Angewandte Chemie, Accepted Article.
Narrow HOMO‐LUMO gaps and high charge carrier mobilities make larger acenes potentially high‐efficient materials for organic electronic applications. The performance of such molecules was shown to significantly increase with increasing number of fused benzene rings. Bulk quantities, however, can only be obtained reliably for acenes up to heptacene. Theoretically, (oligo)acenes and (poly)acenes are predicted to possess open‐shell singlet biradical and polyradical ground states, respectively, for which experimental evidence is still scarce. We have now been able to dramatically lower the HOMO‐LUMO gap of acenes without the necessity of unfavorable elongation of their conjugated π system, i.e. by implementation of two boron atoms into the anthracene skeleton. With ancillary support by cyclic (alkyl)(amino)carbenes, these neutral 9,10‐diboraanthracenes were shown to feature disjointed, open‐shell singlet biradical ground states.