Selective and Reversible Solvent Uptake in Tetra‐4‐(4‐pyridyl)phenylmethane‐based Supramolecular Organic Frameworks

The dynamic behavior of supramolecular organic frameworks (SOFs) based on the rigid tetra‐4‐(4‐pyridyl)phenylmethane (TPPM) organic tecton has been elucidated through 3D electron diffraction, X‐ray powder diffraction and differential scanning calorimetry (DSC) analysis. The SOF undergoes a reversible single‐crystal‐to‐single‐crystal transformation when exposed to vapours of selected organic solvents, moving from a closed structure with isolated small voids to an expanded structure with solvated channels along the b axis. The observed selectivity is dictated by the fitting of the guest in the expanded SOF, following the degree of packing coefficient. The effect of solvent uptake on TPPM solid‐state fluorescence was investigated, evidencing a significant variation in the emission profile only in the presence of chloroform.