Recently synthesized benzoannulated fused oligothiophenes and oligoselenophenes are introduced as air-stable organic semiconductors for high-performance organic field-effect transistors. To evaluate electronic mobility intrinsic to the materials, the technique of single-crystal transistors is employed for two representative compounds of benzoannulated pentathienoacene f-B5TB and its selenium analog f-BT3STB. High mobility of approximately 1.1cm2Vs is achieved for the selenium compound due to its considerable Se---Se orbital interactions. The materials simultaneously bear features of high mobility and high duration in ambient atmosphere.

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