Fluorescent Organic Lewis-Pair Nanoparticles: Excited-State Intramolecular Proton Transfer Molecule...

The excited-state intramolecular proton transfer (ESIPT) reaction, one of the fundamental photochemical processes, is known to occur in 2-(2'-hydroxyphenyl)benzothiazole (HBT), showing an enol-to-keto phototautomerization. In this article, Lewis-pair adduct formation is demonstrated between HBT (Lewis base) and diphenylborinic anhydride (DPBA; Lewis acid), in which the proton transfer occurs in the ground state to form the keto tautomer of HBT. The HBT/DPBA Lewis-pair adduct exhibits strong pale-blue fluorescence at 480 nm in dichloroethane. Additionally, organic Lewis-pair nanoparticles of HBT/DPBA are successfully synthesized on the basis of a reprecipitation protocol in which HBT in conjunction with DPBA dissolved in acetone was rapidly injected into water under ultrasonication. DPBA here also acts as a stabilizing or protecting agent to form spherical nanoparticles with well dispersion. The nanoparticles also exhibit strong keto-type emission centered at 490 nm, changing the emission color to bluish-green. Quantum chemical calculations find the sole formation of the keto tautomer of HBT counterpart in the Lewis pair. Importantly, the present synthesis methodology based on Lewis acid-base chemistry does not require complicated operations to organically synthesize solid-state emitters and thus will play a key role in simply controlling the emission behavior for the new type of organic nanoparticles.