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Issue 9, 2019
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UV-irradiation of self-assembled triphenylamines affords persistent and regenerable radicals

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Abstract

UV-irradiation of assembled urea-tethered triphenylamine dimers results in the formation of persistent radicals, whereas radicals generated in solution are reactive and quickly degrade. In the solid-state, high quantities of radicals (approximately 1 in 150 molecules) are formed with a half-life of one week with no significant change in the single crystal X-ray diffraction. Remarkably, after decay, re-irradiation of the solid sample regenerates the radicals to their original concentration. The photophysics upon radical generation are also altered. Both the absorption and emission are significantly quenched without external oxidation likely due to the delocalization of the radicals within the crystals. The factors that influence radical stability and generation are correlated to the rigid supramolecular framework formed by the urea tether of the triphenylamine dimer. Electrochemical evidence demonstrates that these compounds can be oxidized in solution at 1.0 V vs. SCE to generate radical cations, whose EPR spectra were compared with spectra of the solid-state photogenerated radicals. Additionally, these compounds display changes in emission due to solvent effects from fluorescence to phosphorescence. Understanding how solid-state assembly alters the photophysical properties of triphenylamines could lead to further applications of these compounds for magnetic and conductive materials.

Graphical abstract: UV-irradiation of self-assembled triphenylamines affords persistent and regenerable radicals

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Publication details

The article was received on 16 Oct 2018, accepted on 09 Jan 2019 and first published on 10 Jan 2019


Article type: Edge Article
DOI: 10.1039/C8SC04607G
Chem. Sci., 2019,10, 2670-2677
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    UV-irradiation of self-assembled triphenylamines affords persistent and regenerable radicals

    A. J. Sindt, B. A. DeHaven, D. F. McEachern, D. M. M. M. Dissanayake, M. D. Smith, A. K. Vannucci and L. S. Shimizu, Chem. Sci., 2019, 10, 2670
    DOI: 10.1039/C8SC04607G

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