc32568c
[20]	Krause, M.; Dunsch, L. ChemPhysChem 2004, 5, 1445. doi: 10.1002/cphc.200400085
[21]	Wang, T. S.; Chen, N.; Xiang, J. F.; Li, B.; Wu, J. Y.; Xu, W.; Jiang, L.; Tan, K.; Shu, C. Y.; Lu, X.; Wang, C. R. J. Am. Chem. Soc. 2009, 131, 16646. doi: 10.1021/ja9077842
[22]	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.; Shu, C. Y.; Wang, C. R. J. Am. Chem. Soc. 2010, 132, 16362. doi: 10.1021/ja107843b

¹⁵N同位素标记的金属氮化物内嵌富勒烯的合成与表征

Synthesis and Characterizations of ¹⁵N Isotope Labeling Metal Nitride Clusterfullerene

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 22

Related Articles 0

Recommended Articles

Metrics

Comments

15N同位素标记的金属氮化物内嵌富勒烯的合成与表征