Acyclic diene metathesis polymerization of a structurally symmetrical perylene bisimide (PBI)-containing α,ω-diene has been performed, yielding an unsaturated polymer with increased molecular weight (Mn = 21.2–87.6 kDa) and decreased polydispersity index (PDI = 2.31–1.76) as the reaction time was prolonged. The subsequent hydrogenation of the as-synthesized polymer was readily accomplished, affording the desired polyethylene (PE) with a saturated backbone and precisely repeating substituted bulky PBI branches. This PBI-substituted PE derivative displayed high glass transition temperatures (Tg = 51.8–75.8 °C), a relatively wide range of light absorption (λ = 230–590 nm), and a highly ordered architecture, which should facilitate electron mobility and be suitable for utilization in optoelectronic devices. It can therefore serve as a superior model for simple construction of functional PE polymers with precisely repeating bulky branches and a soluble PBI polymer with an ordered architecture.
