Novel Approach for Detecting Vapors of Acids and Bases with Proton-Transfer Luminescent Dyes Encapsulated within Metal–Organic Frameworks

Luminescent metal-organic frameworks (LMOFs) are one of the most promising materials for being implemented as active layers in the fabrication of photonic devices such as luminescent sensors of harmful chemicals. It is highly desirable that these materials undergo quantifiable spectroscopic (absorption or emission) changes in the presence of vapors of those analytes, as in many industrial processes, these toxic compounds are in the gas phase. Although great progresses have been achieved in the field, in most of the examples reported hitherto, the detection of chemicals by LMOFs is attained in solution. Herein, we present a novel approach consisting of the encapsulation of proton transfer dyes (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS, and 3-hydroxyflavone, 3-HF) within the pores of two distinct MOFs. The trapped proton transfer dyes (PT-dyes) may exist as different structures (enol, anion, or zwitterion), each of these exhibiting unique optical properties. Indeed, our findings reveal that the dyes can be encapsulated as anionic or enol species. Remarkably, the PT-dye@MOF composites exhibit a high luminescence quantum yield (up to 30%), which is sensitive (showing shifting in the emission wavelengths with a concomitant quenching/enhancement of the intensity) in the presence of vapors of an acid (HCl) and a base (triethylamine). These results open a novel avenue for the development of smarter vapoluminescent MOF-based materials.