Preparation and Photophysics of 2-(1-Pyrenyl)acrylic Acid and Its Methyl and 2′,2′,6′,6′-Tetramethyl-4′-Piperidyl Esters

Abstract

Novel probes represented connection of pyrene as chromophore and sterically hindered amine stabilizers (HAS) in the form of esters of 2-(1-pyrenyl)acrylic acid were synthesized. HAS was in the form of parent amine (PAP) as well as stable nitroxyl radical form (PAP-NO.). Photophysics of these probes were compared with their precursor as 2-(1-pyrenyl)acrylic acid (PAA) and its methyl ester (PAM). The fluorescence spectrum of PAA strongly depends on the acidity of the solution. The spectrum in neutral methanol indicates that it originates from the anionic form -COO(-). Changes of acidity or basicity of methanol solution resulted in the changes of shape, position as well as the intensity of fluorescence band. This is due to the presence of protolytic equilibria, either in the ground state or in the singlet excited state, leading to the formation of molecular form -COOH and the cationic form -COOH(2) (+). The ester analogues did not show any changes in various pH conditions. Fluorescence of all probes depends on the polarity of solvents and the presence of oxygen. Intermolecular quenching was studied with external quenchers TEMPO and oxygen and the data were compared with the intramolecular quenching using 1'-oxo-2',2',6',6'-tetramethyl-4'-piperidinyl-2-(1-pyrenyl)acrylate (PAP-NO.).