Among conducting polymers, poly-p-phenylenevinylenes (PPVs) have attained a special place in polymer electronics. The optoelectronic properties initially exposed by PPVs in organic light-emitting diodes (OLEDs) turned these organic electronic conjugated systems from the solo academic interest into a technologically very promising area. The easiness of the tuning of their optoelectronic properties through synthetic modifications make PPVs an outstanding and suitable compound for technological applications and fundamental science development. Unfortunately, the synthesis and structural optoelectronic characterization of novel PPVs is a long and difficult task that sometimes yields unclear results. However, phenylenevinylene oligomers (oPV) can be synthesized and characterized in a very straightforward manner, and their performance in novel applications can be directly related to their structural analogue polymer, methodology designated as the oligomer approach. Herein, we describe the oligomer approach using the Mizoroki-Heck reaction as a synthetic route for oPVs and PPVs, and the importance of an extensive characterization for novel applications, such as photocatalysis and matrix-assisted laser desorption/ionization (MALDI) matrices, where these electronic conjugated systems have very promising applications
