物理化学学报 >> 2016, Vol. 32 >> Issue (8): 1929-1932.doi: 10.3866/PKU.WHXB201605092

论文 上一篇    下一篇

利用原位变温EPR研究富勒烯双体笼间的弱C―C键

谭天1,杨佳慧1,朱春华2,王官武2,陈家富2,苏吉虎1,*()   

  1. 1 中国科学技术大学,合肥微尺度物质科学国家实验室,近代物理系,合肥230026
    2 中国科学技术大学,合肥微尺度物质科学国家实验室,化学系,合肥230026
  • 收稿日期:2016-03-22 发布日期:2016-07-29
  • 通讯作者: 苏吉虎 E-mail:sujihu@ustc.edu.cn
  • 基金资助:
    国家重点基础研究发展规划项目(973)(2013CB921802)

AWeak Intercage C―C Bond in a [C60]fullerene Dimer Studied by In situ Variable Temperature EPR Spectroscopy

Tian TAN1,Jia-Hui YANG1,Chun-Hua ZHU2,Guan-Wu WANG2,Jia-Fu CHEN2,Ji-Hu SU1,*()   

  1. 1 Hefei National Laboratory for Physical Science at Microscale, Department of Modern Physics, University of Science and Technology of China, Hefei 230026, P. R. China
    2 Hefei National Laboratory for Physical Science at Microscale, Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China
  • Received:2016-03-22 Published:2016-07-29
  • Contact: Ji-Hu SU E-mail:sujihu@ustc.edu.cn
  • Supported by:
    The project was supported by the National Key Basic Research Program of China (973)(2013CB921802)

摘要:

本文研究了(C60)2-[P(O)(OCH3)]2富勒烯双体内的笼间C―C键的热力学性质(该双体的结构详见文献, Chem. Commun. 2011, 47, 6111)。原位、变温电子顺磁共振波谱实验结果表明,该C―C键的键离解能(BDE)为72.4 kJ·mol-1 (17.3 kcal·mol-1),仅约为常见氢键的两倍,或约为常见有机C―C键的五分之一。因此,该二聚体于较高温度时容易发生均裂反应,形成单体自由基;降温时又容易发生自由基聚合反应。基于该笼间C―C键所具有的这些热力学特性,我们对其可被用于制备有序的富勒烯分子元器件等材料作展开讨论。

关键词: C60富勒烯双体, 笼间C―C键, 热力学性质, 键离解能, 电子顺磁共振波谱学

Abstract:

This work studied the thermodynamic properties of a single intercage C―C bond in a [C60]fullerene dimer, (C60)2-[P(O)(OCH3)]2, previously synthesized by Wang et al. (Chem. Commun. 2011, 47, 6111). Data obtained from in situ variable temperature electron paramagnetic resonance (EPR) indicated a relatively low bond dissociation enthalpy (BDE) for this bond of 72.4 kJ ·mol-1 (17.3 kcal ·mol-1). This value is only approximately twice that of a typical hydrogen bond, or one fifth of the values determined for bonds in diamond or saturated hydrocarbons. The application of this pre-synthesized dimer to the formation of aligned fullerenes is discussed.

Key words: [C60]fullerene dimer, Singly intercage C―C bond, Thermodynamic property, Bond dissociation enthalpy, Electron paramagnetic resonance spectroscopy

MSC2000: 

  • O642