Improved photoluminescence of di, tri, and tetra-aminobenzene molecules hydrogen-bonded by polyethyleneimine and their application for metal ion sensing

Abstract

Higher photoluminescence quantum yield (PLQY) is always a required property for fluorescent molecule dyes used as probes in aqueous environment because of non-radiative relaxation via O–H vibrations. 1,2,4-triaminobenzene (TriAB) dihydrochloride has been reported as a red-emitting fluorescent dye, although its photoluminescence (PL) intensity is very low. Here, a bright orange-emitting fluorophore was prepared by simply mixing TriAB and polyethyleneimine (PEI) in water at pH 7 and applied to metal ion sensing. The PLQY was increased from 3.1 % to 10.0 % by the addition of PEI into an aqueous TriAB solution. Our experiments by exchanging H2O for D2O and changing the pH from 7 to 1 revealed that the role of PEI in enhancing the PL intensity is attributed to the interaction between the amino groups of TriAB and PEI via hydrogen bonding, the prevention of contact between TriAB and water molecules, and thus the suppression of the non-radiative relaxation via O–H vibrations of H2O. We further demonstrated this role for 1,4-diaminobenzene and 1,2,4,5-tetraaminobenzene.