Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units

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

    Research output: Contribution to journalArticle

    24 Citations (Scopus)

    Abstract

    A series of [5]carbohelicene derivatives substituted by electron-withdrawing maleimide and electron-donating methoxy, such as maleimide-substituted [5]carbohelicene (HeliIm) and methoxy-substituted HeliIm (MeO-HeliIm), were newly designed and synthesized to examine the electrochemical properties, excited-state dynamic and circularly polarized luminescence (CPL). First, electrochemical measurements and DFT calculations of [5]carbohelicene derivatives were performed by comparing with the structural isomers: picene derivatives. Introduction of an electron-withdrawing maleimide group onto a [5]carbohelicene core contributes to the stabilized LUMO state in HeliIm as compared to that of [5]carbohelicene (Heli), whereas the energy level of HOMO state in MeO-HeliIm increases by introducing electron-donating methoxy (MeO) groups onto a HeliIm skeleton. The HOMO-LUMO gap of MeO-HeliIm is smaller than those of HeliIm and Heli, which is similar to the steady-state spectroscopic measurements. The absolute fluorescence quantum yield (ΦFL) of HeliIm (0.37) largely increased as compared to [5]carbohelicene, Heli (0.04), whereas ΦFL of MeO-HeliIm (0.22) was slightly smaller than that of HeliIm. Theses photophysical processes including intersystem crossing are successfully explained by the kinetic discussions. Since [5]carbohelicene derivatives show the chirality, measurements of circular dichroism (CD) and circularly polarized luminescence (CPL) were successfully performed. In particular, HeliIm and MeO-HeliIm have provide excellent circularly polarized luminescence (CPL) and the values of the anisotropy factor glum were estimated to be ∼2.4 × 10-3 and ∼2.3 × 10-3, relatively. This is the first observation of CPL in [5]carbohelicene derivatives.

    Original languageEnglish
    Pages (from-to)7860-7869
    Number of pages10
    JournalJournal of Physical Chemistry C
    Volume120
    Issue number14
    DOIs
    Publication statusPublished - 2016 Apr 21

    Fingerprint

    Luminescence
    luminescence
    Derivatives
    Electrons
    electrons
    theses
    musculoskeletal system
    chirality
    Chirality
    dichroism
    Dichroism
    Quantum yield
    Electrochemical properties
    Excited states
    isomers
    Discrete Fourier transforms
    Isomers
    energy levels
    Electron energy levels
    Anisotropy

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Electronic, Optical and Magnetic Materials
    • Surfaces, Coatings and Films
    • Energy(all)

    Cite this

    Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units. / Sakai, Hayato; Kubota, Takako; Yuasa, Junpei; Araki, Yasuyuki; Sakanoue, Tomo; Takenobu, Taishi; Wada, Takehiko; Kawai, Tsuyoshi; Hasobe, Taku.

    In: Journal of Physical Chemistry C, Vol. 120, No. 14, 21.04.2016, p. 7860-7869.

    Research output: Contribution to journalArticle

    Sakai, Hayato ; Kubota, Takako ; Yuasa, Junpei ; Araki, Yasuyuki ; Sakanoue, Tomo ; Takenobu, Taishi ; Wada, Takehiko ; Kawai, Tsuyoshi ; Hasobe, Taku. / Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 14. pp. 7860-7869.
    @article{adb018ecb34e4dca96e92bd45c890fee,
    title = "Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units",
    abstract = "A series of [5]carbohelicene derivatives substituted by electron-withdrawing maleimide and electron-donating methoxy, such as maleimide-substituted [5]carbohelicene (HeliIm) and methoxy-substituted HeliIm (MeO-HeliIm), were newly designed and synthesized to examine the electrochemical properties, excited-state dynamic and circularly polarized luminescence (CPL). First, electrochemical measurements and DFT calculations of [5]carbohelicene derivatives were performed by comparing with the structural isomers: picene derivatives. Introduction of an electron-withdrawing maleimide group onto a [5]carbohelicene core contributes to the stabilized LUMO state in HeliIm as compared to that of [5]carbohelicene (Heli), whereas the energy level of HOMO state in MeO-HeliIm increases by introducing electron-donating methoxy (MeO) groups onto a HeliIm skeleton. The HOMO-LUMO gap of MeO-HeliIm is smaller than those of HeliIm and Heli, which is similar to the steady-state spectroscopic measurements. The absolute fluorescence quantum yield (ΦFL) of HeliIm (0.37) largely increased as compared to [5]carbohelicene, Heli (0.04), whereas ΦFL of MeO-HeliIm (0.22) was slightly smaller than that of HeliIm. Theses photophysical processes including intersystem crossing are successfully explained by the kinetic discussions. Since [5]carbohelicene derivatives show the chirality, measurements of circular dichroism (CD) and circularly polarized luminescence (CPL) were successfully performed. In particular, HeliIm and MeO-HeliIm have provide excellent circularly polarized luminescence (CPL) and the values of the anisotropy factor glum were estimated to be ∼2.4 × 10-3 and ∼2.3 × 10-3, relatively. This is the first observation of CPL in [5]carbohelicene derivatives.",
    author = "Hayato Sakai and Takako Kubota and Junpei Yuasa and Yasuyuki Araki and Tomo Sakanoue and Taishi Takenobu and Takehiko Wada and Tsuyoshi Kawai and Taku Hasobe",
    year = "2016",
    month = "4",
    day = "21",
    doi = "10.1021/acs.jpcc.6b01344",
    language = "English",
    volume = "120",
    pages = "7860--7869",
    journal = "Journal of Physical Chemistry C",
    issn = "1932-7447",
    publisher = "American Chemical Society",
    number = "14",

