Understanding the mechanical properties of metal-organic frameworks (MOFs) is crucial not only to yield robust practical applications, but also to advance fundamental research underpinning the flexibility of a myriad of open-framework chemical compounds. Herein we present one of the most comprehensive structural analyses yet on MOF-mechanics: elucidating the complex elastic response of an isoreticular series of topical Zr-based MOFs, explaining all the important mechanical properties, and ide...

We show clear experimental evidence of cooperative terahertz (THz) dynamics observed below 3 THz (similar to 100 cm(-1)), for a low-symmetry Zr-based metal-organic framework structure, termed MIL-140A [ZrO(O2C-C6H4-CO2)]. Utilizing a combination of high-resolution inelastic neutron scattering and synchrotron radiation far-infrared spectroscopy, we measured low-energy vibrations originating from the hindered rotations of organic linkers, whose energy barriers and detailed dynamics have been el...

The comprehensive elastic properties of Zeolitic Imidazolate Frameworks (ZIF-1 to ZIF-4) have been computed using density functional theory (DFT). We employed the periodic CRYSTAL14 code to calculate the single-crystal elastic coefficients (C-ij) at the B3LYP level of theory. While the chemical compositions of ZIFs-1 to -4 are the same, each structure features a distinct network topology, crystal symmetry and porosity configuration, which translate into differential structure-function mechani...

We present the frequency-dependant (dynamic) dielectric response of a group of topical polycrystalline zeolitic imidazolate-based metal-organic framework (MOF) materials in the extended infrared spectral region. Using synchrotron-based FTIR spectroscopy in specular reflectance, in conjunction with density functional theory (DFT) calculations, we have revealed detailed structure-property trends linking the THz region dielectric response to framework porosity and structural density. The work de...

We employed a combination of theoretical and experimental techniques to study the metal-organic framework (MOF)-mechanics central to the paddle-wheel Cu-3(BTC)(2) porous structure, commonly designated as HKUST-1. Lattice dynamics of the hybrid framework at below 18 THz were measured by means of Raman and synchrotron far-infrared spectroscopy, and systematically correlated to collective vibrational modes computed from ab initio density functional theory (DFT). We have identified a number of in...

This review is concerned with the recent advances in metal organic framework (MOF) materials. We highlight the unique combination of physicochemical and thermomechanical characteristics associated with MOF-type materials and illustrate emergent applications in three challenging technological sectors: energy, environmental remediation and biomedicine. MOFs represent an exciting new class of nanoporous crystalline solids constituting metal ions/clusters and multifunctional organic linkages, whi...

We present an unambiguous identification of low-frequency terahertz vibrations in the archetypal imidazole-based metal-organic framework (MOF) materials: ZIF-4, ZIF-7, and ZIF-8, all of which adopt a zeolite-like nanoporous structure. Using inelastic neutron scattering and synchrotron radiation far-infrared absorption spectroscopy, in conjunction with density functional theory (DFT), we have pinpointed all major sources of vibrational modes. Ab initio DFT calculations revealed the complex nat...