Size-Dependent Thermal Shifts to MOF Nanocrystal Optical Gaps Induced by Dynamic Bonding

Conventional semiconductor nanocrystals exhibit wide-ranging optical behavior, whereas the size-dependent photophysical properties of metal-organic framework (MOF) nanocrystals remain an open research frontier. Here, we present size- and temperature-dependent optical absorption spectra of common MOFs with particle sizes ranging from tens of nanometers to several micrometers. All materials exhibit optical gaps that decrease at elevated temperatures, which we attribute to the dynamic nature of MOF metal-linker bonds. Accordingly, whereas the labile titanium-carboxylate bonds of MIL-125 give rise to bandgaps that red-shift by ∼600 meV over 300 K, the more rigid zinc-imidazolate bonds of ZIF-8 produce a red-shift of only ∼10 meV. Furthermore, smaller particles induce far larger decreases to optical gaps. Taken together, these results suggest MOF bonding becomes more flexible with smaller nanocrystal sizes, offering a powerful tool for manipulating optical behavior through composition, temperature, and dimensionality.