Unveiling the electronic effect of substituent on sensitized photopolymerization: An experimental and theoretical investigation

摘要: Abstract Dyes with D-A structure bearing electron donor (ED) and withdrawing (EW) moieties were widely adopted in photosensitized polymerization. However, the individual functions of ED EW groups rarely discussed. In this work, anthracene derivatives (ANDs) possessing aldehyde (ANCHO) methoxy group (ANOCH3) at 9-position carried out as photosensitizers for ONI. Photopolymerization photobleaching results indicate that ANOCH3/ONI presents higher sensitizing performance than anthracene, while ANCHO no ability although calculated free energy change photoinduced transfer (PET) reaction ANCHO/ONI is also negative. To disclose electronic effect substitution on PET reaction, experiments theoretical calculation jointly employed. Cyclic voltammetry result indicates makes hard to be oxidized. Moreover, intermolecular charge property hampers formation stable ANCHO-ONI complex. On contrary, not only decreases oxidation potential ANOCH3, but further stabilizes ground ANOCH3-ONI complex, which was considered responsible its enhanced ability.