Visible light-promoted nickel-NHC photocatalysts for free radical photopolymerization and 3D printing application†

Abstract

The evaluation of Ni^II complexes bearing bidentate N-heterocyclic carbene (NHC) ligands has shown their great potential as catalysts in various reactions. However, their luminescence properties and photocatalytic applications remain underexplored. Two novel nickel-based NHC complexes, [Ni(py-NHC)₂](PF₆)₂ () and [Ni(ph-NHC)₂] (), were synthesized with ligands N-mesityl-N′-2-pyridylimidazolium tetrafluorophosphate and 1-mesityl-3-phenyl-1H-imidazol-3-ium tetrafluorophosphate, respectively. The complexes were thoroughly characterized using spectroscopy techniques, including FTIR, UV-Vis, ¹H NMR, and fluorescence, along with elemental analysis, cyclic voltammetry, and mass spectrometry. and exhibited emission properties and lifetimes of 3.8 and 9.1 ns, respectively. The photocatalytic properties of and were investigated for initiating free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet light. This process incorporated di-tert-butyl-diphenyl iodonium hexafluorophosphate and ethyl dimethylaminobenzoate as additives. achieved the highest monomer conversion under air or in laminate and was effective in on–off LED irradiation. Proposed oxidative and reductive mechanisms were supported by photolysis, fluorescence quenching, and electron spin resonance data. The optimized system was applied in 3D printing, producing smooth-surfaced, high-resolution patterns.