We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 stru...

We report the development of a forcefield capable of reproducing accurate lattice dynamics of metal-organic frameworks. Phonon spectra, thermodynamic and mechanical properties, such as free energies, heat capacities and bulk moduli, are calculated using the quasi-harmonic approximation to account for anharmonic behaviour due to thermal expansion. Comparison to density functional theory calculat...

The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. ...

The role of the structure of three isoreticular metal-organic frameworks (IRMOFs) on their adsorption behavior has been studied in this work, selecting different kinds of volatile organic compounds (VOCs) as adsorbates (alkanes, alkenes, cycloalkanes, aromatics and chlorinated). For this purpose, three samples (IRMOF-1, IRMOF-8 and IRMOF-10) with cubic structure and without functionalities on t...

We determine the saturation storage density for hydrogen on several metal−organic framework (MOF) and covalent−organic framework (COF) materials by spillover. We use density functional theory on periodic frameworks to achieve reliable and accurate predictions for these materials. We find that one hydrogen can be stored at each C atom of the linker, and an additional H for each CO2 group. For IR...

We present an ab-initio derived force field to describe the structural and mechanical properties of metal-organic frameworks (or coordination polymers). The aim is a transferable interatomic potential that can be applied to MOFs regardless of metal or ligand identity. The initial parametrization set includes MOF-5, IRMOF-10, IRMOF-14, UiO-66, UiO-67, and HKUST-1. The force field describes the p...

In the present work, interaction strength of Carbon Monoxide (CO) with a set forty-two, strategically selected, functionalized benzenes was calculated. Our ab initio calculations at MP2/6-311++G** level theory reveal that phenyl hydrogen sulfate (-OSO3H) showed highest CO (?19.5 kJ/mol), which approximately three times stronger compared unfunctionalized benzene (?5.3 kJ/mol). Moreover, top-perf...

A manganese(II) acetylacetonate complex has been immobilized to the metal-organic framework IRMOF-3 through a one-step post-synthetic route for the first time, providing an effective and recyclable heterogeneous catalyst for epoxidation of alkenes.

The synthesis and physical properties of dioxole functionalized metal-organic frameworks (MOFs) are reported. Combination of benzo[d][1,3]dioxole-4,7-dicarboxylic acid (dioxole-BDC) and Zn(II) under solvothermal conditions yields either an isoreticular metal-organic framework analog (IRMOF-1-dioxole) or a new MOF material (MOF-1-dioxole). With the addition of a co-ligand, namely 4,4'-bipyridine...