Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

Takashi Otani; Ami Tsuyuki; Taiki Iwachi; Satoshi Someya; Kotaro Tateno; Hidetoshi Kawai; Takao Saito; Kyalo Stephen Kanyiva; Takanori Shibata

doi:10.1002/anie.201700507

Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

Takashi Otani^*, Ami Tsuyuki, Taiki Iwachi, Satoshi Someya, Kotaro Tateno, Hidetoshi Kawai, Takao Saito, Kyalo Stephen Kanyiva, Takanori Shibata

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

117 Citations (Scopus)

Abstract

A facile two-step synthesis of aza[7]helicenes possessing a 6-5-6-6-6-5-6 skeleton from commercially available 2,9-dichloro-1,10-phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent-mediated intramolecular double-NH/CH couplings was developed. Single-crystal X-ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φs) under both neutral (Φ: 0.25–0.55) and acidic conditions (Φ: up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (g_lum: up to 0.009).

Original language	English
Pages (from-to)	3906-3910
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	14
DOIs	https://doi.org/10.1002/anie.201700507
Publication status	Published - 2017 Mar 27

Keywords

X-ray diffraction
azahelicene
circularly polarized luminescence
fluorescence
oxidative coupling

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201700507

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title = "Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency",

abstract = "A facile two-step synthesis of aza[7]helicenes possessing a 6-5-6-6-6-5-6 skeleton from commercially available 2,9-dichloro-1,10-phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent-mediated intramolecular double-NH/CH couplings was developed. Single-crystal X-ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φs) under both neutral (Φ: 0.25–0.55) and acidic conditions (Φ: up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (glum: up to 0.009).",

keywords = "X-ray diffraction, azahelicene, circularly polarized luminescence, fluorescence, oxidative coupling",

author = "Takashi Otani and Ami Tsuyuki and Taiki Iwachi and Satoshi Someya and Kotaro Tateno and Hidetoshi Kawai and Takao Saito and Kanyiva, {Kyalo Stephen} and Takanori Shibata",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = mar,

day = "27",

doi = "10.1002/anie.201700507",

language = "English",

volume = "56",

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T1 - Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

AU - Otani, Takashi

AU - Tsuyuki, Ami

AU - Iwachi, Taiki

AU - Someya, Satoshi

AU - Tateno, Kotaro

AU - Kawai, Hidetoshi

AU - Saito, Takao

AU - Kanyiva, Kyalo Stephen

AU - Shibata, Takanori

PY - 2017/3/27

Y1 - 2017/3/27

N2 - A facile two-step synthesis of aza[7]helicenes possessing a 6-5-6-6-6-5-6 skeleton from commercially available 2,9-dichloro-1,10-phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent-mediated intramolecular double-NH/CH couplings was developed. Single-crystal X-ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φs) under both neutral (Φ: 0.25–0.55) and acidic conditions (Φ: up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (glum: up to 0.009).

AB - A facile two-step synthesis of aza[7]helicenes possessing a 6-5-6-6-6-5-6 skeleton from commercially available 2,9-dichloro-1,10-phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent-mediated intramolecular double-NH/CH couplings was developed. Single-crystal X-ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φs) under both neutral (Φ: 0.25–0.55) and acidic conditions (Φ: up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (glum: up to 0.009).

KW - X-ray diffraction

KW - azahelicene

KW - circularly polarized luminescence

KW - fluorescence

KW - oxidative coupling

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Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

Abstract

Keywords

ASJC Scopus subject areas

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