High Volumetric Hydrogen Adsorption in a Porous Anthracene-Decorated Metal-Organic Framework.

We report an unprecedented ligand-based binding domain for D within a porous metal-organic framework (MOF) material as confirmed by neutron powder diffraction studies of D-loaded MFM-132a. A tight pocket of 6 Å diameter is formed by the close packing of three anthracene panels, and it is here rather than the open metal sites where D binds preferentially. As a result, MFM-132a shows exceptional volumetric hydrogen adsorption (52 g L at 60 bar and 77 K) and the highest density of adsorbed H within its pores among all the porous materials reported to date under the same conditions.

Porous Metal-Organic Polyhedral Frameworks with Optimal Molecular Dynamics and Pore Geometry for Methane Storage.

Natural gas (methane, CH) is widely considered as a promising energy carrier for mobile applications. Maximizing the storage capacity is the primary goal for the design of future storage media. Here we report the CH storage properties in a family of isostructural (3,24)-connected porous materials, MFM-112a, MFM-115a, and MFM-132a, with different linker backbone functionalization.

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.

Non-Interpenetrated Metal-Organic Frameworks Based on Copper(II) Paddlewheel and Oligoparaxylene-Isophthalate Linkers: Synthesis, Structure, and Gas Adsorption.

Two metal-organic framework materials, MFM-130 and MFM-131 (MFM = Manchester Framework Material), have been synthesized using two oligoparaxylene (OPX) tetracarboxylate linkers containing four and five aromatic rings, respectively. Both fof-type non-interpenetrated networks contain Kagomé lattice layers comprising [Cu2(COO)4] paddlewheel units and isophthalates, which are pillared by the OPX linkers. Desolvated MFM-130, MFM-130a, shows permanent porosity (BET surface area of 2173 m(2)/g, pore volume of 1.

Interpenetration, porosity, and high-pressure gas adsorption in Zn4O(2,6-naphthalene dicarboxylate)3.

Microporous coordination polymers (MCPs) have emerged as strong contenders for adsorption-based fuel storage and delivery in large part because of their high specific surface areas. The strategy of increasing surface area by increasing organic linker length has shown only sporadic success; as demonstrated by many members of the iconic Zn4O-based IRMOF series, for example, accessible porosity is often limited by interpenetration or pore collapse upon guest removal. In this work, we focus on Zn4O(ndc)3 (IRMOF-8, ndc = 2,6-naphthalene dicarboxylate), which exhibits typical surface areas of only 1000-2000 m(2)/g even though a surface area of more than 4000 m(2)/g is expected from geometric analysis of the originally reported crystal structure.

Mesoporous metal and metal alloy particles synthesized by aerosol-assisted confined growth of nanocrystals.

From droplets to "spheres": A platform technology enables the rapid and continuous synthesis of mesoporous metal and metal alloy particles (see picture). The confined growth of nanocrystals in aerosol droplets leads to the formation of these particles with defined composition.

Saturation properties of a supercritical gas sorbed in nanoporous materials.

The description of experimental gas adsorption data in terms of an accurate model is key to understand the adsorption mechanism and its limits. As a basic feature such a model should predict correctly the conditions under which saturation occurs. However, in the absence of bulk condensation properties for a supercritical adsorbate this matter remains open to discussions.

Modifying cage structures in metal-organic polyhedral frameworks for H2 storage.

Three isostructural metal-organic polyhedral cage based frameworks (denoted NOTT-113, NOTT-114 and NOTT-115) with (3,24)-connected topology have been synthesised by combining hexacarboxylate isophthalate linkers with {Cu(2)(RCOO)(4)} paddlewheels. All three frameworks have the same cuboctahedral cage structure constructed from 24 isophthalates from the ligands and 12 {Cu(2)(RCOO)(4)} paddlewheel moieties. The frameworks differ only in the functionality of the central core of the hexacarboxylate ligands with trimethylphenyl, phenylamine and triphenylamine moieties in NOTT-113, NOTT-114 and NOTT-115, respectively.

Gas and liquid phase adsorption in isostructural Cu3[biaryltricarboxylate]2 microporous coordination polymers.

N-Heteroarene substitution into biphenyl-based linkers enhances the uptake of electron-rich organosulfur molecules in a series of isostructural microporous coordination polymers.

Linker-directed vertex desymmetrization for the production of coordination polymers with high porosity.

Five non-interpenetrated microporous coordination polymers (MCPs) are derived by vertex desymmetrization using linkers with symmetry inequivalent coordinating groups, and these MCPs include properties such as rare metal clusters, new network topologies, and supramolecular isomerism. Gas sorption in polymorphic frameworks, UMCM-152 and UMCM-153 (based upon a copper-coordinated tetracarboxylated triphenylbenzene linker), reveals nearly identical properties with BET surface areas in the range of 3300-3500 m(2)/g and excess hydrogen uptake of 5.7 and 5.

Metal-organic polyhedral frameworks: high h(2) adsorption capacities and neutron powder diffraction studies.

Neutron powder diffraction experiments on D(2)-loaded NOTT-112 reveal that the axial sites of exposed Cu(II) ions in the smallest cuboctahedral cages are the first, strongest binding sites for D(2) leading to an overall discrimination between the two types of exposed Cu(II) sites at the paddlewheel nodes. Thus, the Cu(II) centers within the cuboctahedral cage are the first sites of D(2) binding with a Cu-D(2) distance of 2.23(1) A.

