Near UV–vis LED-excitable two-branched sensitizers for cationic, radical, and thiol-ene photopolymerizations

• These two two-branched sensitizers have high maximum molar extinction coefficients values.
• These two sensitizers match the emission of new light sources, i.e., UV–vis LEDs at 365–450 nm.
• The photoinitiating systems based on the sensitizers are highly efficient for versatile photopolymerizations.

Two novel branched sensitizers bearing biphenyl or fluorenyl groups as the linking skeleton and triphenylamine-stilbene-thiomethyl benzonitrile as peripheral branches were designed. Strong absorption of light in the UV–vis range (λmax = 389–397 nm, εmax = 60,200–90,300 M−1 cm−1) matched the emission of new light sources, i.e., UV–vis light-emitting diodes at 365–450 nm. The reactive species produced from the photoinitiating systems based on these chromophores themselves or combined with an iodonium salt, N-vinylcarbazole, or an amine were highly efficient for versatile photopolymerizations (radical, cationic, and thiol-ene polymerizations) upon soft exposure conditions (365–450 nm light-emitting diodes). The UV–vis spectra, theoretical calculation of molecular orbitals, electrochemistry, and fluorescence quenching measurements were studied to reveal the photochemical mechanism.