Continuous-flow synthesis and application of polymer-supported BODIPY Photosensitisers for the generation of singlet oxygen; process optimised by in-line NMR spectroscopy

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 alpha-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. Graphical abstract 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.