Oxidative Polycondensation of Pyrazolone-Based Schiff Bases: Synthesis, Structural Characterization, Thermal and Electrical Properties

Abstract

Schiff base derivatives, namely 3-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1-phenyl-1-pyrazole-5-one (3-APPHNA) and 4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3-one (4-APPHNA), were synthesized via the condensation reaction of 3-amino-1-phenyl-2-pyrazolin-5-one (3-APP) and 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, (4-APP) with 2-hydroxynaphthaldehyde (2-HNA) in ethanol. Synthesized monomers were then converted into their oligomeric derivatives via oxidative polycondensation carried out using NaOCl. The structural, thermal, optical, electrochemical, and morphological properties of the obtained monomers were comprehensively characterized using fourier transform infrared (FT-IR), proton nuclear magnetic resonance (¹H-NMR), carbon-13 nuclear magnetic resonance (¹³C-NMR), ultraviolet-visible spectrophotometer (UV–vis), thermogravimetry-derivative thermogravimetry (TG-DTG), and cyclic voltammetric analyses. Spectroscopic studies confirmed the successful synthesis of Schiff bases and the presence of stable azomethine bonds. Molecular weight, glass transition temperature, and surface morphologies of oligomers were determined by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and field emission scanning electron microscope (FE-SEM) measurements, respectively. The M_n values of oligo(3-APPHNA) and oligo(4-APPHNA) were found to be 3400 and 2900 Da, respectively. The results revealed an oxidative oligomerization process yielding relatively narrow molecular weight distributions. Oligo(4-APPHNA) has shown more pronounced semiconductor properties compared to other oligomers, considering its 2.30 eV optical band gap and frequency-dependent electrical behavior. Additionally, dielectric measurements showed that oligo(4-APPHNA) exhibited higher dielectric constant, dielectric loss, and AC conductivity values throughout the investigated frequency range. These findings suggest that the synthesized oligomers are promising candidate materials for future optoelectronic and semiconductor applications, but further research at the device level is needed.