The formation of s-indaceno[1,2-b:5,6-b′]ditetracene and as-indaceno[2,3-b:6,7-b′]ditetracene containing indenofluorene cores from a common precursor has been achieved by a dehydrogenative surface-assisted cyclization on Au(111) and confirmed by bond-resolved non-contact atomic force microscopy. On-surface generated as-indaceno[2,3-b:6,7-b′]ditetracenes undergo fusion, which leads to T-shaped adducts by an intermolecular cycloaddition. The same type of cycloaddition, which has no parallel in solution chemistry, has been observed between as-indaceno[2,3-b:6,7-b′]ditetracene and pentacene or octacene. These examples of surface-assisted cycloaddition provide perspectives for the rational design and synthesis of molecular nanostructures.
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