Synthesis of pyridyl functionalized 3-pyrrolyl BODIPY based fluoroprobes and application towards highly selective detection of picric acid

Abstract

A series of pyridyl-coupled 3-pyrrolyl BODIPY fluoroprobes were synthesized by varying the position of the pyridyl/N-methylated pyridyl group at the α-/meso-position of the 3-pyrrolyl BODIPY scaffold and thoroughly characterized by HRMS and 1D/2D NMR techniques. Our studies indicated that only the water-soluble N-methylated p-pyridyl 3-pyrrolyl BODIPY among various pyridyl-coupled 3-pyrrolyl BODIPYs synthesized here showed an effective and exclusive sensing for picric acid (HPA). The N-methylated p-pyridyl 3-pyrrolyl BODIPY rapidly detects HPA in an aqueous medium with exceptional selectivity, sensitivity (LOD = 7.90 pM), and high binding affinity (K_a = 4·94 × 10⁸ M⁻¹) through both chromogenic and fluorogenic signalling modes. Our studies support the formation of a charge transfer complex between cationic N-methylated p-pyridyl 3-pyrrolyl BODIPY and picrate as verified by absorption, fluorescence, electrochemical, and NMR techniques. DFT and TD-DFT studies further support the structural and experimental observations, including the sensing mechanism of HPA.