Bicarbazole-based oxalates as photoinitiating systems for photopolymerization under UV–Vis LEDs

Photoinitiators are critical to initiate chain reactions in photopolymerization. For such applications, the absorption of photoinitiator must be compatible with the emission of light sources and enables the fast manufacturing of three-dimensional network or structures. Light-emitting diode (LED) is a new kind of energy-saving and environmental protection light source, exhibiting a substantial response in the near UV and visible range to replace the traditional mercury lamp and other light sources in photopolymerization. Here, we introduce methyl oxalate into bicarbazole chromophore ( BiCz ). By variation of the single or double substituents in the BiCz , we demonstrate that the absorption spectra can be adjusted and redshift to visible range and show good absorption in the near UV and visible range (365–475 nm). We explore their photochemistry based on experimental results and theoretical calculations and the mechanism of photoreactions have been verified. The super photostability by themselves and good hydrogen abstraction ability from amine co-initiator make them as excellent near UV and visible light active photoinitiators. Critically, the photoinitiation of the free-radical polymerization of acrylate monomers with low content (0.1% concentration) upon LED irradiation at 365–475 nm, exhibits excellent application potential in light curing and other fields.