Comparative Study of Bis-Schiff Case Containing Conjugated Oligomers Based on Phosphate and Silane Moieties: Investigation of Photophysical and Thermal Properties.

Abstract

Oligo(azomethine)s bearing phosphate and silane moieties were the subject of an investigation within this study. The initial stage involved the synthesis of two Schiff base monomers, denoted as SCH-1 and SCH-2 (SCHs), each possessing a pair of hydroxyl functional groups. This was achieved through a loss of water between the aldehyde and diamine precursors. Subsequently, the Schiff base entities were subjected to oligomerization through HCl-mediated elimination due to the interaction between the hydroxyl groups of the Schiff bases and the chlorine moieties of dichlorodiethylsilane (Si) or phenyl dichlorophosphate (P). This procedure yielded distinct P-oligo(azomethine) (P1-P, P2-P) and Si-oligo(azomethine) (P1-Si and P2-Si) structures corresponding to each precursor. The molecular structures of the synthesized Schiff base monomers and oligo(azomethine)s were elucidated employing Fourier transform infrared, 1H NMR, and 13C NMR techniques. Thermal properties of the resulting products were assessed by utilizing thermogravimetric analysis (TG-DTG/DTA and DSC) techniques. Scanning electron microscopy (SEM) was employed to acquire high-resolution images and detailed surface information on the samples. Additionally, X-ray diffraction was employed to analyze the phase properties of the solid samples. Furthermore, the optical band gap (E g) values of the resulting P-oligo(azomethine)s and Si-oligo(azomethine)s were determined utilizing UV-vis spectrophotometer. The relatively low band gap values exhibited by the synthesized oligo(azomethine)s were indicative of their potential suitability as semiconductive materials in the realm of electronic and optoelectronic device fabrication. Photoluminescence (PL) measurements disclosed a green emission profile upon excitation by blue light. The oligo(azomethine)s incorporating methoxy groups demonstrated a red shift in comparison to their counterparts with methyl groups. Remarkably, no discernible fluctuations in fluorescence were observed over a 3600 s interval under consistent conditions. This observation underscored the inherent stability of the PL emission across the spectral range of exciting light. Thermal analyses unveiled high thermal stability of the synthesized oligo(azomethine)s, sustaining their structural integrity up to 220 °C. The char % of P-oligo(azomethine)s and Si-oligo(azomethine)s were observed to fall within the range of 29.45-55.47% at 1000 °C. SEM images revealed the absence of pores on the surface of P2-Si, which exhibited the highest limiting oxygen index and thermal heat release index (T HRI) values.