The syntheses, and optoelectronic and structural properties of 2,7-donor- and acceptor-functionalized dibenzo[a,e]pentalenes, accessed in a versatile synthetic route, are presented and discussed.

Ambipolar organic semiconductors are of high interest for organic field-effect transistors. For n-type conduction, low LUMO energies are required. Dibenzo[a,e]pentalenes (DBPs) are promising compounds; however, few derivatives exist with energetically low-lying LUMO levels. Here, we present DBP derivatives with LUMO energies down to -3.73 eV and small bandgaps down to 1.63 eV determined through cyclic voltammetry, UV/vis absorption spectroscopy, and TDDFT calculations. Single-crystal X-ray diffraction analysis revealed a 1D π-stacking mode. The addition of arylalkynyl substituents at the five-membered rings in a facile and versatile synthetic route allowed for tuning of the band gaps and LUMO energies. The synthetic route can easily be modified to access a variety of DBP derivatives. The LUMO energies of the DBP derivatives presented herein make them attractive for an application in n-type or ambipolar field-effect transistors.

Dibenzo[a,e]pentalenes, functionalized with thioether or sulfone groups, show high electron mobilities in n-channel OFETs using well-aligned crystals.

Spiroconjugated charge-transfer dyes with N–CO-substructure are presented, whose optical properties are tuned by extending the donor or acceptor part.