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Fluorescent organic dyes that absorb and emit in the near-infrared (NIR, 700–1000 nm) and shortwave infrared (SWIR, 1000–1700 nm) regions have the potential to produce noninvasive high-contrast biological images and videos. BODIPY dyes are well known for their high quantum yields in the visible energy region. To tune these chromophores to the NIR region, fused nitrogen-based heterocyclic indolizine donors were added to a BODIPY scaffold. The indolizine BODIPY dyes were synthesized via microwave-assisted Knoevenagel condensation with indolizine aldehydes. The non-protonated dyes showed NIR absorption and emission at longer wavelengths than an aniline benchmark. Protonation of the dyes produced a dramatic 0.35 eV bathochromic shift (230 nm shift from 797 nm to 1027 nm) to give a SWIR absorption and emission (λmaxemis = 1061 nm). Deprotonation demonstrates that material emission is reversibly switchable between the NIR and SWIR.
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Comparison of Vinyldimethylaniline and Indolizine Donor Groups on Si‐Substituted Xanthene Core Shortwave Infrared Fluorophores
Abstract Small organic molecules absorbing and emitting in the shortwave infrared (SWIR, 1000–2000 nm) region are desirable for biological imaging applications due to low auto‐fluorescence, reduce photon scattering, and good tissue penetration depth of photons which allows forin vivoimaging with high resolution and sensitivity. Si‐substituted xanthene‐based fluorophores with indolizine donors have demonstrated some of the longest wavelengths of absorption and emission from organic dyes. This work seeks to compare an indolizine heterocyclic nitrogen with dimethyl aniline nitrogen donors on otherwise identical Si‐substituted xanthene fluorophoresviaoptical spectroscopy, computational chemistry and electrochemistry. Three donors are compared including an indolizine donor, a ubiquitous dimethyl aniline donor, and a vinyl dimethyl aniline group that keeps the number of π‐bonds consistent with indolizine. Significantly higher quantum yields and molar absorptivity are observed in these studies for a dimethylamine‐based donor relative to a simple indolizine donor absorbing and emitting at similar wavelengths (~1312 nm emission). Substantially longer wavelengths are obtainable by appending aniline‐based groups to the indolizine donor (~1700 nm) indicating longer wavelengths can be accessed with indolizine donors while stronger emitters can be accessed with anilines in place of indolizine.
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- Award ID(s):
- 1757220
- PAR ID:
- 10513062
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemPhotoChem
- Volume:
- 8
- Issue:
- 8
- ISSN:
- 2367-0932
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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