Synthesis of carbazole-based Schiff base and fluorescence turn on sensor sensitive to Cr3+ ion: Oxidative and electrochemical polymerization and investigation of electrochromic properties

Abstract

In this study, a Schiff base monomer (ECBA) was initially synthesized from condensation reaction of 3-amino 9-ethyl carbazole (AEC) with 2,4-dihydroxy benzaldehyde (DHBA). Then, its poly(ECBA-1) polymer was synthesized via oxidative polycondensation in methanol/THF (v/v:4/1) medium by NaOCl oxidant. The structures of the obtained monomer and poly(ECBA-1) were confirmed by 1H NMR, 13C NMR and FT-IR. The optical and electrochemical properties of compounds were examined by UV–Vis, fluorescence spectroscopy and cyclic voltammetry (CV) measurements, respectively. The Highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels and electrochemical (E’g) and optical band gap (Eg) values were determined for monomer and polymer compounds by cyclic voltammetry and UV–Vis spectrophotometry. Thermal stabilities of the monomer and poly(ECBA-1) were determined from thermogravimetric-differential thermal analysis (TG-DTA) measurements. The molecular weight distribution and Tg temperature of the poly(ECBA-1) were determined by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) measurements, respectively. The surface morphologies of the synthesized polymers and copolymer were investigated by scanning electron microscopy (SEM). By fluorescence titration, ECBA was found to be selective towards Cr3+ ion among Ag+, K+, Mn2+, Hg2+, Co2+, Ca2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+, Fe3+, Cr3+, Cr+6 ions. The selectivity of Cr3+ion was confirmed by the absence of interference from other competitive cationic species. The limit of detection (LOD) and binding constant (Ka) values for the fluorescent probe were calculated as 6.07 x 10-7 M and 1.25 x 104 M−1, respectively. In addition, homopolymer and copolymer synthesis was carried out on Pet ITO selected as working electrode via electropolymerization method by the synthesized ECBA monomer. Homopolymer synthesis was carried out by Cyclic Voltammetry (CV) method and copolymer synthesis was carried out by batch electrolysis method using EDOT with ECBA monomer. Spectroelectrochemical measurements were taken to investigate the electrochromic properties of the prepared homopolymer poly(ECBA-2) and copolymer (Poly(ECBA-co-EDOT)). The copolymer was found to have a more stable structure than the homopolymer.