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Several 2‐phenylamino‐1,4‐naphthoquinone‐based dyes and two related benzo[2,3‐b]–phenazines were synthesised and characterised by proton nuclear magnetic resonance spectroscopy and electron ionisation mass spectrometry. The electrochemical and spectral properties of these compounds were investigated. The synthesised dyes were found to be capable photosensitisers for radical (reducible/oxidisable) and cationic polymerisations, respectively. In radical polymerization, better results in the oxidisable process were achieved.

Photoredox pairs consisting of 1,4‐naphthoquinone dyes and commercially available hydrogen donors (2‐mercaptobenzoxazole, 2‐mercaptobenzothiazole, 2‐mercaptobenzimidazole and 2,5‐dimercapto‐1,3,4‐thiadiazole) are found to be effective initiator systems for the radical polymerisation of trimethylolpropane triacrylate under visible light. The efficiency of these initiator systems is discussed in terms of the free energy change for the electron transfer process from the dye to the hydrogen donor. The results show that the photoinitiation ability of tested photoredox pairs depends on the structure of both the dye and the hydrogen donor.

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Several dyes based on the 6,7-dichloro-5,8-quinolinedione skeleton have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and electron ionisation mass spectrometry. The spectroscopic and electrochemical properties of these dyes were investigated. Photoredox pairs consisting of the synthesised dyes and commercially available hydrogen donors (2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2,5-dimercapto-1,3,4-thiadiazole) were tested for use as effective initiator systems for radical polymerisation of trimethylolpropane triacrylate with visible light. The efficiencies of these initiator systems are discussed in terms of the free energy change for the electron transfer process from the dye to the hydrogen donor.

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Several 6‐pyridinium benzo[a]phenazine‐5‐oxide derivatives have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic and electrochemical properties of these dyes were examined. The dyes were used as reducible sensitisers for selected electron donors (phenylthioacetic acid, phenoxyacetic acid, N‐phenylglycine, and ethyl 4‐N,N‐dimethylaminobenzoate) and as oxidisable sensitisers for electron acceptors (onium and N‐alkoxypyridinium salts). These photoredox pairs were found to be effective visible‐wavelength photoinitiators for the free radical polymerisation of trimethylolpropane triacrylate under visible light. The cationic photopolymerisation of cyclohexene oxide by the studied dyes and the onium salt photoredox pairs was ineffective. The obtained results are discussed on the basis of both free energy change for electron transfer to or from the benzo[a]phenazine dyes and the photochemical properties of the dyes, particularly their photobleaching. The proposed mechanism of dye fading is supported by density functional theory calculations and spectroscopic characterisation of the radical cation of the dye.