Polymerization reactions induced by light are gaining increasing importance in the field of polymer synthesis; however, effective photopolymerization under visible light emitting diodes (LEDs), as opposed to UV light, remains limited and warrants further research and development. In this work, a family of bisbenzothieno[b]-fused boron dipyrromethene (BODIPY) derivatives, which have not been previously tested for photopolymerization, were designed. They contain seven fused aromatic rings with broad absorption properties and were introduced with amine and iodonium salt to form three-component photoinitiating systems (PISs) for the first time. Remarkably, under visible light irradiation, e.g. LED@405 nm and LED@660 nm, these PISs were able to initiate the free radical polymerization of acrylate monomers and cationic polymerization of epoxy monomers at room temperature, displaying different photopolymerization kinetics. This excellent initiation ability at both ends of the visible spectrum (i.e. the highest and lowest photon energy) indicated a remarkable panchromatic initiation ability. The exceptional photochemical reactivity of these BODIPY dyes and the underlying photoinitiation mechanisms of the PISs were thoroughly investigated through steady-state photolysis, fluorescence quenching experiments, and theoretical calculations. Finally, three-dimensional patterns with excellent spatial resolution were successfully printed using the BODIPY dye with the highest photoinitiation efficiency via direct laser writing, highlighting its significant potential for 3D printing applications.

中文翻译：

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双苯并噻吩并[b]-熔融 BODIPYs 在全色光引发中用于自由基和阳离子光聚合及其在 3D 打印中的应用


光诱导的聚合反应在聚合物合成领域越来越重要;然而，与紫外光相比，在可见光发光二极管 （LED） 下的有效光聚合仍然有限，需要进一步研究和开发。在这项工作中，设计了一族双苯并噻吩并 [b] -熔融硼二吡咯甲烯 （BODIPY） 衍生物，这些衍生物以前没有经过光聚合测试。它们包含七个具有广泛吸收特性的熔融芳香环，并与胺和碘盐一起引入，首次形成三组分光引发系统 （PIS）。值得注意的是，在可见光照射下，例如 LED@405 nm 和 LED@660 nm，这些 PISs 能够在室温下引发丙烯酸酯单体的自由基聚合和环氧单体的阳离子聚合，表现出不同的光聚合动力学。可见光谱两端的这种出色的起始能力（即最高和最低的光子能量）表明了非凡的全色起始能力。通过稳态光解、荧光猝灭实验和理论计算，彻底研究了这些 BODIPY 染料的特殊光化学反应性和 PIS 的潜在光引发机制。最后，使用具有最高光引发效率的 BODIPY 染料通过直接激光写入成功打印出具有出色空间分辨率的三维模型，凸显了其在 3D 打印应用中的巨大潜力。