Near-Infrared-III-Absorbing and -Emitting Dyes: Energy-Gap Engineering of Expanded Porphyrinoids via Metallation

Yue Wang, Koki Ogasahara, Daisuke Tomihama, Radomir Mysliborski, Masatoshi Ishida, Yongseok Hong, Yusuke Notsuka, Yoshihisa Yamaoka, Tomotaka Murayama, Atsuya Muranaka, Masanobu Uchiyama, Shigeki Mori, Yuhsuke Yasutake, Susumu Fukatsu, Dongho Kim, Hiroyuki Furuta

研究成果: Contribution to journalArticle査読

2 被引用数 (Scopus)

抄録

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.

本文言語英語
ページ(範囲)16161-16166
ページ数6
ジャーナルAngewandte Chemie - International Edition
59
37
DOI
出版ステータス出版済み - 9 7 2020

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)

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