Highly Stable Organic Bisradicals Protected by Mechanical Bonds

Kang Cai, Haochuan Mao, Wei Guang Liu, Yunyan Qiu, Yi Shi, Long Zhang, Dengke Shen, Hongliang Chen, Yang Jiao, Huang Wu, Zhichang Liu, Yuanning Feng, Charlotte L. Stern, Michael R. Wasielewski, William A. Goddard, J. Fraser Stoddart

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1 Citation (Scopus)


Two new highly charged [2]catenanes-namely, mHe[2]C·6PF6 and mHo[2]C·6PF6-were synthesized by exploiting radical host-guest templation between derivatives containing BIPYâ\¢+ radical cations and the meta analogue of cyclobis(paraquat-p-phenylene). In contrast to related [2]catenanes that have been isolated as air-stable monoradicals, both mHe[2]C·6PF6 and mHo[2]C·6PF6 exist as air-stable singlet bisradicals, as evidenced by both X-ray crystallography in the solid state and EPR spectroscopy in solution. Electrochemical studies indicate that the first two reduction peaks of these two [2]catenanes are shifted significantly to more positive potentials, a feature which is responsible for their extraordinary stability in air. The mixed-valence nature of the mono- A nd bisradical states endows them with unique NIR absorption properties, e.g., NIR absorption bands for the mono- A nd bisradical states observed at â1800 and â1450 nm, respectively. These [2]catenanes are potentially useful in applications that include NIR photothermal conversion, UV-vis-NIR multiple-state electrochromic materials, and multiple-state memory devices. Our findings highlight the principle of "mechanical-bond-induced stabilization" as an efficient strategy for designing persistent organic radicals.

Original languageEnglish
Pages (from-to)7190-7197
Number of pages8
JournalJournal of the American Chemical Society
Issue number15
Publication statusPublished - Apr 15 2020

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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  • Cite this

    Cai, K., Mao, H., Liu, W. G., Qiu, Y., Shi, Y., Zhang, L., Shen, D., Chen, H., Jiao, Y., Wu, H., Liu, Z., Feng, Y., Stern, C. L., Wasielewski, M. R., Goddard, W. A., & Stoddart, J. F. (2020). Highly Stable Organic Bisradicals Protected by Mechanical Bonds. Journal of the American Chemical Society, 142(15), 7190-7197. https://doi.org/10.1021/jacs.0c01989