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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33 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)4429-4437
Number of pages9
JournalJournal of the American Chemical Society
Issue number9
Publication statusPublished - 2020 Mar 4

Bibliographical note

Funding Information:
The present work at Kyushu University was supported by JSPS KAKENHI Grant Numbers (JP19H04586 and JP19K05439). Funding from the Tokuyama Research Foundation is gratefully acknowledged. The work at Yonsei University was supported by the Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science.

Publisher Copyright:
© 2020 American Chemical Society.

All Science Journal Classification (ASJC) codes

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


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