Water-soluble phosphate-pillar[5]arene (WPP5)-based artificial light-harvesting system for photocatalytic cross-coupling dehydrogenation

Abstract

A novel water-soluble phosphate-pillar[5]arene (WPP5)-based artificial light-harvesting system (LHS) was successfully fabricated through the supramolecular assembly of phenyl-pyridyl-acrylonitrile derivative (PBT), WPP5, and organic pigment Eosin Y (ESY). Initially, after host–guest interaction, WPP5 could bind well with PBT and form WPP5 ⊃ PBT complexes in water, which further assembled into WPP5 ⊃ PBT nanoparticles. WPP5 ⊃ PBT nanoparticles performed an outstanding aggregation-induced emission (AIE) capability because of the J-aggregates of PBT in WPP5 ⊃ PBT nanoparticles, which were appropriate as fluorescence resonance energy transfer (FRET) donors for artificial light-harvesting. Moreover, due to the emission region of WPP5 ⊃ PBT overlapped well with the UV–Vis absorption of ESY, the energy of WPP5 ⊃ PBT (donor) could be significantly transferred to ESY (acceptor) via FRET process in WPP5 ⊃ PBT-ESY nanoparticles. Notably, the antenna effect (AEWPP5⊃PBT-ESY) of WPP5 ⊃ PBT-ESY LHS was determined to be 30.3, which was much higher than that of recent artificial LHSs for photocatalytic cross-coupling dehydrogenation (CCD) reactions, suggesting a potential application in photocatalytic reaction. Furthermore, through the energy transfer from PBT to ESY, the absolute fluorescence quantum yields performed a remarkable increase from 14.4% (for WPP5 ⊃ PBT) to 35.7% (for WPP5 ⊃ PBT-ESY), further confirming their FRET processes in WPP5 ⊃ PBT-ESY LHS. Subsequently, in order to output the harvested energy for catalytic reactions, WPP5 ⊃ PBT-ESY LHSs were used as photosensitizers to catalyze the CCD reaction of benzothiazole and diphenylphosphine oxide. Compared to free ESY group (21%), a significant cross-coupling yield of 75% in WPP5 ⊃ PBT-ESY LHS was observed, because more UV region energy of PBT was transferred to ESY for CCD reaction, which suggested more potential in improving the catalytic activity of organic pigment photosensitizers in aqueous systems.