Incorporation of ESIPT into pillar[5]arene for solid-state dual emission responsive to <i>n</i>-hexane vapor

Abstract Pillar[5]arene is a promising macrocyclic receptor of a chemical sensor showing shape-selective encapsulation of neutral molecules into the cavity, but the poor fluorescence properties remain a challenge. Herein, we report a pillar[5]arene coupled with 2-(2-hydroxyphenyl)benzoxazole (HBO), which displays bright fluorescence in both solution and the solid state. Owing to the excited-state intramolecular proton transfer (ESIPT) in the HBO moiety, greatly improved fluorescence is observed for the pillar[5]arene derivative in CHCl3 (Φlum = 11%) and powder form (Φlum = 25%). Moreover, the emission color changes from light green to blue when the powder sample is exposed to n-hexane vapor. The color change derives from variable dual emission via ESIPT and excimer-forming pathways, as suggested by fluorescence lifetime measurements at different wavelengths. Powder x-ray diffraction indicates that increased crystallinity and a small alteration in the solid-state structure leads to visible fluorescent chromism upon vapor encapsulation.