In situ laser annealing as pathway for the metal free synthesis of tailored nanographenes.

Tailored synthesis of nanographenes, and especially graphene nanoribbons (GNR), has been achieved on metal substrates via a bottom-up approach from organic precursors, which paves the way to their application in nanoelectronics and optoelectronics. Since quantum confinement in nanographenes leads to the creation of peculiar band structures, strongly influenced by their topological characteristics, it is important to be able to exactly engineer them in order to precisely tune their electronic, optical and magnetic properties. However practical application of these materials requires post-synthesis transfer to insulating substrates. Recently, cyclodehydrofluorination of fluorinated organic precursors has been shown to be a promising pathway to achieve metal-free bottom-up synthesis of nanographenes. Here we present how to apply in situ laser annealing to induce cyclodehydrofluorination leading to nanographene formation directly on non-metallic surfaces. In this work, we analyze the changes in the Raman fingerprint of the fluorinated precursor tetrafluoro-diphenyl-quinquephenyl (TDQ) during the laser annealing process in high vacuum (HV), demonstrating that both heating and photo-induced processes influence the cyclization process. Hence, in situ laser annealing allows not only to influence chemical reactions, but also to have a fast and contact-free monitoring of the reaction products. Optimization of the laser annealing process adds a new level of control in the tailored synthesis of nanographenes on non-metallic substrates. This is a very promising pathway to unravel the full application potential of nanographenes in general and GNR in particular, enabling a fast optimization of precursor molecules and substrate geometry engineered for specific applications.

Carbon Origami via an Alumina-Assisted Cyclodehydrofluorination Strategy.

The synthesis of pristine non-planar nanographenes (NGs) via a cyclodehydrofluorination strategy is reported and the creation of highly strained systems via alumina-assisted C-F bond activation is shown. Steric hindrance could execute an alternative coupling program leading to rare octagon formation offering access to elusive non-classical NGs. The combination of two alternative ways of folding could lead to the formation of various 3D NG objects, resembling the Japanese art of origami. The power of the presented "origami" approach is proved by the assembly of 12 challenging nanographenes that are π-isoelectronic to planar hexabenzocoronene but forced out of planarity.

Intramolecular aryl-aryl coupling via C-F bond activation tolerant towards C-I functionality.

Herein we report a transition-metal free activation of a particularly stable aromatic carbon-fluorine bond allowing intramolecular aryl-aryl coupling which is orthogonal to carbon-iodine functionality.

Rational synthesis of atomically precise graphene nanoribbons directly on metal oxide surfaces.

Atomically precise graphene nanoribbons (GNRs) attract great interest because of their highly tunable electronic, optical, and transport properties. However, on-surface synthesis of GNRs is typically based on metal surface-assisted chemical reactions, where metallic substrates strongly screen their designer electronic properties and limit further applications. Here, we present an on-surface synthesis approach to forming atomically precise GNRs directly on semiconducting metal oxide surfaces. The thermally triggered multistep transformations preprogrammed in our precursors' design rely on highly selective and sequential activations of carbon-bromine (C-Br) and carbon-fluorine (C-F) bonds and cyclodehydrogenation. The formation of planar armchair GNRs terminated by well-defined zigzag ends is confirmed by scanning tunneling microscopy and spectroscopy, which also reveal weak interaction between GNRs and the rutile titanium dioxide substrate.

The Rolling-Up of Oligophenylenes to Nanographenes by a HF-Zipping Approach.

Intramolecular aryl-aryl coupling is the key transformation in the rational synthesis of nanographenes and nanoribbons. In this respect the C-F bond activation was shown to be a versatile alternative enabling the synthesis of several unique carbon-based nanostructures. Herein we describe an unprecedentedly challenging transformation showing that the C-F bond activation by aluminum oxide allows highly effective domino-like C-C bond formation. Despite the flexible nature of oligophenylene-based precursors efficient regioselective zipping to the target nanostructures was achieved. We show that fluorine positions in the precursor structure unambiguously dictate the "running of the zipping-program" which results in rolling-up of linear oligophenylene chains around phenyl moieties yielding target nanographenes. The high efficiency of zipping makes this approach attractive for the synthesis of unsubstituted nanographenes which are difficult to obtain in pure form by other methods.