Poly(p-phenylene vinylene) PPV derivatives represent a pivotal class of π-conjugated materials with promising applications
in organic electronic devices such as OLEDs, OFETs, and OPVs. Despite their significance, understanding the structure–
property relationships in PPV derivatives remains challenging, particularly for oligomers. In this study, we synthesized
PPV derivative oligomers via ROMP. The oligomers exhibited molecular weights of 3.46 kDa and 6.16 kDa, demonstrating
well-controlled polymerization. The incorporation of alkyl side chains onto the oligomer backbone enhanced solubility and
refined optical properties. UV–Vis analysis determined the optical band gaps (
Egop) of the synthesized oligomers to range
from 2.14 to 2.47 eV. Furthermore, TGA revealed two-step decomposition processes with onset decomposition temperatures
(Td, onset) of 221.8°C and 218.5°C, and thermal decomposition maximum temperatures (Td, max) at 356.8°C and 324.0°C
for Oligo-DO-PPV and Oligo-TO-PPV, respectively. These findings underscore the potential of ROMP as a versatile approach
for tailoring PPV oligomers and provide critical insights into their structure–property relationships. This work advances our
understanding of PPV oligomers, paving the way for future applications in optoelectronic devices.