Highly pure millimeter-sized MOF-5 single crystals were synthesized and characterized. Photoluminescence (PL) spectroscopy and time-correlated single photon counting (TCSPC) demonstrate a solvent-guest dependency of MOF-5 emission and its ligand-centred nature. These results allow measuring the true MOF-5 luminescence free of solvent at a wavelength of 355 nm, a significantly lower wavelength than previously published. MOF-5 emission was also evaluated with different solvents and various degrees of water intake, explaining previously published observations. Comparison between lifetimes shows the fluorophore stabilization within the frameworks and demonstrates the progressive influence of the Zn4O subunits on the fluorescence during hydration. Overall, this work highlights the necessity to obtain phase-pure material, especially when moisture sensitivity can play a role, before ascribing electronic transitions. This study is a rigorous new take on the iconic MOF-5 and on its photoluminescence properties.