Synthesis and hydrogen storage properties of Be(12)(OH)(12)(1,3,5-benzenetribenzoate)(4).

The first crystalline beryllium-based metal-organic framework has been synthesized and found to exhibit an exceptional surface area useful for hydrogen storage. Reaction of 1,3,5-benzenetribenzoic acid (H(3)BTB) and beryllium nitrate in a mixture of DMSO, DMF, and water at 130 degrees C for 10 days affords the solvated form of Be(12)(OH)(12)(1,3,5-benzenetribenzoate)(4) (1). Its highly porous framework structure consists of unprecedented saddle-shaped [Be(12)(OH)(12)](12+) rings connected through tritopic BTB(3-) ligands to generate a 3,12 net.

On the nature of the adsorbed hydrogen phase in microporous metal-organic frameworks at supercritical temperatures.

Hydrogen adsorption measurements on different metal-organic frameworks (MOFs) over the 0-60 bar range at 50 and 77 K are presented. The results are discussed with respect to the materials' surface area and thermodynamic properties of the adsorbed phase. A nearly linear correlation between the maximum hydrogen excess amount adsorbed and the Brunauer-Emmett-Teller (BET) surface area was evidenced at both temperatures.

Thermodynamics of hydrogen adsorption in MOF-177 at low temperatures: measurements and modelling.

Hydrogen adsorption measurements and modelling for the Zn-based microporous metal-organic framework (MOF) Zn4O(1,3,5-benzenetribenzoate)2, MOF-177, were performed over the 50-77 K and 0-40 bar ranges. The maximum excess adsorption measured under these conditions varies over about 105-70 mg g(-1). An analysis of the isotherms near saturation shows that hydrogen is ultimately adsorbed in an incompressible phase whose density is comparable to that of the bulk liquid.

Enhancement of H2 adsorption in coordination framework materials by use of ligand curvature.

Solvothermal reaction of the ligands H(4)L(110) ((2,7-phenanthrenediyl)diisophthalic acid) and H(4)L(111) ([2,7-(9,10-dihydrophenanthrenediyl)]diisophthalic acid) with Cu(NO(3))(2) x 2.5 H(2)O in a slightly acidified mixture of DMF/1,4-dioxane/H(2)O afforded the solvated framework compounds [Cu(2)(L(110))(H(2)O)(2)](DMF)(7.5)(H(2)O)(5) (NOTT-110) and [Cu(2)(L(111))(H(2)O)(2)](DMF)(7.

Exceptionally high H2 storage by a metal-organic polyhedral framework.

The desolvated polyhedral framework material NOTT-112 shows an excess H(2) uptake of 7.07 wt% between 35 and 40 bar at 77 K, and a total H(2) uptake of 10 wt% at 77 bar and 77 K.

Structure and charge control in metal-organic frameworks based on the tetrahedral ligand tetrakis(4-tetrazolylphenyl)methane.

Use of the tetrahedral ligand tetrakis(4-tetrazolylphenyl)methane enabled isolation of two three-dimensional metal-organic frameworks featuring 4,6- and 4,8-connected nets related to the structures of garnet and fluorite with the formulae Mn(6)(ttpm)(3)5 DMF3 H(2)O (1) and Cu[(Cu(4)Cl)(ttpm)(2)](2)CuCl(2)5 DMF11 H(2)O (2) (H(4)ttpm=tetrakis(4-tetrazolylphenyl)methane). The fluorite-type solid 2 displays an unprecedented post-synthetic transformation in which the negative charge of the framework is reduced by extraction of copper(II) chloride. Desolvation of this compound generates Cu(4)(ttpm)(2)0.

Reversible structural transition in MIL-53 with large temperature hysteresis.

The metal-organic framework, MIL-53, can have a structural transition from an open-pored to a closed-pored structure by adsorbing different guest molecules. The aid of guest molecules is believed to be necessary to initiate this "breathing" effect. Using both neutron powder diffraction and inelastic neutron scattering techniques, we find that MIL-53 exhibits a reversible structural transition between an open-pored and a closed-pored structure as a function of temperature without the presence of any guest molecules.

Expanded sodalite-type metal-organic frameworks: increased stability and H(2) adsorption through ligand-directed catenation.

The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)phenyl-s-triazine (H3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2.2H2O affords the noncatenated compound Cu3[(Cu4Cl)3(TPB-3tz)8]2.

Hydrogen storage in a microporous metal-organic framework with exposed Mn2+ coordination sites.

Use of the tritopic bridging ligand 1,3,5-benzenetristetrazolate (BTT3-) enables formation of [Mn(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]2.42DMF.11H2O.

Saturation of hydrogen sorption in Zn benzenedicarboxylate and Zn naphthalenedicarboxylate.

We report excess hydrogen saturation values from high-pressure isotherms of metal organic framework structures taken at 77 K. Zn benzendicarboxylate (IRMOF-1) and Zn naphthalendicarboxylate (IRMOF-8) linker structures show identical saturation values of 137 hydrogen molecules on a per unit cell basis, despite the higher sorption potential of IRMOF-8 of 6.1 kJ/mol over that of IRMOF-1 of 4.