2-Formyl boron-dipyrromethene as a key synthon to prepare functionalized meso-boron dipyrromethenyl porphyrin building blocks

Abstract

A series of functionalized meso-boron dipyrromethenyl porphyrin building blocks were synthesized by condensing one equivalent of readily available 2-formyl boron dipyrromethene (2-formyl BODIPY) with two equivalents of meso-anisyl dipyrromethane and one equivalent of functionalized aldehyde under mild acid catalyzed conditions followed by column chromatographic purification and afforded in 5–7% yields. The meso-BODIPYnyl porphyrins are freely soluble in common organic solvents and characterized by mass, spectral and electrochemical techniques. The presence of a BODIPY unit directly at the meso-position alters the π-delocalization of the porphyrin macrocycle. The compounds are weakly fluorescent because of effective charge transfer between the porphyrin and BODIPY units leading to the formation of a low lying charge transfer state. The meso-BODIPYnyl porphyrin–BF₂–smaragdyrin conjugate was synthesized by coupling a meso-BODIPYnyl porphyrin building block containing a meso-iodophenyl group with ethynyl BF₂–smaragdyrin under Pd(0) coupling conditions. The spectral and electrochemical studies indicated that the photo-induced electron transfer is the predominant process in the meso-BODIPYnyl porphyrin–BF₂–smaragdyrin conjugate.