Room-Temperature Phosphorescence-active Boronate Particles: Characterization and Ratiometric Afterglow-sensing Behavior by Surface Grafting of Rhodamine B

We found that boronate particles (BP), as a self-assembled system prepared by sequential dehydration of benzene-1,4-diboronic acid with pentaerythritol, showed greenish room-temperature phosphorescence (RTP). This emission was observed in both solid and dispersion state in water. To understand the RTP properties, X-ray crystallographic analysis, and density functional theory (DFT) and time-dependent DFT at M06-2X/6-31G(d,p) level were performed using 3,9-dibenzo-2,4,8,10-tetraoxa-3,9-diboraspiro[5.5]undecane (1) as a model compound. Our interest in functionalizing the RTP-active particles led us to graft Rhodamine B onto their surface. The resulting system emitted a dual afterglow via a Forster-type resonance energy transfer process from the BP in the excited triplet state to Rhodamine B acting as an acceptor fluorophore. This emission behavior was used for ratiometric afterglow sensing of water content in THF with a detection limit of 0.28 %, indicating that this study could pave the way for a new strategy for developing color-variable afterglow chemosensors for various analytes.