On‐Surface Interchain Coupling and Skeletal Rearrangement of Indenofluorene Polymers.

On‐surface synthesis serves as a powerful approach to construct π‐conjugated carbon nanostructures that are not accessible by conventional wet chemistry. Nevertheless, this method has been limited by the types and numbers of available on‐surface transformations. While the majority of successful cases exploit thermally triggered dehalogenative carbon–carbon coupling and cyclodehydrogenation, rearrangement of appropriate functional moieties has received limited research attention. Here, the unprecedented interchain coupling and thermally induced skeleton rearrangement are described of (dihydro)indeno[2,1‐b]fluorene (IF) polymers on an Au(111) surface under ultrahigh vacuum conditions, leading to different ladder polymers as well as fully fused graphene nanoribbon segments containing pentagonal and heptagonal rings. Au‐coordinated nanoribbons are also observed. All structures are unambiguously characterized by high‐resolution scanning probe microscopy. The current results provide an avenue to fabricating a wider variety of π‐conjugated polymers and carbon nanostructures comprising nonhexagonal rings as well as rarely explored organometallic nanoribbons. [ABSTRACT FROM AUTHOR]