4.8 Article

Naphthalimide-Fused Dipyrrins: Tunable Halochromic Switches and Photothermal NIR-II Dyes

Journal

ADVANCED SCIENCE
Volume 9, Issue 19, Pages -

Publisher

WILEY
DOI: 10.1002/advs.202105886

Keywords

dipyrrins; donor-acceptor systems; halochromism; near-infrared dyes; photothermal agents

Funding

  1. Foundation for Polish Science [TEAM POIR.04.04.00-00-5BF1/17-00]
  2. National Science Centre of Poland [UMO-2018/29/B/ST5/01842]
  3. National Research Foundation of Korea (NRF) - Korea government (MSIT) [2021R1A2C3006308]
  4. National Research Foundation of Korea [2021R1A2C3006308] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)

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A family of tunable halochromic switches is developed using a naphthalimide-fused dipyrrin as the core pi-conjugated motif. The electronic properties of these switches can be tuned by substitution of aryl groups with different donor-acceptor strengths. Protonation results in conformational changes and enhanced electronic coupling, leading to halochromic effects and absorption switching between NIR-I and NIR-II ranges. Additionally, selected switches demonstrate a NIR-II photothermal effect switchable by acid-base chemistry.
A family of tunable halochromic switches is developed using a naphthalimide-fused dipyrrin as the core pi-conjugated motif. Electronic properties of these dipyrrins are tuned by substitution of their alpha and meso positions with aryl groups of variable donor-acceptor strength. The first protonation results in a conformational change that enhances electronic coupling between the dipyrrin chromophore and the meso substituent, leading to halochromic effects that occasionally exceed 200 nm and switch the absorption between the near-infrared (NIR)-I and NIR-II ranges. A NIR-II photothermal effect, switchable by acid-base chemistry is demonstrated for selected dipyrrins. Further protonation is possible for derivatives bearing additional amino groups, leading to up to four halochromic switching step. The most electron-rich dipyrrins are also susceptible to chemical oxidation, yielding NIR-absorbing radical cations and closed-shell dications.

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