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



邱玲a, 梁家艺a, 张竹霞a,b,c,*(), 王太山d,*()   

  1. 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 Qiua, Jiayi Lianga, Zhuxia Zhanga,b,c(), Taishan Wangd()   

  1. 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)

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 Ih-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-Ih and Sc315N@C78 were obtained. Mass spectrometry was used to characterize the molecular weight of Sc315N@C80-Ih and Sc315N@C78. According to the isotopic distributions of Sc315N@C80-Ih and Sc315N@C78 in mass spectra, their molecular weight values have increased by 1 compared to those of unlabeled Sc3N@C80-Ih 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-Ih 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 Ih-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 Ih-symmetric C80 carbon cage.

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