A Coordination Network Featuring Two Distinct Copper(II) Coordination Environments for Highly Selective Acetylene Adsorption.

Single crystals of 2D coordination network {Cu2 L2 ⋅ (DMF)3 (H2 O)3 }n (1-DMF) were prepared by reaction of commercial reagents 3-formyl-4-hydroxybenzoic acid (H2 L) and Cu(NO3 )2 in dimethylformamide (DMF). The single-crystal structure shows two distinct Cu(II) coordination environments arising from the separate coordination of Cu(II) cations to the carboxylate and salicylaldehydato moieties on the linker, with 1D channels running through the structure. Flexibility is exhibited on solvent exchange with ethanol and tetrahydrofuran, while porosity and the unique overall connectivity of the structure are retained. The activated material exhibits type I gas sorption behaviour and a BET surface area of 950 m2 g-1 (N2 , 77 K). Notably, the framework adsorbs negligible quantities of CH4 compared with CO2 and the C2 Hn hydrocarbons. It exhibits exceptional selectivity for C2 H2 /CH4 and C2 H2 /C2 Hn , which has applicability in separation technologies for the isolation of C2 H2 .

Exceptional Adsorption and Binding of Sulfur Dioxide in a Robust Zirconium-Based Metal-Organic Framework.

We report a record-high SO2 adsorption capacity of 12.3 mmol g-1 in a robust porous material, MFM-601, at 298 K and 1.0 bar. SO2 adsorption in MFM-601 is fully reversible and highly selective over CO2 and N2. The binding domains for adsorbed SO2 and CO2 molecules in MFM-601 have been determined by in situ synchrotron X-ray diffraction experiments, giving insights at the molecular level to the basis of the observed high selectivity.

Characterisation of redox states of metal-organic frameworks by growth on modified thin-film electrodes.

The application of metal-organic framework (MOF) materials in electrochemical and electrochromic devices remains rare. One of the main reasons for this is the inability to readily access their detailed electrochemistry. The inherent insolubility of these materials does not allow interrogation by traditional solution-based electrochemical or spectroscopic methods. In this study, we report a straightforward alternative approach to the spectroelectrochemical study of MOFs. We have used two systems as exemplars in this study, MFM-186 and MFM-180. The method involves chemical modification of a working electrode to attach MOF materials without using corrosive reagents such as inorganic acids or bases which otherwise could limit their application in device development. MFM-186 demonstrates the formation of a stable radical species [MFM-186]˙+ on electrochemical oxidation, and this has been characterised by electrochemical, spectroelectrochemical and EPR spectroscopic techniques coupled to DFT analysis.

Binding CO2 by a Cr8 Metallacrown.

The {Cr8 } metallacrown [CrF(O2 Ct Bu)2 ]8 , containing a F-lined internal cavity, shows high selectivity for CO2 over N2 . DFT calculations and absorption studies support the multiple binding of F-groups to the C-center of CO2 (C⋅⋅⋅F 3.190(9)-3.389(9) Å), as confirmed by single-crystal X-ray diffraction.

Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks.

Modulation and precise control of porosity of metal-organic frameworks (MOFs) is of critical importance to their materials function. Here we report modulation of porosity for a series of isoreticular octacarboxylate MOFs, denoted MFM-180 to MFM-185, via a strategy of selective elongation of metal-organic cages. Owing to the high ligand connectivity, these MOFs do not show interpenetration, and are robust structures that have permanent porosity. Interestingly, activated MFM-185a shows a high Brunauer-Emmett-Teller (BET) surface area of 4,734 m2 g-1 for an octacarboxylate MOF. These MOFs show remarkable CH4 and CO2 adsorption properties, notably with simultaneously high gravimetric and volumetric deliverable CH4 capacities of 0.24 g g-1 and 163 vol/vol (298 K, 5-65 bar) recorded for MFM-185a due to selective elongation of tubular cages. The dynamics of molecular rotors in deuterated MFM-180a-d16 and MFM-181a-d16 were investigated by variable-temperature 2H solid-state NMR spectroscopy to reveal the reorientation mechanisms within these materials. Analysis of the flipping modes of the mobile phenyl groups, their rotational rates, and transition temperatures paves the way to controlling and understanding the role of molecular rotors through design of organic linkers within porous MOF materials.

Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework.

Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232 cm3 g-1 at 295 K and 1 bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a.

Structural and dynamic studies of substrate binding in porous metal-organic frameworks.

Porous metal-organic frameworks (MOFs) are the subject of considerable research interest because of their high porosity and capability of specific binding to small molecules, thus underpinning a wide range of materials functions such as gas adsorption, separation, drug delivery, catalysis, and sensing. MOFs, constructed by the designed assembly of metal ions and functional organic linkers, are an emerging class of porous materials with extended porous structures containing periodic binding sites. MOFs thus provide a new platform for the study of the chemistry and reactivity of small molecules in confined pores using advanced diffraction and spectroscopic techniques. In this review, we focus on recent progress in experimental investigations on the crystallographic, dynamic and kinetic aspects of substrate binding within porous MOFs. In particular, we focus on studies on host-guest interactions involving open metal sites or pendant functional groups in the pore as the primary binding sites for guest molecules.

Functionalization in flexible porous solids: effects on the pore opening and the host-guest interactions.

The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF(3), -CH(3), -NH(2), -OH, -CO(2)H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and (57)Fe Mössbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF(3))(2)) exhibits a nitrogen accessible porosity (S(BET) approximately 100 m(2) g(-1)). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.