Two novel bent-shaped thienoacenes, naphtho[2,3-b]naphtho[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DNTT) and anthra[2,3-b]anthra[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DATT) were synthesized from thieno[2,3-b]thiophene and their corresponding aromatic anhydrides by three steps: Friedel–Crafts acylation, acid-promoted cyclization, and reductive aromatization. The structural curvature improved the solubility of these thienoacenes in organic solvents. The bent-DNTT based FET device was fabricated by the spin-coating method. The device exhibited p-type characteristics with a mobility of 5.1 × 10−5 cm2 V−1 s−1. Its thin-film structure was fully characterized as an edge-on orientation with large intermolecular orbital coupling.
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