A Switchable Near‐Infrared‐Absorbing Dye Based on Redox‐Bistable Benzitetraazaporphyrin
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- Shunsuke Yanagi
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
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- Akihisa Matsumoto
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
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- Naoyuki Toriumi
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
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- Yusuke Tanaka
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
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- Kazunori Miyamoto
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
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- Atsuya Muranaka
- Advanced Elements Chemistry Laboratory Cluster for Pioneering Research (CPR) RIKEN 2-1 Hirosawa Wako-shi Saitama 351-0198 Japan
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- Masanobu Uchiyama
- Graduate School of Pharmaceutical Sciences The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033 Japan
書誌事項
- 公開日
- 2023-02-06
- 資源種別
- journal article
- 権利情報
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- http://creativecommons.org/licenses/by-nc-nd/4.0/
- DOI
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- 10.1002/anie.202218358
- 10.1002/ange.202218358
- 公開者
- Wiley
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説明
<jats:title>Abstract</jats:title><jats:p>Activatable near‐infrared (NIR) dyes responsive to external stimuli are used in medical and other applications. Here, we describe the design and synthesis of bench‐stable 18π‐ and 20π‐electron benzitetraazaporphyrins (BzTAPs) possessing redox‐switchable NIR properties. X‐Ray, NMR, and UV/Visible‐NIR analyses revealed that 20π‐electron BzTAP <jats:bold>1</jats:bold> exhibits NIR absorption and antiaromaticity with a paratropic ring‐current, while 18π‐electron BzTAP <jats:bold>2</jats:bold> shows weakly aromatic character with NIR inertness. Notably, the NIR‐silent BzTAP <jats:bold>2</jats:bold> was readily converted to the NIR‐active BzTAP <jats:bold>1</jats:bold> in the presence of mild reducing agents such as amine. The intense NIR absorption band of BzTAP <jats:bold>1</jats:bold> is in sharp contrast to the very weak absorption bands of previously reported antiaromatic porphyrinoids. Molecular orbital analysis revealed that symmetry‐lowering perturbation of the 20π‐electron porphyrinoid skeleton enables the HOMO–LUMO transition of <jats:bold>1</jats:bold> to be electric‐dipole‐allowed. BzTAPs are expected to be useful for constructing activatable NIR probes working in reductive environments.</jats:p>
収録刊行物
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- Angewandte Chemie International Edition
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Angewandte Chemie International Edition 62 (11), 2023-02-06
Wiley
