Diaceno[a,e]pentalenes: An Excellent Molecular Platform for High‐Performance Organic Semiconductors

Three diacenoa,e]pentalene analogues with pendant sterically bulky di‐tert‐butylphenyl groups have been designed and synthesized. With the extension of the conjugated molecular framework, the molecular arrangement is apparently tuned by the balance between the π‐extended surface and pendant alkyl or aryl substituents. Theoretical calculations of the morphologies were in good agreement with the experimental results. Ambient‐stable field‐effect transistors based on dianthracenoa,e]pentalene ( DAP ) have been fabricated, which exhibited excellent hole mobilities (up to 6.55 cm² V^?1 s^?1). Thus, this study has shown that diacenoa,e]pentalenes are stable even with an extraordinarily large π‐surface area, and may thus serve as excellent molecular platforms for further exploring high‐performance semiconducting materials.