Metal‐Bridging Cyclic Bilatriene Analogue Affords Stable π‐Radicaloid Dyes with Near‐Infrared II Absorption
Abstract Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α‐linked conjugated pyrrole units, whereas an N‐confused analogue used in this work possesses β‐linked pyrrole moieties at the terminal, demonstrating a unique metal binding capability. Unprecedentedly, the metal‐COD cations are accommodated at the outer nitrogen sites, which induced the formation of open‐shell metal‐radicaloid species. The resulting compounds are highly stable under ambient conditions and demonstrated facile redox conversion to afford the corresponding cation and anion species. Furthermore, the radicaloid complexes showed a distinct second near‐infrared absorption (NIR‐II) capability extending up to 1500 nm along with high photostability. These features emphasized that the complexes can be potential NIR‐II light‐responsible photothermal and photoacoustic imaging contrast agents based on the metal‐radicaloid dye platform.
Authors
- Shigeki Mori (ORCID: https://orcid.org/0000-0001-6731-2357)
- Yuki Ide (ORCID: https://orcid.org/0000-0003-0648-0503)
- Jun Tae Song (ORCID: https://orcid.org/0000-0003-1047-6152)
- Hiroyuki Furuta (ORCID: https://orcid.org/0000-0002-3881-8807)
- Tatsumi Ishihara (ORCID: https://orcid.org/0000-0002-7434-3773)
- Anupam Ghosh (ORCID: https://orcid.org/0000-0001-9865-6945)
- Yoshihisa Yamaoka (ORCID: https://orcid.org/0000-0001-6395-7721)
- Masatoshi Ishida
- Takahisa Ikeue (ORCID: https://orcid.org/0000-0002-1673-1532)
Institutions
- Kyushu University (JP)
- Shimane University (JP)
- Hokkaido University (JP)
- Komatsu University (JP)
- Matsuyama University (JP)
- Rigaku (Japan) (JP)
- Kyushu International University (JP)
- Ehime University (JP)
- Tokyo Metropolitan University (JP)
Publication Details
- Journal
- Angewandte Chemie
- Published
- 2024-12-10
- DOI
- https://doi.org/10.1002/ange.202418751
- Primary Topic
- Luminescence and Fluorescent Materials
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Japan Society for the Promotion of Science London
- Ministry of Education, Culture, Sports, Science and Technology
- Izumi Science and Technology Foundation
- Japan Society for the Promotion of Science
- Japan Science and Technology Agency
- Precursory Research for Embryonic Science and Technology