Synthesis and fluorescence properties of red-to-near-infrared-emitting push–pull dyes based on benzodioxazole scaffolds

Abstract

Fluorescence imaging with high temporal and spatial resolution has emerged as one of the most promising techniques to monitor biomolecules and biological processes in living systems. Among many kinds of small molecular fluorescent dyes, 2,1,3-benzoxadiazole (BD) derivatives have been widely applied in many chemical and biological applications due to their excellent photophysical properties. However, only a limited number of BD dyes with long emission wavelengths were reported. Herein, we have reported a new class of red-to near-infrared-emitting small molecular dyes 2a–3a based on benzodioxazole scaffolds, which are named VBDfluors. To bathochromically shift both absorption and emission, the conjugation system was extended by introducing electron-withdrawing group-substituted vinyl groups at position 7 via a Knoevenagel condensation reaction. The basic photophysical properties of VBDfluors were detected and summarized. The VBDfluors display excellent photophysical properties, including emission in the red-to-NIR region, large Stokes shifts, good stability/photostability and cell permeability. The geometry of the molecules was optimized by density functional theory (DFT) and time-dependent DFT (TDDFT) methods. Bioimaging results indicated that 2a and 3a exhibited excellent cell permeability and could be utilized for visualization of lipid droplets in living cells.