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; Stephen Kyalo 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, Stephen Kyalo Kanyiva, Takanori Shibata

Global Center for Science and Engineering

Research output: Contribution to journal › Article

57 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

Fingerprint

Keywords

azahelicene
circularly polarized luminescence
fluorescence
oxidative coupling
X-ray diffraction

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Cite this

Otani, T., Tsuyuki, A., Iwachi, T., Someya, S., Tateno, K., Kawai, H., Saito, T., Kanyiva, S. K., & Shibata, T. (2017). Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency. Angewandte Chemie - International Edition, 56(14), 3906-3910. https://doi.org/10.1002/anie.201700507

Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency. / Otani, Takashi; Tsuyuki, Ami; Iwachi, Taiki; Someya, Satoshi; Tateno, Kotaro; Kawai, Hidetoshi; Saito, Takao; Kanyiva, Stephen Kyalo ; Shibata, Takanori.

In: Angewandte Chemie - International Edition, Vol. 56, No. 14, 27.03.2017, p. 3906-3910.

Research output: Contribution to journal › Article

Otani, Takashi ; Tsuyuki, Ami ; Iwachi, Taiki ; Someya, Satoshi ; Tateno, Kotaro ; Kawai, Hidetoshi ; Saito, Takao ; Kanyiva, Stephen Kyalo ; Shibata, Takanori. / Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency. In: Angewandte Chemie - International Edition. 2017 ; Vol. 56, No. 14. pp. 3906-3910.

@article{4d4e0710bdf14abab47cc82ecc41c0fc,

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

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

year = "2017",

month = mar,

day = "27",

doi = "10.1002/anie.201700507",

language = "English",

volume = "56",

pages = "3906--3910",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "14",

}

TY - JOUR

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, Stephen Kyalo

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 - azahelicene

KW - circularly polarized luminescence

KW - fluorescence

KW - oxidative coupling

KW - X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=85014734420&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85014734420&partnerID=8YFLogxK

U2 - 10.1002/anie.201700507

DO - 10.1002/anie.201700507

M3 - Article

C2 - 28267252

AN - SCOPUS:85014734420

VL - 56

SP - 3906

EP - 3910

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 14

ER -

Access to Document

10.1002/anie.201700507