“…Tetrahydrofuran (THF) was dried over sodium/benzophenone and freshly distilled before use. The intermediate compounds including 3,4‐dibromo‐2,5‐diformylthiophene 1 , dithieno[3,2‐b:2′,3′‐d]thiophene‐2,6‐dicarboxylic acid diethyl ester 2 , 2,6‐dibromodithieno[3,2‐b;2’,3’‐d]thiophene M1 , 2,6‐bis[2′‐(3′‐dodecylthienyl)]‐dibromodithieno‐[3,2‐b;2′,3′‐d]thiophene M2 , 3,6‐bis(4‐bromophenyl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione 5 , 3,6‐bis(4‐bromophenyl)‐2,5‐bis(2‐ethylhexyl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione 6 , 1,4‐diketo‐2,5‐ di(2‐ethylhexyl)pyrrolo[3,4‐c]pyrrole‐3,6‐di‐phenyl‐4‐pinacolato boron ester (PDDP), 2,5‐bis(5‐bromo‐3‐((2‐dodecyl)oxy)thiophen‐2‐yl)thiazolo[5,4‐d]thiazole (TTz‐Br), 1,3‐dibromo‐5‐octylthieno[3,4‐c]pyrrole‐4,6‐dione (TPD‐Br) were prepared according to a slightly modified procedure in literature, with details shown in Supporting Information.…”