Probing Dielectric Properties of Metal-Organic Frameworks: MIL-53(Al) as a Model System for Theoretical Predictions and Experimental Measurements via Synchrotron Far- and Mid-Infrared Spectroscopy.

Emerging nanoporous materials, such as metal-organic frameworks (MOFs), are promising low-k dielectrics central to next-generation electronics and high-speed communication. Hitherto, the dielectric characterization of MOFs is scarce, with very limited experimental data for guiding new materials design and synthesis. Herein we demonstrate the efficacy of high-resolution synchrotron infrared (IR) specular reflectance experiments to study the dynamic dielectric properties of a flexible MOF structure: bistable MIL-53(Al) that exhibits switching between a large pore (LP) and a narrow pore (NP) architecture. We show that the ratio of LP:NP content of a polycrystalline sample can be changed via increased mechanical stress applied for pelletizing the MIL-53(Al) powder. We quantify the frequency-dependent dielectric constants over ∼1 to 120 THz, identifying all dielectric transitions as a function of stress and phase mixtures, showing how porosity modifies MOF's dielectric properties.