Donor–Acceptor Conjugated Polymers Based on Bisisoindigo: Energy Level Modulation toward Unipolar n‑Type Semiconductors

Four bisisoindigo (bis-IID) derivatives containing different numbers of electron withdrawing fluorine (F) or nitrogen (N) atoms and eight alternating copolymers of them with 2,2′-bithophene (BT) or 3,3′,4,4′-tetrafluoro-2,2′-bithiophene (4FBT) were synthesized. Depending on the numbers of F and N atoms incorporated, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of the polymers were feasibly tuned in the ranges of −5.51 to −6.06 eV and −3.64 to −4.01 eV, respectively. Top gate and bottom contact (TGBC) organic thin-film transistors (OTFTs) were fabricated to study the semiconducting properties of the polymers. Five polymers, i.e., P0F-BT, P2F-BT, P4F-BT, P2N2F-BT, and P0F-4FBT that contain 0–4 F and N atoms in the repeating unit, with HOMO and LUMO energy levels above −5.90 and −3.80 eV, respectively, all showed ambipolar OTFT characteristics. Three other polymers P2F-4FBT, P4F-4FBT, and P2N2F-4FBT that contain 6 or 8 F and N atoms with HOMO levels below −5.90 eV and LUMO levels below −3.80 eV were all unipolar n-type semiconductors, with electron mobilities up to 0.93, 0.71, and 1.24 cm2/V·s, respectively