Beschreibung:
<jats:title>Abstract</jats:title><jats:p>The molecular structure of the hydrocarbon 5,6;11,12‐di‐<jats:italic>o</jats:italic>‐phenylenetetracene (DOPT), its material characterization and evaluation of electronic properties is reported for the first time. A single‐crystal X‐ray study reveals two different motifs of intramolecular overlap with herringbone‐type arrangement displaying either face‐to‐edge or co‐facial face‐to‐face packing depicting intensive π–π interactions. Density functional theory (DFT) calculations underpin that a favorable electronic transport mechanism occurs by a charge hopping process due to a π‐bond overlap in the DOPT polymorph with co‐facial arene orientation. The performance of polycrystalline DOPT films as active organic semiconducting layer in a state‐of‐the‐art organic field effect transistor (OFET) device was evaluated and proves to be film thickness dependent. For 40 nm layer thickness it displays a saturation hole mobility (μ<jats:sub>hole</jats:sub>) of up to 0.01 cm<jats:sup>2</jats:sup> V<jats:sup>−1</jats:sup> s<jats:sup>−1</jats:sup> and an on/off‐ratio (I<jats:sub>on</jats:sub>/I<jats:sub>off</jats:sub>) of 1.5×10<jats:sup>3</jats:sup>.</jats:p>