Red-to-Near-Infrared Emitting PyrrolylBODIPY Dyes: Synthesis, Photophysical Properties and Bioimaging Application

Near-infrared (NIR) fluorophores with characteristics such as deep tissue penetration, minimal damage to the biological samples, and low background interference, are highly sought-after materials for in vivo and deep-tissue fluorescence imaging. Herein, series of 3-pyrrolylBODIPY derivatives and 3,5-dipyrrolylBODIPY derivatives have been prepared by a facile regioselective nucleophilic aromatic substitution reaction (SNAr) on 3,5-halogenated BODIPY derivatives (3,5-dibromo or 2,3,5,6-tetrachloroBODIPYs) with pyrroles. The installation of a pyrrolic unit onto the 3-position of the BODIPY chromophore leads to a dramatic red shift of both the absorption (up to 160 nm) and the emission (up to 260 nm) in these resultant 3-pyrrolylBODIPYs with respect to that of the BODIPY chromophore. Their further 5-positional functionalization provides a facile way to fine tune their photophysical properties, and these resulting dipyrrolylBODIPYs and functionalized pyrrolylBODIPYs show strong absorption in the deep red-to-NIR regions (595-684 nm) and intense NIR fluorescence emission (650-715 nm) in dichloromethane. To demonstrate the applicability of these functionalized pyrrolylBODIPYs as NIR fluorescent probes for cell imaging, pyrrolylBODIPY 6a containing mitochondrion-targeting butyltriphenylphosphonium cationic species was also prepared. It selectively localized in mitochondria of HeLa cells, with low cytotoxicity and intense deep red fluorescence emission.