Near‐Infrared‐III‐Absorbing and ‐Emitting Dyes: Energy‐Gap Engineering of Expanded Porphyrinoids via Metallation
| Autor: | Masanobu Uchiyama, Dongho Kim, Koki Ogasahara, Yue Wang, Radomir Mysliborski, Yusuke Notsuka, Masatoshi Ishida, Susumu Fukatsu, Yongseok Hong, Daisuke Tomihama, Yuhsuke Yasutake, Yoshihisa Yamaoka, Hiroyuki Furuta, Shigeki Mori, Tomotaka Murayama, Atsuya Muranaka |
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| Rok vydání: | 2020 |
| Předmět: |
Materials science
010405 organic chemistry Band gap Near-infrared spectroscopy Photoacoustic imaging in biomedicine General Medicine General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Catalysis 0104 chemical sciences Metal visual_art visual_art.visual_art_medium Molecular orbital Absorption (electromagnetic radiation) Photoacoustic spectroscopy |
| Zdroj: | Angewandte Chemie International Edition. 59:16161-16166 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.202006026 |
| Popis: | The synthesis of organometallic complexes of modified 26π-conjugated hexaphyrins with absorption and emission capabilities in the third near-infrared region (NIR-III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis-PdII and bis-PtII complexes of hexaphyrin via N-confusion modification led to substantial metal dπ -pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO-LUMO energy gap. A remarkable long-wavelength shift of the lowest S0 →S1 absorption beyond 1700 nm was achieved with the bis-PtII complex, t-Pt2 -3. The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t-Pt2 -3 potentially useful as a NIR-III PA contrast agent. The rigid bis-PdII complexes, t-Pd2 -3 and c-Pd2 -3, are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR-III-emissive and photoacoustic-response capabilities. |
| Databáze: | OpenAIRE |
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