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Understanding the nature and hierarchy of on surface reactions is a majorchal- lenge for designing coordination and covalent nanostructures by means ofmultistep synthetic routes. In particular, intermediates and final products arehard to predict since reaction paths and their activation windows depend on thechoice of both the molecular precursor design and the substrate. Here we reporta systematic study of the effect of the catalytic metal surface to reveal how asingle precursor can give rise to very distinct polymers that range fromcoordination and covalent non planar polymer chains of distinct chirality, toatomically precise graphene nanoribbons and nanoporous graphene. Our precursorconsists on adding two phenyl substituents to 10,10'-dibromo 9,9'-bianthracene,a well-studied precursor in the on-surface synthesis of graphene nanoribbons.The critical role of the monomer design on the reaction paths is inferred fromthe fact that the phenyl substitution leads to very distinct products in eachone of the studied metallic substrates.

Critical role of phenyl substitution and catalytic substrate on the surface-assisted polymerization of dibromobianthracene derivatives