Abstract
Direct C–H arylation (DA) polymerization, often known as DArP, is an emerging protocol to the synthesis of π-functional polymers that has garnered a lot of attention due to its virtues of requiring a minimum number of synthetic steps and producing a simpler byproduct. However, the regioselectivity of the C–H bonds is significantly less effective in the DArP-derived polymers, which is one of the reasons why only a small number of these polymers exhibit photovoltaic characteristics that are equal to counterparts generated via Stille coupling. In this work, a low-defect π-polymer PBDTF-TPD (DA) is facilely obtained via DArP between 4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']-dithiophene (BDTF) and thieno [3,4-c]pyrrole-4,6-dione (TPD) that possesses regioselective π-C−H bonds toward arylation. As a result, DArP-derived PBDTF-TPD (DA) and Stille-derived PBDTF-TPD (St) share the similar opto-electrochemical properties, photovoltaic performance, and morphology, indicating that DArP polymerization leads to defined structures with minimal branching defects. Specifically, this study demonstrates that the (PCE = 8.91%) of a rationally designed monomer for DArP using an ideal approach is equivalent to that of the Stille-derived analogue PBDTF-TPD (St, PCE = 9.57%).
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