PyrrolylBODIPYs: Syntheses, Properties, and Application as Environment-Sensitive Fluorescence Probes

Four pyrrole B-ring-functionalized pyrrolylBODIPYs and their B-ring unsubstituted analogues were synthesized from easily accessible starting 5-halo-2-formylpyrroles and were characterized by nuclear magnetic resonance, high-resolution mass spectrometry, X-ray analysis, and optical/electronic properties. In great contrast to the substitution(s) at the other two pyrrolic units, electron-donating substituent(s) at pyrrole B-ring bring significant blue shift of the absorption and emission bands. Cyclic voltammetry and density functional theory calculations indicate that this blue shift may be attributed to the increased highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels and the overall increase in the energy band gaps. These pyrrolylBODIPYs generally show intense absorption (centered at 570-624 nm) and fluorescence emission (582-654 nm) in nonpolar solvents. A gradual decrease in the fluorescence intensity was observed for these dyes with the increase in solvent dipolar moment, which combines with the red to far-red absorption/emission, rendering these pyrrolylBODIPYs potential applications as environment-sensitive fluorescence probes as demonstrated in this work for bovine serum albumin.