Synthesis of meso‐CF₃‐Substituted BODIPY Compounds with Redshifted Absorption

The one‐pot synthesis of meso ‐CF 3 ‐substituted boron–dipyrromethene (BODIPY) compounds is achieved for the first time through the condensation of pyrroles with CF 3 COOH in the presence of PhSiCl 3 . The PhSiCl 3 plays a vital role, as it provides the source of Cl – ions for the generation of acyl chloride. X‐ray crystallographic analysis revealed that the core skeleton of meso ‐CF 3 ‐BODIPY becomes nonplanar and twisted owing to the introduction of the –CF 3 group. The introduction of the –CF 3 group to the BODIPY core results in a remarkable bathochromic shift of the absorption to the near‐infrared (NIR) region. A meso ‐CF 3 ‐BODIPY with dimethylamino groups is a turn‐on fluorescent probe for pH, and the singlet‐oxygen generation of dibromo‐substituted meso ‐CF 3 ‐BODIPY is more effective (ca. 2.4‐fold rate enhancement) than that of the parent meso ‐CF 3 ‐BODIPY.