Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

J. Reynisson, R. Wilbrandt, V. Brinck, B.W. Laursen, K. Nørgaard, N. Harrit, A.M. Brouwer

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    Trioxatriangulenium (TOTA(+), 4,8,12-trioxa-4,8,12,]2c-tetrahydro-dibenzo[cd,mn]-pyrenylium) is a closed shell carbenium ion, which is stable in non-nucleophilic polar solvents at ambient temperatures. In alcohols, small quantities of the leuco ether are formed in a reversible reaction. The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown to contribute in varying degrees. Quenching is also observed in the presence of halide ions. Quenching rate constants are derived from lifetime measurements while charge transfer (CT) complex formation constants follow from the steady-state Stern-Volmer plots. CT-complex formation with three discogenic triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties.
    Original languageEnglish
    JournalPhotochemical & Photobiological Sciences
    Volume1
    Issue number10
    Pages (from-to)763-773
    ISSN1474-905X
    DOIs
    Publication statusPublished - 2002

    Cite this

    Reynisson, J., Wilbrandt, R., Brinck, V., Laursen, B. W., Nørgaard, K., Harrit, N., & Brouwer, A. M. (2002). Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state. Photochemical & Photobiological Sciences, 1(10), 763-773. https://doi.org/10.1039/b204954f
    Reynisson, J. ; Wilbrandt, R. ; Brinck, V. ; Laursen, B.W. ; Nørgaard, K. ; Harrit, N. ; Brouwer, A.M. / Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state. In: Photochemical & Photobiological Sciences. 2002 ; Vol. 1, No. 10. pp. 763-773.
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    title = "Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state",
    abstract = "Trioxatriangulenium (TOTA(+), 4,8,12-trioxa-4,8,12,]2c-tetrahydro-dibenzo[cd,mn]-pyrenylium) is a closed shell carbenium ion, which is stable in non-nucleophilic polar solvents at ambient temperatures. In alcohols, small quantities of the leuco ether are formed in a reversible reaction. The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown to contribute in varying degrees. Quenching is also observed in the presence of halide ions. Quenching rate constants are derived from lifetime measurements while charge transfer (CT) complex formation constants follow from the steady-state Stern-Volmer plots. CT-complex formation with three discogenic triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties.",
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    Reynisson, J, Wilbrandt, R, Brinck, V, Laursen, BW, Nørgaard, K, Harrit, N & Brouwer, AM 2002, 'Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state', Photochemical & Photobiological Sciences, vol. 1, no. 10, pp. 763-773. https://doi.org/10.1039/b204954f

    Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state. / Reynisson, J.; Wilbrandt, R.; Brinck, V.; Laursen, B.W.; Nørgaard, K.; Harrit, N.; Brouwer, A.M.

    In: Photochemical & Photobiological Sciences, Vol. 1, No. 10, 2002, p. 763-773.

    Research output: Contribution to journalJournal articleResearchpeer-review

    TY - JOUR

    T1 - Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

    AU - Reynisson, J.

    AU - Wilbrandt, R.

    AU - Brinck, V.

    AU - Laursen, B.W.

    AU - Nørgaard, K.

    AU - Harrit, N.

    AU - Brouwer, A.M.

    PY - 2002

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    N2 - Trioxatriangulenium (TOTA(+), 4,8,12-trioxa-4,8,12,]2c-tetrahydro-dibenzo[cd,mn]-pyrenylium) is a closed shell carbenium ion, which is stable in non-nucleophilic polar solvents at ambient temperatures. In alcohols, small quantities of the leuco ether are formed in a reversible reaction. The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown to contribute in varying degrees. Quenching is also observed in the presence of halide ions. Quenching rate constants are derived from lifetime measurements while charge transfer (CT) complex formation constants follow from the steady-state Stern-Volmer plots. CT-complex formation with three discogenic triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties.

    AB - Trioxatriangulenium (TOTA(+), 4,8,12-trioxa-4,8,12,]2c-tetrahydro-dibenzo[cd,mn]-pyrenylium) is a closed shell carbenium ion, which is stable in non-nucleophilic polar solvents at ambient temperatures. In alcohols, small quantities of the leuco ether are formed in a reversible reaction. The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown to contribute in varying degrees. Quenching is also observed in the presence of halide ions. Quenching rate constants are derived from lifetime measurements while charge transfer (CT) complex formation constants follow from the steady-state Stern-Volmer plots. CT-complex formation with three discogenic triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties.

    KW - 7-I poly

    U2 - 10.1039/b204954f

    DO - 10.1039/b204954f

    M3 - Journal article

    VL - 1

    SP - 763

    EP - 773

    JO - Photochemical & Photobiological Sciences

    JF - Photochemical & Photobiological Sciences

    SN - 1474-905X

    IS - 10

    ER -