Deep blue emitting dual state fluorescent triphenylamine-dicyclohexylurea derivative: Multi-stimuli responsive...

A new deep blue emissive organic fluorophore (N-cyclohexyl-N-(cyclohexylcarbamoyl)-4-(diphenylamino)benzamide (NCDPB)) was designed and synthesized, which showed strong fluorescence both in solution and solid-state. Solid-state structural analysis of NCDPB revealed non-planar twisted molecular conformation with extended hydrogen bonding between the amide functionalities. The propeller shaped triphenylamine (TPA) and non-planar cyclohexyl unit prevented close π…π stacking and produced strong deep blue emission in the solid state (λ_max = 400 nm, quantum yield (Φ_f) = 12.6 %). NCDPB also exhibited strong solvent polarity dependent tunable emission in solution (λ_max = 402-462 nm, Φ_f = 1.15 (compared to quinine sulphate)). NCDPB showed reversible fluorescence switching between two fluorescence states upon mechanical crushing and heating/solvent exposure. Mechanical crushing caused red shifting of fluorescence from 400 to 447 nm and heating/solvent exposure reversed the fluorescence. Further, NCDPB also displayed off-on reversible/self-reversible fluorescence switching upon exposure to trifluoracetic acid (TFA) and NH₃. The repeated fluorescence switching cycles indicated high reversibility without any significant change of fluorescence intensity. The drastically different fluorescence of NCDPB in CH₃OH and EtOH was utilized to distinguish them and monitor CH₃OH contamination in ethanol and benzene. It showed limit of detection (LOD) of methanol up to 0.25 % and 7 % in benzene and ethanol, respectively. The water sensitive fluorescence modulation of NCDPB in organic solvents was used to sensing water contamination in common organic solvents. Thus, integration of twisted TPA with H-bonding urea produced dual state emitting organic fluorophore with multi-responsive fluorescence switching and solvent sensing.