A fluorescent paramagnetic Mn metal–organic framework based on semi-rigid pyrene tetracarboxylic acid: sensing of solvent polarity and explosive nitroaromatics

An Mn metal–organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H₄L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-LMOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt's solvent polarity parameter (E_T^N). Further, the applicability of Mn-Lto the sensing of nitroaromaticsviafluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF.