Templated approach to well-defined, oxidatively coupled conjugated polymers

Templated polymerization is a process whereby the molecular weight and dispersity of a parent polymer can be mirrored onto a second, daughter polymer. While ubiquitous in nature and explored in bio-inspired polymers, templated synthesis has scarcely been used towards the controlled synthesis of conjugated polymers. Conjugated polymers are useful for electronic and optical applications, yet very few examples can be prepared in a controlled manner. Here we show that it is possible to use ring-opening metathesis polymerization to prepare macromolecular templates with controlled molecular weights and dispersities. Chemical oxidative polymerization is then used to prepare the final well-defined conjugated polymers. By combining these techniques, we demonstrate a versatile approach to well-defined conjugated polymers, where traditional synthetic routes are generally limited in control and/or scope. Templated oxidative polymerization affords organic soluble, oxidatively doped PEDOT-based polymers with controlled molecular weights and low dispersities (D similar to 1.2). To our knowledge, this is the first report of a templated approach being used to definitively control the molecular weight, dispersity, and solubility of conjugated polymers during oxidative polymerization.