Acenes, polyaromatic hydrocarbons composed of linearly fused benzene rings have received immense attention due to their performance as semiconductors in organic optoelectronic applications. Their appealing physicochemical properties, such as extended delocalization, high charge carrier mobilities, narrow HOMO-LOMO gaps and partially radical character in the ground state make them very attractive targets for many potential applications. However, the intrinsic synthetic challenges of unsubstituted members such as high reactivity and poor solubility are still limiting factors for their wider exploitation. Herein, we report a simple general synthesis of a new family of angularly fused acenoacenes with improved stability compared to their isoelectronic linear counterparts. The synthesis and comprehensive characterization of pentacenopentacene, pentacenohexacene and hexacenohexacene, with lengths between decacene and dodecacene, are disclosed.

Centre d'Elaboration de Matériaux et d'Etudes Structurales CEMES CNRS 29 rue Jeanne Marvig 31055 Toulouse France

Institute of Organic Chemistry and Biochemistry Czech Academy of Science IOCB CAS Flemingovo nám 542 160 00 Praha 6 Czech Republic

Institute of Physics Polish Academy of Sciences Al Lotników 32 46 02 668 Warsaw Poland

Japan Institute for Chemical Reaction Design and Discovery Hokkaido University Sapporo Hokkaido 001 0021 Japan

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