On-Surface Synthesis of Indenofluorene Polymers by Oxidative Five-Membered Ring Formation

On-surface synthesis is a successful approach to the creation of carbon-based nanostructures that cannot be obtained via standard solution chemistry. In this framework, we have established a novel synthetic pathway to one-dimensional conjugated polymers composed of indenofluorene units. Our concept is based on the use of <i>ortho-</i>methyl groups on a poly­(<i>para</i>-phenylene) backbone. In this situation, surface-assisted oxidative ring closure between a methyl and the neighboring aryl moiety gives rise to a five-membered ring. The atomically precise structures and electronic properties of the obtained indenofluorene polymers have been unambiguously characterized by STM, nc-AFM, and STS, supported by theoretical calculations. This unprecedented synthetic protocol can potentially be extended to other polyphenylenes and eventually graphene nanoribbons, to incorporate five-membered rings at desired positions for the fine-tuning of electronic properties