A series of novel sulfur-containing bent N-heteroacenes were constructed and characterized by NMR and UV/Vis spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction. By introducing sulfur-containing groups (thio, sulfinyl, and sulfonyl) into bent azaacenes, their electronic delocalization was improved and frontier energy levels were modulated. The target products displayed tunable optical and electronic properties through altering the valence of sulfur and fused length of the azaacenes. For the first time, typical products were utilized as organic field effect transistor materials, affording promising results.
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