Bis-Metal Complexes of Doubly N-Confused Dioxohexaphyrins as Potential Near-Infrared-II Photoacoustic Dyes

Keito Shimomura, Hiroto Kai, Yuma Nakamura, Yongseok Hong, Shigeki Mori, Koji Miki, Kouichi Ohe, Yusuke Notsuka, Yoshihisa Yamaoka, Masatoshi Ishida, Dongho Kim, Hiroyuki Furuta

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We investigated the detailed photophysical properties of a series of bis-metal (Zn and Cu) dioxohexaphyrin complexes as potential second near-infrared (NIR-II)-light responsive dyes. A cisoid-configured 28π-electron-conjugated dioxohexaphyrin analogue (c-3a) containing two peculiar "confused pyrrole"moieties in the framework is identified as a reduced isomer derivative of a transoid 26π-dioxohexaphyrin (t-2a). The symmetry-altered structure of c-3a affords a heteroleptic inner environment within the NNNN/NNOO donor core, which imparts its highly flexible electronic features and nonplanar geometry. The macrocycle c-3a can be transformed into the corresponding 26π-electron congener (c-2a) having a coplanar rectangular structure by unique solvent-mediated redox reactivity. Furthermore, upon metal complexation, saddle-distorted bis-metal complexes (c-M2-2a) were formed as the 26π-conjugated structural isomer of the trans-dioxohexaphyrin species (i.e., t-M2-2a). These isoelectronic dioxohexaphyrins demonstrate precise geometry-dependent photophysical properties. Broad tailing NIR-II absorption, weak emissive character, and rapid-decay of the S1 state are observed for c-Zn2-2a. In contrast, the coplanar t-M2-2a exhibits efficient photoacoustic response upon laser excitation with NIR-II light (λ > 1000 nm). To the best of our knowledge, this is the first example of an expanded porphyrin-based photoacoustic contrast agent responsive to NIR-II light.

元の言語英語
ページ(範囲)4429-4437
ページ数9
ジャーナルJournal of the American Chemical Society
142
発行部数9
DOI
出版物ステータス出版済み - 3 4 2020

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Shimomura, K., Kai, H., Nakamura, Y., Hong, Y., Mori, S., Miki, K., Ohe, K., Notsuka, Y., Yamaoka, Y., Ishida, M., Kim, D., & Furuta, H. (2020). Bis-Metal Complexes of Doubly N-Confused Dioxohexaphyrins as Potential Near-Infrared-II Photoacoustic Dyes. Journal of the American Chemical Society, 142(9), 4429-4437. https://doi.org/10.1021/jacs.9b13475