| Abstract: | The first synthesis of the fully conjugated ethynylene‐linked polymer incorporating boron dipyrrine complex (BODIPY) and zinc porphyrin in the main chain was performed based on the exclusive Sonogashira polycondensation. Comprehensive experimental and theoretical investigations lead to an elaborate synthetic route to circumvent the possible side reactions of BODIPY in the presence of the palladium catalyst. Additionally, optimization of the synthetic conditions found that dichloromethane as the solvent suppresses the formation of the pseudo‐trans dimer of the copper acetylide and mitigates the undesired oxidative homocoupling reaction. Eventually, the exclusive Sonogashira polycondensation in dichloromethane provided the alternating BODIPY–porphyrin ethynylene‐conjugated polymer, which displayed absorption up to the near‐infrared wavelengths. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2457–2465 |
