Thioether- and sulfone-functionalized dibenzopentalenes as n-channel semiconductors for organic field-effect transistorsElectronic supplementary information (ESI) available: Additional synthetic procedures, CVs, NMR spectra, TGA und DSC measurements, X-ray crystallographic data for 2b and 2c, Cartesian coordinates of calculated structures and images of crystals grown by the DPC method of 2c, 2d and 3. CCDC 1532986 and 1582024. For ESI and crystallographic data in CIF or other electronic format s

Dibenzo[ a , e ]pentalenes (DBPs) are promising candidates to be used as ambipolar or n-type semiconductors in organic field-effect transistors (OFETs). For n-channel conduction, low LUMO energy levels are required. Furthermore, a close molecular packing in the solid state is advantageous. Here we present thioether-functionalized DBPs with LUMO energies down to −3.47 eV as well as a DBP sulfone with a LUMO energy of −3.94 eV. X-ray crystallography revealed 1-D π-stacking or herringbone packing in the solid state with close intramolecular distances between the DBP cores. Two thio-DBPs and the DBP sulfone showed n-channel conduction in FET measurements on well-aligned crystals with electron mobilities of up to 0.18 cm 2 V −1 s −1 , to date the highest reported values for n-channel conduction in DBP derivatives. The short synthetic route will in the future allow for facile access to a variety of thio- and sulfone-DBPs for n-channel or ambipolar semiconduction. Dibenzo[ a , e ]pentalenes, functionalized with thioether or sulfone groups, show high electron mobilities in n-channel OFETs using well-aligned crystals.