Synthesis of Molecularly Defined Conjugated Oligomers and Polymers through Dehydrative Coupling

Abstract

The development of scalable methods for the synthesis of conjugated materials remains among the most important aspects for their integration into devices at a commercial level. Drawing inspiration from nature as well as polymers made on a scale of many millions of tons annually, one type of reaction often used is a dehydration reaction in which two monomers react together eliminating a small molecule such as water. Although dehydration reactions are widely used to synthesize non-conjugated polymers, advances in utilizing dehydration methods to prepare conjugated poly(hetero)arenes are lacking. Herein, we describe the development of a dehydration type reaction where two thiazole N-oxides are coupled to afford the corresponding dimer with simply an addition of a base. This dimer formation occurs in 10 minutes, at room temperature, forming an C(sp2)–C(sp2) bond without the need for transition metals. Various conjugated small molecules and polymers were synthesized using this simple method. Extending this reaction to synthesis of molecularly defined oligomers as well as other classes of poly(hetero)arenes could be a powerful tool allowing access to a wider variety of conjugated materials.