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Continuous-flow synthesis and application of polymer-supported BODIPY Photosensitisers for the generation of singlet oxygen; process optimised by in-line NMR spectroscopy
Journal of Flow Chemistry ( IF 2.7 ) Pub Date : 2020-02-13 , DOI: 10.1007/s41981-019-00067-4
Christopher G. Thomson , Callum M. S. Jones , Georgina Rosair , David Ellis , Jose Marques-Hueso , Ai-Lan Lee , Filipe Vilela

Commercial polystyrene Merrifield-type resins have been post-synthetically functionalised with BODIPY photosensitisers via a novel aryl ester linking strategy in continuous-flow. A unique synthetic advantage of post-synthetically modifying heterogeneous materials in flow was identified. The homogeneous analogues of the polymer-supported BODIPYs were synthesised and used as reference to assess photophysical properties altered by the polymer-support and linker. The homogeneous and polymer-supported BODIPYs were applied in visible-light photosensitisation of singlet oxygen for the conversion of α-terpinene to ascaridole. Materials produced in flow were superior to batch in terms of functional loading and photosensitisation efficiency. Flow photochemical reactions generally outperformed batch by a factor of 4 with respect to rate of reaction. The polymer-supported BODIPY resins could be irradiated for 96 h without loss of photosensitising ability. Additional material synthetic modification and conditions optimisation using an in-line NMR spectrometer resulted in a 24-fold rate enhancement from the initial material and conditions.

Glow with the flow! Metal-free synthesis of polymer-supported BODIPY photosensitisers in flow has been achieved and shown to be superior to conventional batch synthesis. The materials were successfully applied as visible light (>500 nm) photosensitisers for the production of singlet oxygen and could be recycled multiple times. Pressure and flow rate optimisation was guided by in-line 1H-NMR spectroscopy leading to significant enhancement in process efficiency.



中文翻译:

聚合物负载的BODIPY光敏剂的连续流合成和应用,用于产生单线态氧;在线NMR光谱法对工艺进行优化

商业化的聚苯乙烯Merrifield型树脂已经通过BODIPY光敏剂通过新型的芳基酯连接策略在连续流动中进行了后合成功能化。确定了合成后修饰流中异质材料的独特合成优势。合成了聚合物负载的BODIPY的均相类似物,并用作评估由聚合物载体和接头改变的光物理性质的参考。均相和聚合物负载的BODIPY用于单线态氧的可见光光敏化,以转化α-松油烯为scar啶。在功能负载和光敏效率方面,流动生产的材料优于批次。相对于反应速率,流式光化学反应的性能通常比批次高4倍。可以将聚合物负载的BODIPY树脂辐照96 h,而不会损失光敏能力。使用在线NMR光谱仪进行的其他材料合成修饰和条件优化使初始材料和条件的速率提高了24倍。

发光流淌!已经实现了流态化的聚合物负载的BODIPY光敏剂的无金属合成,并且显示出优于常规的批处理合成。该材料已成功用作可见光(> 500 nm)光敏剂,用于生产单线态氧,并且可以多次回收。在线1H-NMR光谱指导了压力和流速的优化,从而显着提高了工艺效率。

更新日期:2020-04-21
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