RAFT Polymerization of Semifluorinated Monomers Mediated by a NIR Fluorinated Photocatalyst

Near‐infrared (NIR) light plays an increasingly important role in the field of photoinduced electron/energy transfer‐reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization due to its unique properties. Yet, the NIR photocatalyst with good stability for PET‐RAFT polymerization remains promising. Here, a strategy of NIR PET‐RAFT polymerization of semifluorinated monomers using fluorophenyl bacteriochlorin as a photocatalyst with strong absorption at the NIR light region (710–780 nm) is reported. In which, the F atoms are used to modify reduced tetraphenylporphyrin structure with enhanced photostability of photocatalyst. Under the irradiation of NIR light (λmax = 740 nm), the PET‐RAFT polymerization of semifluorinated methylacrylic monomers presents living/control characteristics and temporal modulation. By the PET‐RAFT polymerization‐induced self‐assembly (PISA) strategy, stable fluorine‐containing micelles are constructed in various solvents. In addition, the fluorinated hydrophobic surface is fabricated via a surface‐initiated PET‐RAFT (SI‐PET‐RAFT) polymerization using silicon wafer bearing RAFT agents with tunable surface hydrophobicity. This strategy not only enlightens the application of further modified compounds based on porphyrin structure in photopolymerization, but also shows promising potential for the construction of well‐defined functional fluoropolymers. The near‐infrared (NIR) photoinduced electron/energy transfer‐reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization of semifluorinated monomers is achieved using fluorophenyl bacteriochlorin as a photocatalyst. Based on the technology, the nano‐objects and tunable hydrophobic surfaces can be fabricated.