Polarity-Induced Excited-State Intramolecular Proton Transfer (ESIPT) in a Pair of Supramolecular Isomeric Multifunctional Dynamic Metal–Organic Frameworks

A pair of supramolecular isomers of Cd^II-based MOF have been synthesized by utilizing a flexible N,N′-donor linker and a dicarboxylate with ESIPT (excited-state intramolecular proton transfer) fluorophore by varying the reaction media. One of the MOFs has a 3D four-fold interpenetrating framework with guest solvent in the structure that undergoes a solvent-dependent crystalline-to-crystalline structural transformation, which has been extensively studied by powder XRD and IR spectroscopy. The other MOF is structurally rigid in nature and has a two-fold interpenetrating structure without any guest molecules. Both the compounds show moderate CO₂ adsorption and one of them, the MOF with the four-fold interpenetrating structure, also shows moderately high H₂ adsorption. Furthermore, both the compounds show interesting luminescence behavior. In the solid state, the two compounds show single-peak spectra, whereas upon suspension of these compounds in polar solvents, the maxima split into two peaks with a large Stokes shift. On the other hand, in nonpolar solvents, only one emission maximum is observed. This solvatochromic dual-emission phenomenon is due to ESIPT, which has been extensively studied.