Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent "push-Pull" Tetrathia[9]helicenes

Yuki Yamamoto, Hayato Sakai, Junpei Yuasa, Yasuyuki Araki, Takehiko Wada, Tomo Sakanoue, Taishi Takenobu, Tsuyoshi Kawai, Taku Hasobe

    Research output: Contribution to journalArticle

    34 Citations (Scopus)

    Abstract

    A series of fluorescent "push-pull" tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited-state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the "push-pull" character, which was enhanced by further introduction of an electron-releasing Me2N group or an electron-withdrawing NC group onto the quinoxaline unit (denoted as Me2N-QTTH and NC-QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (ΦFL) were achieved. In particular, the maximum ΦFL of Me2N-QTTH was 0.43 in benzene (NC-QTTH: ΦFL=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; ΦFL=0.02). These enhancements were also explained by kinetic discussion of the excited-state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the ΦFL values thus enabled us to show the excellent CPL properties. The value of anisotropy factor gCPL (normalized difference in emission of right-handed and left-handed circularly polarized light) was estimated to be 3.0×10-3 for NC-QTTH. Controlled push-pull: A series of fluorescent "push-pull" thiahelicenes based on quinoxaline-fused tetrathia[9]helicene derivatives was synthesized to control the excited state dynamics and circularly polarized luminescence properties. The maximum ΦFL values of 0.43 and 0.30 were obtained in benzene.

    Original languageEnglish
    Pages (from-to)4263-4273
    Number of pages11
    JournalChemistry - A European Journal
    Volume22
    Issue number12
    DOIs
    Publication statusPublished - 2016 Mar 14

    Fingerprint

    Quinoxalines
    Excited states
    Luminescence
    Benzene
    Fluorescence
    Derivatives
    Electrons
    Quantum yield
    Light polarization
    Density functional theory
    Anisotropy
    Kinetics
    helicenes

    Keywords

    • excited-state dynamics
    • fluorescence
    • helicenes
    • luminescence
    • push-pull molecules

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent "push-Pull" Tetrathia[9]helicenes. / Yamamoto, Yuki; Sakai, Hayato; Yuasa, Junpei; Araki, Yasuyuki; Wada, Takehiko; Sakanoue, Tomo; Takenobu, Taishi; Kawai, Tsuyoshi; Hasobe, Taku.

    In: Chemistry - A European Journal, Vol. 22, No. 12, 14.03.2016, p. 4263-4273.

    Research output: Contribution to journalArticle

    Yamamoto, Y, Sakai, H, Yuasa, J, Araki, Y, Wada, T, Sakanoue, T, Takenobu, T, Kawai, T & Hasobe, T 2016, 'Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent "push-Pull" Tetrathia[9]helicenes', Chemistry - A European Journal, vol. 22, no. 12, pp. 4263-4273. https://doi.org/10.1002/chem.201504048
    Yamamoto, Yuki ; Sakai, Hayato ; Yuasa, Junpei ; Araki, Yasuyuki ; Wada, Takehiko ; Sakanoue, Tomo ; Takenobu, Taishi ; Kawai, Tsuyoshi ; Hasobe, Taku. / Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent "push-Pull" Tetrathia[9]helicenes. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 12. pp. 4263-4273.
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    abstract = "A series of fluorescent {"}push-pull{"} tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited-state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the {"}push-pull{"} character, which was enhanced by further introduction of an electron-releasing Me2N group or an electron-withdrawing NC group onto the quinoxaline unit (denoted as Me2N-QTTH and NC-QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (ΦFL) were achieved. In particular, the maximum ΦFL of Me2N-QTTH was 0.43 in benzene (NC-QTTH: ΦFL=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; ΦFL=0.02). These enhancements were also explained by kinetic discussion of the excited-state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the ΦFL values thus enabled us to show the excellent CPL properties. The value of anisotropy factor gCPL (normalized difference in emission of right-handed and left-handed circularly polarized light) was estimated to be 3.0×10-3 for NC-QTTH. Controlled push-pull: A series of fluorescent {"}push-pull{"} thiahelicenes based on quinoxaline-fused tetrathia[9]helicene derivatives was synthesized to control the excited state dynamics and circularly polarized luminescence properties. The maximum ΦFL values of 0.43 and 0.30 were obtained in benzene.",
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    AU - Yuasa, Junpei

    AU - Araki, Yasuyuki

    AU - Wada, Takehiko

    AU - Sakanoue, Tomo

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