We describe a robust screening technique that correlates the surface area of metal-organic frameworks to the proton T2 relaxation behavior of imbibed solvent at low field (13 MHz). In frameworks with small pore sizes (<1 nm) or strong solvent-framework interactions, diffusional exchange between the pore-confined and inter-particle solvent populations remains slow compared to the T2 of the pore-confined solvent, allowing for a direct porosity analysis of the T2 spectrum obtained from Laplace inversions. Increases in framework pore-size (>1 nm) lead to corresponding increases in the rate of solvent exchange, as confirmed by T2 relaxation exchange (REXSY) experiments; increases in the pore size also increases the T2 of the pore-confined solvent. The combination of these two effects results in comparable rates of relaxation and exchange, which precludes the direct analysis of Laplace inversions. Thus, two- and three-site kinetics models were applied to extract porosity from relaxation decays, thereby improving the utility of the porosity screening tool.

The charge-neutral, aluminium-based metal-organic framework containing accessible 2,2′-bipyridine (bpy) sites, MOF-253, is a suitable host material for the immobilization of various copper catalysts. The catalytic performance of CuCl2, Cu(NO3)2, Cu(BF4)2 and Cu(CF3SO3)2 before and after coordination to the bpy ligands in MOF-253 was studied in the Meinwald rearrangement of α-pinene oxide to campholenic aldehyde (CA). The coordination environment of Cu2+ in MOF-253 was further studied via EPR spectroscopy. Although the catalytic activity of the copper salts decreased upon heterogenization through coordination with the bpy linker, the selectivity to campholenic aldehyde markedly increased. Furthermore, the catalytic performance of the MOF loaded with copper salts was shown to vary greatly with the choice of charge compensating anion, allowing for improvement of the heterogeneous catalyst.

Two Ni2+-containing metal-organic frameworks, Ni 2(dobdc) and Ni2(dobpdc), are shown to be active for the oligomerization of propene in the gas phase. The metal-organic frameworks exhibit activity comparable to Ni2+-exchanged aluminosilicates but maintain high selectivity for linear oligomers. Thus, these frameworks should enable the high yielding synthesis of linear propene oligomers for use in detergent and diesel fuel applications. © 2014 American Chemical Society.

A thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal-organic framework Cu3(btc)2 (btc(3-) = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu(2+) or Cr(2+) cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane-methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.

We present a comprehensive investigation of the CO₂ adsorption properties of an isostructural series of metal-organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT^3- = 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO₂ adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO₂ binding sites, including CO₂ positions and orientations, as well as the experimentally determined isosteric heats of CO₂ adsorption.

The crystallographic characterization of framework-guest interactions in metal-organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH₄, N₂, O₂, Ar, and P₄ adsorption in Co₂(dobdc) (dobdc^4- = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal-organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co-CH₄ and Co-Ar interactions observed in Co₂(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal-CH₄ interaction and the first crystallographically characterized metal-Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co₂(dobdc), with differential enthalpies of adsorption as weak as -17(1) kJ mol^-1 (for Ar). Moreover, the structures of Co₂(dobdc)·3.8N₂, Co₂(dobdc)·5.9O₂, and Co₂(dobdc)·2.0Ar reveal the location of secondary (N₂, O₂, and Ar) and tertiary (O₂) binding sites in Co₂(dobdc), while high-pressure CO₂, CO, CH₄, N₂, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.

Purification of the C₈ alkylaromatics o-xylene, m-xylene, p-xylene, and ethylbenzene remains among the most challenging industrial separations, due to the similar shapes, boiling points, and polarities of these molecules. Herein, we report the evaluation of the metal-organic frameworks Co₂(dobdc) (dobdc^4- = 2,5-dioxido-1,4-benzenedicarboxylate) and Co₂( m-dobdc) ( m-dobdc^4- = 4,6-dioxido-1,3-benzenedicarboxylate) for the separation of xylene isomers using single-component adsorption isotherms and multicomponent breakthrough measurements. Remarkably, Co₂(dobdc) distinguishes among all four molecules, with binding affinities that follow the trend o-xylene > ethylbenzene > m-xylene > p-xylene. Multicomponent liquid-phase adsorption measurements further demonstrate that Co₂(dobdc) maintains this selectivity over a wide range of concentrations. Structural characterization by single-crystal X-ray diffraction reveals that both frameworks facilitate the separation through the extent of interaction between each C₈ guest molecule with two adjacent cobalt(II) centers, as well as the ability of each isomer to pack within the framework pores. Moreover, counter to the presumed rigidity of the M₂(dobdc) structure, Co₂(dobdc) exhibits an unexpected structural distortion in the presence of either o-xylene or ethylbenzene that enables the accommodation of additional guest molecules.

Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)₂ (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)₆ with TCNE yields V(TCNE)₂·0.95CH₂Cl₂, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)₂, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m²/g). The porous structure of V(TCNE)₂ is accessible to the small gas molecules H₂, N₂, O₂, CO₂, ethane, and ethylene. While V(TCNE)₂ exhibits thermally activated electron transfer with O₂, all the other studied gases engage in physisorption. The T* value of V(TCNE)₂ is slightly modulated upon adsorption of H₂ (T* = 583 K) or CO₂ (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

Metal-organic frameworks (MOFs) are known to facilitate energy-efficient separations of important industrial chemical feedstocks. Here, we report how a class of green MOFs-namely CD-MOFs-exhibits high shape selectivity toward aromatic hydrocarbons. CD-MOFs, which consist of an extended porous network of γ-cyclodextrins (γ-CDs) and alkali metal cations, can separate a wide range of benzenoid compounds as a result of their relative orientation and packing within the transverse channels formed from linking (γ-CD)6 body-centered cuboids in three dimensions. Adsorption isotherms and liquid-phase chromatographic measurements indicate a retention order of ortho- > meta- > para-xylene. The persistence of this regioselectivity is also observed during the liquid-phase chromatography of the ethyltoluene and cymene regioisomers. In addition, molecular shape-sorting within CD-MOFs facilitates the separation of the industrially relevant BTEX (benzene, toluene, ethylbenzene, and xylene isomers) mixture. The high resolution and large separation factors exhibited by CD-MOFs for benzene and these alkylaromatics provide an efficient, reliable, and green alternative to current isolation protocols. Furthermore, the isolation of the regioisomers of (i) ethyltoluene and (ii) cymene, together with the purification of (iii) cumene from its major impurities (benzene, n-propylbenzene, and diisopropylbenzene) highlight the specificity of the shape selectivity exhibited by CD-MOFs. Grand canonical Monte Carlo simulations and single component static vapor adsorption isotherms and kinetics reveal the origin of the shape selectivity and provide insight into the capability of CD-MOFs to serve as versatile separation platforms derived from renewable sources.

The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped CO2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO2 from various gas mixtures, and yield insights into the conservation of Mg(2+) within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.