    }

    TY - JOUR

    T1 - Synthetic Control of Photophysical Process and Circularly Polarized Luminescence of [5]Carbohelicene Derivatives Substituted by Maleimide Units

    AU - Sakai, Hayato

    AU - Kubota, Takako

    AU - Yuasa, Junpei

    AU - Araki, Yasuyuki

    AU - Sakanoue, Tomo

    AU - Takenobu, Taishi

    AU - Wada, Takehiko

    AU - Kawai, Tsuyoshi

    AU - Hasobe, Taku

    PY - 2016/4/21

    Y1 - 2016/4/21

    N2 - A series of [5]carbohelicene derivatives substituted by electron-withdrawing maleimide and electron-donating methoxy, such as maleimide-substituted [5]carbohelicene (HeliIm) and methoxy-substituted HeliIm (MeO-HeliIm), were newly designed and synthesized to examine the electrochemical properties, excited-state dynamic and circularly polarized luminescence (CPL). First, electrochemical measurements and DFT calculations of [5]carbohelicene derivatives were performed by comparing with the structural isomers: picene derivatives. Introduction of an electron-withdrawing maleimide group onto a [5]carbohelicene core contributes to the stabilized LUMO state in HeliIm as compared to that of [5]carbohelicene (Heli), whereas the energy level of HOMO state in MeO-HeliIm increases by introducing electron-donating methoxy (MeO) groups onto a HeliIm skeleton. The HOMO-LUMO gap of MeO-HeliIm is smaller than those of HeliIm and Heli, which is similar to the steady-state spectroscopic measurements. The absolute fluorescence quantum yield (ΦFL) of HeliIm (0.37) largely increased as compared to [5]carbohelicene, Heli (0.04), whereas ΦFL of MeO-HeliIm (0.22) was slightly smaller than that of HeliIm. Theses photophysical processes including intersystem crossing are successfully explained by the kinetic discussions. Since [5]carbohelicene derivatives show the chirality, measurements of circular dichroism (CD) and circularly polarized luminescence (CPL) were successfully performed. In particular, HeliIm and MeO-HeliIm have provide excellent circularly polarized luminescence (CPL) and the values of the anisotropy factor glum were estimated to be ∼2.4 × 10-3 and ∼2.3 × 10-3, relatively. This is the first observation of CPL in [5]carbohelicene derivatives.

    AB - A series of [5]carbohelicene derivatives substituted by electron-withdrawing maleimide and electron-donating methoxy, such as maleimide-substituted [5]carbohelicene (HeliIm) and methoxy-substituted HeliIm (MeO-HeliIm), were newly designed and synthesized to examine the electrochemical properties, excited-state dynamic and circularly polarized luminescence (CPL). First, electrochemical measurements and DFT calculations of [5]carbohelicene derivatives were performed by comparing with the structural isomers: picene derivatives. Introduction of an electron-withdrawing maleimide group onto a [5]carbohelicene core contributes to the stabilized LUMO state in HeliIm as compared to that of [5]carbohelicene (Heli), whereas the energy level of HOMO state in MeO-HeliIm increases by introducing electron-donating methoxy (MeO) groups onto a HeliIm skeleton. The HOMO-LUMO gap of MeO-HeliIm is smaller than those of HeliIm and Heli, which is similar to the steady-state spectroscopic measurements. The absolute fluorescence quantum yield (ΦFL) of HeliIm (0.37) largely increased as compared to [5]carbohelicene, Heli (0.04), whereas ΦFL of MeO-HeliIm (0.22) was slightly smaller than that of HeliIm. Theses photophysical processes including intersystem crossing are successfully explained by the kinetic discussions. Since [5]carbohelicene derivatives show the chirality, measurements of circular dichroism (CD) and circularly polarized luminescence (CPL) were successfully performed. In particular, HeliIm and MeO-HeliIm have provide excellent circularly polarized luminescence (CPL) and the values of the anisotropy factor glum were estimated to be ∼2.4 × 10-3 and ∼2.3 × 10-3, relatively. This is the first observation of CPL in [5]carbohelicene derivatives.

    UR - http://www.scopus.com/inward/record.url?scp=84964766289&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=84964766289&partnerID=8YFLogxK

    U2 - 10.1021/acs.jpcc.6b01344

    DO - 10.1021/acs.jpcc.6b01344

    M3 - Article

    AN - SCOPUS:84964766289

    VL - 120

    SP - 7860

    EP - 7869

    JO - Journal of Physical Chemistry C

    JF - Journal of Physical Chemistry C

    SN - 1932-7447

    IS - 14

    ER -