Meso-(2-Benzimidazolyl)-substituted BODIPYs: Synthesis, structures and spectroscopic properties

Abstract

A series of meso-(2-benzimidazolyl)-substituted boron dipyrromethene (BODIPY) derivatives 3a–3c and 4 have been synthesized and characterized. The absorption and fluorescence bands of 3a are bathochromically shifted by 36 nm and 61 nm, respectively, compared with those of the meso-phenyl BODIPY in toluene. More importantly, the fluorescence quantum yields of these meso-(2-benzimidazolyl)-substituted BODIPYs (up to 0.45 in toluene) are much higher than those of the previously reported meso-heterocyclic BODIPYs. X-ray crystallographic analysis of the single crystal structure of 3a revealed that the dihedral angle of meso-benzimidazolyl ring and indacene plane (40.47[Formula: see text] ) is smaller compared with that of the meso-tolyl substituted BODIPY (61.4[Formula: see text] ). Replacement of the six-membered ring with a five-membered ring, as well as the absence of hydrogen at the imino-nitrogen, generated the reduced repulsion and the hydrogen bonding interaction. The increased planarity not only provided the substantial delocalization of [Formula: see text] electrons and red shifted the absorption and emission bands but also enhanced the fluorescence quantum yield by reducing free rotation induced nonradiative deactivation pathway. Furthermore, 3,5-distyryl coupled BODIPY 4 exhibits a NIR fluorescence band at 712 nm with moderate quantum yield ([Formula: see text] [Formula: see text] 0.3) in nonpolar and polar solvents, which indicate that meso-(2-benzimidazolyl) BODIPY acts as a good candidate for post modification toward NIR dyes for biological applications.