From Branched Polyphenylenes to Graphite Ribbons

This article presents the synthesis of graphitic nanoribbons (∼1 nm wide), containing extended conjugated all-benzenoid segments. These were obtained by intramolecular oxidative cyclodehydrogenation of soluble branched polyphenylenes 6, which were prepared by repetitive Diels−Alder cycloaddition of 1,4-bis(2,4,5-triphenylcyclopentadienone-3-yl)benzene (1) and diethynylterphenyl (5) in good yield. While insolubility of the obtained graphite ribbons 7 precluded standard spectroscopic structure elucidation, the electronic and vibrational properties were probed by solid-state UV−vis, Raman, and infrared spectroscopy. A wide and unstructured absorption band covering the visible range of the electronic spectrum (λmax ∼ 800 nm) is observed, confirming the highly extended conjugated framework. The structure proof of the ribbon-type polymer is supported by the inclusion of appropriate model compounds. The profile of the visible Raman spectrum of the material is similar to that of a discrete polycyclic aromatic hydrocarbon (PAH) C222H42, characterized by two strong bands (at 1603 and 1322 cm-1), corresponding to the G and D bands of graphite. The obtained graphite ribbons are not linear but rather contain “kinks” due to the structural design of the polyphenylene precursor. High-resolution transmission electron microscopy (HRTEM) images of the graphite ribbons 7 disclose two different domains: one is an ordered graphite layer structure with a layer distance of ca. 3.8 Å, and one is disordered due to the existence of “kinks” in the obtained polymers and/or random stacking of graphite ribbons. Attempts to make linear analogues are so far unsuccessful, emphasizing the critical importance of the geometry of the polyphenylene scaffold to successful oxidative cyclodehydrogenation.