Single-chain polymers as homogeneous oxidative photoredox catalysts

Single-chain polymer nanoparticles (SCNPs) are emerging as versatile catalytic platforms that provide excellent control over solubility. The confined nature of SCNPs can improve the rate of catalysis. While significant headway has been made in thermally-induced transition-metal catalysis with SCNPs, light-activated SCNP catalysts have received little attention. We are developing triarylpyrylium tetrafluoroborate (TPT)-functionalized SCNPs as oxidative photocatalysts. Herein, we comprehensively study the impact of light source on both SCNP compaction and TPT absorbance through gel-permeation chromatography and UV/Vis spectroscopy. We observe that compaction is expedited using light sources that excite the photocatalyst (e.g., blue LEDs), which is attributed to the ability of TPT to dimerize sytrenics under similar photoredox conditions. The resultant metal-free SCNP photocatalysts enable the oxidation of benzyl alcohols in good yields. The SCNP is further investigated for the amidation of 4-bromobenzaldehyde, wherein it affords higher yields of the benzamide product compared to both small-molecule and unfolded polymer controls. We attribute the combined results to the colocalization of the TPT photoredox catalyst and pyrene electron relay within the SCNP, which likely aids in single-electron transfer processes. The scope of amidation reactions was also extended to other aryl aldehydes, wherein deactivated substrates afforded the highest yield of the desired amide.