Photoredox Catalysts Based on <i>N</i> ‐(Hexyl)benzothioxanthene‐3,4‐dicarboximide for Photopolymerization and 3D Printing Under Visible Light

Abstract Photoredox catalytic systems are widely used in free radical polymerization as an important photoinitiating approach. However, many reported photoredox catalytic systems are limited by their low stabilities, high excitation powers, and low initiating efficiencies upon excitation in the visible region. Therefore, it is still a great challenge to develop efficient photoinitiating systems for photopolymerization under visible light. In this work, three new effective photosensitizers from N ‐(hexyl)benzothioxanthene‐3,4‐dicarboximide derivatives, namely 2‐hexyl‐1 H ‐thioxantheno[2,1,9‐ def ]isoquinoline‐1,3(2 H )‐dione (BTXI), 5‐bromo‐2‐hexyl‐1 H ‐thioxantheno[2,1,9‐ def ]isoquinoline‐1,3(2 H )‐dione (BTXI‐Br) and 2‐hexyl‐1 H ‐thioxantheno[2,1,9‐ def ]isoquinoline‐1,3(2 H )‐dione 6,6‐dioxide (BTXIO), were designed by density functional theory calculation and synthesized as photoredox catalysts for visible light induced photopolymerization. When combined with initiators such as oxidants, that is, bis (4‐ tert ‐butylphenyl)iodonium hexafluorophosphate or sulfonium salts (i.e., thianthrenium salts, phenoxathiinium salt, phenothiazinium salt, dibenzothiophenium salt) and the reductant ethyl dimethylaminobenzoate to form three‐component initiating systems, they showed good to high performance in visible light photo polymerizations with LED@405 nm and LED@450 nm. In addition, these photoinitiating systems enable the successful digital light processing and direct laser writing of 3D structures with high resolution, demonstrating a promising strategy for 3D printing applications.