Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (9): 659-665.DOI: 10.6023/A18070273 Previous Articles     Next Articles

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超分子自由基:构筑、调控与功能

焦阳, 张希   

  1. 清华大学化学系 有机光电子与分子工程教育部重点实验室 北京 100084
  • 收稿日期:2018-07-16 出版日期:2018-09-15 发布日期:2018-07-23
  • 通讯作者: 张希 E-mail:xi@mail.tsinghua.edu.cn
  • 作者简介:焦阳,2013年本科毕业于清华大学化学工程系,获工学学士学位.同年保送进入清华大学化学系继续学习,并于2018年获得理学博士学位,导师为张希教授.研究方向为超分子自由基的性质调控与功能;张希,清华大学化学系教授.1982~1992年在吉林大学化学系先后获得理学学士、硕士和博士学位.期间于1991~1992年在德国美因茨大学博士结合培养.1992~1994年吉林大学化学系讲师,1994~2003年吉林大学化学系教授.2003年至今,清华大学化学系教授,2008~2014年曾任化学系主任.2007年当选中国科学院院士.现任国家自然科学基金委员会副主任.目前主要从事超分子体系的构筑、调控与功能研究.
  • 基金资助:

    项目受国家自然科学基金(Nos.21434004,91527000)资助.

Supramolecular Free Radicals: Fabrication, Modulation and Functions

Jiao Yang, Zhang Xi   

  1. Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering, Tsinghua University, Bei-jing 100084
  • Received:2018-07-16 Online:2018-09-15 Published:2018-07-23
  • Contact: 10.6023/A18070273 E-mail:xi@mail.tsinghua.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21434004, 91527000).

Modulating the activity of radicals is of great importance for the applications in radical-based materials and radical-mediated reactions. To this end, we have proposed a new concept of "supramolecular free radicals", which refers to the free radicals stabilized or activated through supramolecular approaches. Based on the host-guest chemistry of cucurbiturils (CB), we have fabricated three kinds of supramolecular free radicals to modulate the activity and realize diverse functions. Firstly, radical anions can be stabilized by the steric effect and electrostatic effect of CB. As a result, we have constructed a highly efficient near-infrared photothermal conversion system, which displays selective antibacterial performance. Secondly, owing to the electrostatic effect of CB, radical cations can be activated to induce a significant acceleration of Fenton oxidation reaction. Thirdly, by taking advantage of the dynamic nature of host-guest interactions, we can endow the reaction intermediate with adaptive reactivity, which greatly improves the catalytic efficiency of alcohol oxidation. It is highly anticipated that this series of research opens a new horizon in supramolecular materials and supramolecular catalysis.

Key words: supramolecular free radicals, cucurbiturils, host-guest interactions, near-infrared photothermal conversion, supramolecular catalysis