Taking Advantage of a Luminescent ESIPT-Based Zr-MOF for Fluorochromic Detection of Multiple External Stimuli: Acid and Base Vapors, Mechanical Compression, and Temperature.

Abstract

Luminescent materials responsive to external stimuli have captivated great attention owing to their potential implementation in noninvasive photonic sensors. Luminescent metal-organic frameworks (LMOFs), a type of porous crystalline material, have emerged as one of the most promising candidates for these applications. Moreover, LMOFs constructed with organic linkers that undergo excited-state intramolecular proton-transfer (ESIPT) reactions are particularly relevant since changes in the surrounding environment induce modifications in their emission properties. Herein, an ESIPT-based LMOF, UiO-66-(OH)2, has been synthesized, spectroscopically and photodynamically characterized, and tested for detecting multiple external stimuli. First, the spectroscopic and photodynamic characterization of the organic linker (2,5-dihydroxyterephthalic acid (DHT)) and the UiO-66-(OH)2 MOF demonstrates that the emission properties are mainly governed by the enol → keto tautomerization, occurring in the organic linker via the ESIPT reaction. Afterward, the UiO-66-(OH)2 MOF proves for the first time to be a promising candidate to detect vapors of acid (HCl) and base (Et3N) toxic chemicals, changes in the mechanical compression (exercised pressure), and changes in the temperature. These results shed light on the potential of ESIPT-based LMOFs to be implemented in the development of advanced optical materials and luminescent sensors.