oa Novel low band gap polymers based on pyrrolo[32d:45d’]bisthiazole PBTz and thienylenevinylene TV For Organic Electronic Applications

Novel low band gap polymers based on pyrrolo[3,2-d:4,5-d′]bisthiazole (PBTz) and thienylenevinylene (TV) For Organic Electronic Applications Dhananjaya Patra?,1 Hassan S. Bazzi,1 Lei Fang¬2 and Mohammed Al-Hashimi1 1Department of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar 2Department of Chemistry and Department of Materials Science and Engineering, Texas A&M University, College Station, TX. Corresponding author: [email protected] π-Conjugated organic polymers have been intensively studied over the past two decades due to their potential applications in areas such as organic light-emitting diodes (OLEDs),1 organic thin-film transistors (OTFTs), organic photovoltaics (OPV), and organic laser devices. In addition, they possess excellent properties that enable them to be solution processed offering a path-way for fabrication on large-area printable and cost-effective flexible electronic devices. Several donor-acceptor (D-A) conjugated polymers and small molecules are reported recently with photovoltaic performance over 12%.2-4 Recently significant development has been made in the design and synthesis of high performance polymers with mobilities now easily surpassing μ > 1 cm2 V-1 s-1.5 Among the various conjugated electron-donating building blocks, thienylenevinylene (TV) unit has attracted much interest owing to its coplanarity and extended π-conjugation which are induced by the presence of a vinylene spacer between the two thiophene units. As a result this enhanced interchain interaction the polymers exhibit a higher hole mobility and reduced energy band gaps.4 Recently, the incorporation of vinylene unit into several electron-rich (i.e., donor) and electron deficient (i.e., acceptor) units has been widely studied, especially, targeting at the device application for n-channel and ambipolar OTFTs with promising device performance. Among these units are diketopyrrolopyrrole (DPP), benzoselenadiazole (BSe), phthalimide (PhI), naphthalenediimide (NDI), benzothiadiazole (BT), dithienothiophene (DTT), thienopyrroledione (TPD), and isoindigo (iI) as depicted in Figure 1. For instance, Yoo et al. reported the synthesis of various polymers based on DPP and (E)-2-(2-(thiophen-2-yl)-vinyl)thiophene units by altering the number of thiophene in the repeat unit to induce strong π–π stacking and favorable molecular conformation. By replacing the thiophene unit with the selenophene vinylene selenophene Kang et al. reported an enhanced mobility. Several DPP and TV based polymers reported by Oh and Kim et al. via various side-chain engineering on the DDP units, obtained remarkable mobilities from 8.74 to 17.8 cm2 V − 1 s − 1.5 Reichmanis and co-workers also reported the synthesis of a series of BT oligothiophene and oligo-TV donor-acceptor (D − A) copolymers exhibiting mobilities of up to 0.75 cm2 V − 1 s − 1. Kim and co-workers reported the synthesis and characterization of highly soluble poly(thienylenevinylene) exhibiting carrier mobility of 1 cm2 V − 1 s − 1.6 Al-Hashimi, Heeney and co-workers systematically investigated the role of modifying the heteroatom, by synthesizing a series of vinylene copolymers containing 3-dodecylthiophene, selenophene and tellurophene.7,8 Figure 1. Structures of thiophene (Th), thiazole (Tz) diketopyrrolopyrrole (DPP), benzoselenadiazole (BSe), phthalimide (PhI), naphthalenediimide (NDI), benzothiadiazole (BT), dithienothiophene (DTT), thienopyrroledione (TPD), and isoindigo (iI). Another particularly promising class of building block for the development of high performing polymeric semiconductors for OTFTs is the electron-deficient pyrrolo[3,2-d:4,5-d′]bisthiazole (PBTz)-based heterocycle. In comparison to dithienothiophene (Figure 1), PBTz-unit is a weak acceptor having an electronegative nitrogen atom, which lowers the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies. Therefore, it is expected that the large polarity of the thiazole ring can enhance the intermolecular interaction. In addition, the bridging nitrogen (N) of PBTz offers the opportunity to include an additional solubilizing sidechain, which is not present in the analogous DTT. This potentially offer improved solubility and processability of the polymers. Nonetheless, to the best of our knowledge, there is no single report on the synthesis, polymer characterization, and charge carrier transport properties employing the fused PBTz containing TV units. In this work, we report the synthesis and characterization of a series of four PBTz-TV-based copolymers P1-P4 (Scheme 2) with various alkyl side chains for OTFT applications. Particularly, we have selected a dodecyl alkyl side chain on the thienylenevinylene unit, three branched alkyl side chains such as 2-octyldodecyl (OD), 9-heptadecyl (HD) and 2-ethylhexyl (EH), and a long straight n-hexadecyl (HD) chain on the nitrogen of the pyrrolobisthiazole unit, thus, for improving polymer solubility and effectively to promote π − π interchain interactions. The electrochemical redox properties and related electronic structures (HOMO/LUMO energy levels) were systematically investigated by cyclic voltammetry (CV). In addition, the microstructure and morphology of the polymer thin films were characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD). Finally, the PBTZ-copolymers show band gaps in the range of 1.40 − 1.46 eV and mobilities in the range of 0.002-0.062 cm2 V − 1 s − 1 in bottom-gate/top-contact OTFTs.9 References. 1. Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burn, P. L.; Holmes, A. B. Nature, 1990, 347, 539. 2. Sekitani, T.; Zschieschang, U.; Klauk, H.; Someya, T. Nat. Mater.,2010, 9, 1015.3. Zhao, W.; Li, S.; Yao, H.; Zhang, S.; Zhang, Y.; Yang, B.; Hou, J. J. Am. Chem. Soc., 2017, 139, 7148. 4. Li, N.; Baran, D.; Forberich, K.; Machui, F.; Ameri, T.; Turbiez, M.; Carrasco-O., M.; Drees, M.; Facchetti, A.; Krebse, F.C.; Brabec, C. J. Energy Environ. Sci., 2013, 6, 3407. 5. Kim, J.; Lim, B.; Baeg, K. J.; Noh, Y. Y.; Khim, D.; Jeong, H. G.; Yun, J. M.; Kim, D. Y. Chem. Mater.,2011, 23, 4663. 6. Fu, B. Y.; Baltazar, J.; Hu, Z. K.; Chien, A. T.; Kumar, S.; Henderson, C. L.; Collard, D. M.; Reichmanis, E. Chem. Mater.,2012, 24, 4123 7.Al-Hashimi, M.; Han, Y.; Smith, J.; Bazzi, H. S.; Alqaradawi, S. Y. A.; Watkins, S. E.; Anthopoulos, T. D.; Heeney, M. Chem. Sci.,2016, 7, 1093. 8. Al-Hashimi, M.; Baklar, M. A.; Colleaux, F.; Watkins, S. E.; Anthopoulos, T. D.; Stingelin, N.; Heeney, M. Macromolecules, 2011, 44, 5194. 9. Patra, D.; Lee, J.; Lee, J.; Sredojevic, D. N.; White, A.J.P.; Bazzi, H. S.; Brothers, E. N.; Heeney, M.; Fang, L.; Yoon. M.-H.; Al-Hashimi, M. J. Mater. Chem. C., 2017, 5, 2247.