Do The Twist: Efficient Heavy‐Atom‐Free Visible Light Polymerization Facilitated by Spin‐Orbit Charge Transfer Inter‐system Crossing
Do The Twist: Efficient Heavy‐Atom‐Free Visible Light Polymerization Facilitated by Spin‐Orbit Charge Transfer Inter‐system Crossing
复制标题
扭转局面：自旋轨道电荷转移系统间穿越促进高效重原子自由可见光聚合
DOI：
10.1002/anie.202219140
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Page, Zachariah A.
中科院分区：
文献类型：
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作者：
Uddin, Ain;Allen, Seth R.;Rylski, Adrian K.;O'Dea, Connor J.;Ly, Jack T.;Grusenmeyer, Tod A.;Roberts, Sean T.;Page, Zachariah A.
使用可见光驱动聚合并进行时空控制为当代基于紫外光的软材料生产提供了一种温和的替代方案。在这个光谱区域，光氧化还原催化是最有效的聚合方法，但它依赖于使用重原子，如贵金属或有毒卤素。在本文中，来自带有扭曲芳族基团的硼二吡咯亚甲基（BODIPY）二联体的自旋-轨道电荷转移系间交叉被示出能够在不存在重原子的情况下实现有效的可见光聚合。相对于对照，扭转BODIPY实现了聚合速率的105 -15倍增加和光稳定性的改善。此外，单体极性对聚合速率有明显的影响，这归因于基于超快瞬态吸收和磷光光谱的电荷转移稳定。最后，使用本发明的光系统展示了使用绿色LED的快速和高分辨率3D打印。
The use of visible light to drive polymerizations with spatiotemporal control offers a mild alternative to contemporary UV‐light‐based production of soft materials. In this spectral region, photoredox catalysis represents the most efficient polymerization method, yet it relies on the use of heavy‐atoms, such as precious metals or toxic halogens. Herein, spin‐orbit charge transfer intersystem crossing from boron dipyrromethene (BODIPY) dyads bearing twisted aromatic groups is shown to enable efficient visible light polymerizations in the absence of heavy‐atoms. A ≈5–15× increase in polymerization rate and improved photostability was achieved for twisted BODIPYs relative to controls. Furthermore, monomer polarity had a distinct effect on polymerization rate, which was attributed to charge transfer stabilization based on ultrafast transient absorption and phosphorescence spectroscopies. Finally, rapid and high‐resolution 3D printing with a green LED was demonstrated using the present photosystem.