On-Surface Synthesis and Intermolecular Cycloadditions of Indacenoditetracenes, Antiaromatic Analogues of Undecacene.

Zuzak, Rafal; Stoica, Otilia; Blieck, Rémi; Echavarren, Antonio M; Godlewski, Szymon · ACS Nano · 2021

basic_science · Level V

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Abstract

The formation of <i>s</i>-indaceno[1,2-<i>b</i>:5,6-<i>b</i>']ditetracene and <i>as</i>-indaceno[2,3-<i>b</i>:6,7-<i>b</i>']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 <i>as</i>-indaceno[2,3-<i>b</i>:6,7-<i>b</i>']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 <i>as</i>-indaceno[2,3-<i>b</i>:6,7-<i>b</i>']ditetracene and pentacene or octacene. These examples of surface-assisted cycloaddition provide perspectives for the rational design and synthesis of molecular nanostructures.