Development of Turn-On Probes for Acids Triggered by Aromaticity Enhancement Using Tricyclic Amidine Derivatives

Shota Matsumoto, Yasufumi Fuchi, Kazuteru Usui, Go Hirai, Satoru Karasawa

研究成果: ジャーナルへの寄稿記事

4 引用 (Scopus)

抄録

Two fluorophores consisting of tricyclic amidine derivatives (DHIm and DHPy) were prepared as selective turn-on probes for acids, which were triggered by an aromaticity enhancement. Both amidine derivatives were expanded rings prepared by condensed reactions between the corresponding dibromoalkanes and an aminonaphthyridine analogue. In X-ray analyses, DHIm, in which the dihydroimidazole ring was condensed into aminonaphthyridine, showed high planarity, compared to DHPy, with condensed dihydropyrimidine. The fluorescence properties of DHIm exhibited a higher quantum yield than DHPy due to the difference in planarity. Under acidic conditions, such as in the presence of H+ and M(II), protonations and complexations occurred, exhibiting a higher quantum yield than the neutral DHX (X = Im or Py). The nucleus-independent chemical shift values from the density functional theory calculations suggested that the protonations and complexations caused an enhancement of the aromaticity within the frameworks. These aromaticity changes led to intense fluorescence, and DHX behaved as a selective turn-on probe for acids and metal ions. Interestingly, this fluorescence turn-on system triggered by the aromaticity-based enhancement is not a typical system, such as the photoinduced electron transfer, aggregation-induced enhanced emission, and twisted intramolecular charge transfer systems, but is classified as a novel turn-on system.

元の言語英語
ページ(範囲)6612-6622
ページ数11
ジャーナルJournal of Organic Chemistry
84
発行部数11
DOI
出版物ステータス出版済み - 6 7 2019

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Amidines
Fluorescence
Protonation
Quantum yield
Derivatives
Complexation
Acids
Fluorophores
Chemical shift
Density functional theory
Metal ions
Charge transfer
Agglomeration
X rays
Electrons

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

これを引用

Development of Turn-On Probes for Acids Triggered by Aromaticity Enhancement Using Tricyclic Amidine Derivatives. / Matsumoto, Shota; Fuchi, Yasufumi; Usui, Kazuteru; Hirai, Go; Karasawa, Satoru.

:: Journal of Organic Chemistry, 巻 84, 番号 11, 07.06.2019, p. 6612-6622.

研究成果: ジャーナルへの寄稿記事

Matsumoto, Shota ; Fuchi, Yasufumi ; Usui, Kazuteru ; Hirai, Go ; Karasawa, Satoru. / Development of Turn-On Probes for Acids Triggered by Aromaticity Enhancement Using Tricyclic Amidine Derivatives. :: Journal of Organic Chemistry. 2019 ; 巻 84, 番号 11. pp. 6612-6622.
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abstract = "Two fluorophores consisting of tricyclic amidine derivatives (DHIm and DHPy) were prepared as selective turn-on probes for acids, which were triggered by an aromaticity enhancement. Both amidine derivatives were expanded rings prepared by condensed reactions between the corresponding dibromoalkanes and an aminonaphthyridine analogue. In X-ray analyses, DHIm, in which the dihydroimidazole ring was condensed into aminonaphthyridine, showed high planarity, compared to DHPy, with condensed dihydropyrimidine. The fluorescence properties of DHIm exhibited a higher quantum yield than DHPy due to the difference in planarity. Under acidic conditions, such as in the presence of H+ and M(II), protonations and complexations occurred, exhibiting a higher quantum yield than the neutral DHX (X = Im or Py). The nucleus-independent chemical shift values from the density functional theory calculations suggested that the protonations and complexations caused an enhancement of the aromaticity within the frameworks. These aromaticity changes led to intense fluorescence, and DHX behaved as a selective turn-on probe for acids and metal ions. Interestingly, this fluorescence turn-on system triggered by the aromaticity-based enhancement is not a typical system, such as the photoinduced electron transfer, aggregation-induced enhanced emission, and twisted intramolecular charge transfer systems, but is classified as a novel turn-on system.",
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