Synthesis, Characterization, and Field-Effect Transistors Properties of Novel Copolymers Incorporating Nonplanar Biindeno[2,1‑b]thiophenylidene Building Blocks

A nonplanar but conjugated heteroacene, biindeno­[2,1-b]­thiophenylidene (BTP), is employed to design and synthesize solution-processable polymer semiconductors for organic field-effect transistors (OFETs) applications first. By copolymerizing with isoindigo (IDG), diketopyrrolopyrrole (DPP), and naphthalenediimide (NDI) derivatives, three novel BTP-based copolymers (PBTP-IDG, PBTP-DPP, and PBTP-NDI) have been synthesized and characterized successfully. The results indicate that three BTP-based polymers exhibit broad absorption spectra and good solubility in most common solvents. Because of the dominantly electron-deficient contributions to the whole polymer backbones, the energy levels of the lowest unoccupied molecular orbitals are decreased to ca. −4.0 eV for all these polymers, thus exhibiting good electron affinities. Moreover, the deep-lying energy levels of the highest occupied molecular orbitals (HOMO) have been demonstrated for three BTP-based polymers, with the HOMO values ranging from −5.48 to −5.80 eV. Investigation of the OFETs performance indicates that three BTP-based polymers exhibit well hole transport properties in ambient air and excellent ambipolar performance in a N2 glovebox. Compared with PBTP-IDG and PBTP-NDI, the uniform morphological structure, interconnected polycrystalline grain, and close π–π stacking distance endow PBTP-DPP with higher hole mobility of 1.43 cm2 V–1 s–1. Particularly, the well-balanced hole and electron mobilities of 0.68 and 0.13 cm2 V–1 s–1 have been demonstrated for the PBTP-DPP-based OFETs in a N2 atmosphere, respectively. The results suggest that the nonplanar BTP unit and its derivatives are promising π-conjugated building blocks for the design and synthesis of solution-processable polymer semiconductors with high charge-transporting performance.