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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. 

Near infrared switch-on emission of SO3C7 in albumin allows imaging behind dark fabric which can inhibit latent blood stain detection. 

Dicyanobenzothiadiazole based dyes have shown exceptional tunability of oxidizing strength and absorption energy. The photophysical thermodynamic and kinetic properties are studied with desirable properties shown for future use in photocatalysis. 

Abstract Changes in the viscosity of intracellular microenvironments may indicate the onset of diseases like diabetes, blood‐based illnesses, hypertension, and Alzheimer's. To date, monitoring viscosity changes in the intracellular environment remains a challenge with prior work focusing primarily on visible light‐absorbing viscosity sensing fluorophores. Herein, a series of near‐infrared (NIR, 700–1000 nm) absorbing and emitting indolizine squaraine fluorophores (1PhSQ,2PhSQ,SO₃SQ,1DMASQ,7DMASQ, and1,7DMASQ) are synthesized and studied for NIR viscosity sensitivity.2PhSQexhibits a very high slope in its Forster‐Hoffmann plot at 0.75 which indicates this dye is a potent viscosity sensor. The properties of the squaraine fluorophores are studied computationallyviadensity functional theory (DFT) and time‐dependent (TD)‐DFT. Experimentally, both steady‐state and time‐resolved emission spectroscopy, absorption spectroscopy, and electrochemical characterization are conducted on the dyes. Precise photophysical tuning is observed within the series with emission maxima wavelengths as long as 881 nm for1,7DMASQand fluorescence quantum yields as high as 39.5 and 72.0 % for1PhSQin DCM and THF, respectively. The high tunability of this molecular scaffold renders indolizine squaraine fluorophores excellent prospects as viscosity‐sensitive biological imaging agents with2PhSQgiving a dramatically higher fluorescence quantum yield (from 0.3 to 37.1 %) as viscosity increases. 

In vivo fluorescence imaging in the shortwave infrared (SWIR, 1,000–1,700 nm) and extended SWIR (ESWIR, 1,700–2,700 nm) regions has tremendous potential for diagnostic imaging. Although image contrast has been shown to improve as longer wavelengths are accessed, the design and synthesis of organic fluorophores that emit in these regions is challenging. Here we synthesize a series of silicon-RosIndolizine (SiRos) fluorophores that exhibit peak emission wavelengths from 1,300–1,700 nm and emission onsets of 1,800–2,200 nm. We characterize the fluorophores photophysically (both steady-state and time- resolved), electrochemically and computationally using time-dependent density functional theory. Using two of the fluorophores (SiRos1300 and SiRos1550), we formulate nanoemulsions and use them for general systemic circulatory SWIR fluorescence imaging of the cardiovascular system in mice. These studies resulted in high-resolution SWIR images with well-defined vasculature visible throughout the entire circulatory system. This SiRos scaffold establishes design principles for generating long-wavelength emitting SWIR and ESWIR fluorophores.