Water-Soluble NIR Absorbing and Emitting Indolizine Cyanine and Indolizine Squaraine Dyes for Biological Imaging.

Organic dyes that absorb and emit in the near-infrared (NIR) region are potentially noninvasive, high-resolution, and rapid biological imaging materials. Indolizine donor-based cyanine and squaraine dyes with water-solubilizing sulfonate groups were targeted in this study due to strong absorptions and emissions in the NIR region. As previously observed for nonwater-soluble derivatives, the indolizine group with water-solubilizing groups retains a substantial shift toward longer wavelengths for both absorption and emission with squaraines and cyanines relative to classically researched indoline donor analogues. Very high quantum yields (as much as 58%) have been observed with absorption and emission >700 nm in fetal bovine serum. Photostability studies, cell culture cytotoxicity, and cell uptake specificity profiles were all studied for these dyes, demonstrating exceptional biological imaging suitability.

Donor-Acceptor-Donor NIR II Emissive Rhodindolizine Dye Synthesized by C-H Bond Functionalization.

A NIR II emissive dye was synthesized by the C-H bond functionalization of 1-methyl-2-phenylindolizine with 3,6-dibromoxanthene. The rhodindolizine (RhIndz) spirolactone product was nonfluorescent; however, upon opening of the lactone ring by the formation of the ethyl ester derivative, the fluorophore absorbs at 920 nm and emits at 1092 nm, which are both in the NIR II region. In addition, 4-cyanophenyl- (CNRhIndz) and 4-methoxyphenyl-substituted rhodindolizine (MeORhIndz) could also be prepared by the C-H activation reaction.

Indolizine-Cyanine Dyes: Near Infrared Emissive Cyanine Dyes with Increased Stokes Shifts.

Molecular engineering strategies designed to red-shift cyanine dye absorptions and emissions further into the near-infrared (NIR) spectral region are explored. Through the use of a novel donor group, indolizine, with varying cyanine bridge lengths, dye absorptions and emissions, were shifted deeper into the NIR region than common indoline-cyanines. Stokes shifts resulting from intramolecular steric interactions of up to ∼60 nm in many cases were observed and explained computationally. Molecular brightnesses of up to 5800 deep into the NIR region were observed. Structure-property relationships are explored for the six indolizine-cyanine dyes with varying cyanine bridge length and indolizine substituents showing broad absorption and emission tunability. The dyes are characterized by crystallography, and the photophysical properties are probed by varying solvent for absorption and emission studies. Computational data show involvement of the entire indolizine π-system during light absorption, which suggests these systems can be tunable even further into the NIR region through select derivatizations.

Counter Anion Effect on the Photophysical Properties of Emissive Indolizine-Cyanine Dyes in Solution and Solid State.

Near-infrared emissive materials with tunable Stokes shifts and solid-state emissions are needed for several active research areas and applications. To aid in addressing this need, a series of indolizine-cyanine compounds varying only the anions based on size, dipole, and hydrophilicity were prepared. The effect of the non-covalently bound anions on the absorption and emission properties of identical π-system indolizine-cyanine compounds were measured in solution and as thin films. Interestingly, the anion choice has a significant influence on the Stokes shift and molar absorptivities of the dyes in solution. In the solid-state, the anion choice was found to have an effect on the formation of aggregate states with higher energy absorptions than the parent monomer compound. The dyes were found to be emissive in the NIR region, with emissions peaking at near 900 nm for specific solvent and anion selections.

Near-Infrared Fluorescent Thienothiadiazole Dyes with Large Stokes Shifts and High Photostability.

A series of near-infrared (NIR) organic emissive materials were synthesized and the photophysical properties analyzed. The donor-acceptor-donor materials were designed with thienopyrazine and thienothiadiazole acceptor groups with thiophene-, furan-, and triphenylamine-based donor groups. The absorption and emission spectra were found to be widely tunable on the basis of the donor and acceptor groups selected. Computational analysis confirms these materials undergo an intramolecular charge-transfer event upon photoexcitation. Large Stokes shifts of ∼150 nm were observed and rationalized by computational analysis of geometry changes in the excited state. Fluorescence studies on the dye series reveal maximum peak emission wavelengths near 900 nm and a quantum yield exceeding 16% for 4,6-bis(2-thienyl)thieno[3,4-c][1,2,5]thiadiazole. Additionally, several dyes were found to have reasonable quantum yields within this NIR region (>1%), with emission wavelengths reaching 1000 nm at the emission curve onset. Photostability studies were conducted on these materials in an ambient oxygen environment, revealing excellent stability in the presence of oxygen from all the dyes studied relative to a benchmark cyanine dye (ICG) during photoexcitation with exceptional photostability from the 4,6-bis(5'-dodecyl-[2,2'-bithiophene]-5-yl)thieno[3,4-c][1,2,5]thiadiazole derivative.