Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long

Carbon Dioxide Capture in Metal–Organic Frameworks

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Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

Polyoxometalates (POMs) are discrete anionic metaloxygen clusters which can be regarded as soluble oxide fragments. They exhibit a great diversity of sizes, nuclearities, and shapes. They are built from the connection of {MOx} polyhedra, M being a d-block element in high oxidation state, usually VIV,V, MoVI, or WVI.1 While these species have been known for almost two centuries, they still attract much interest partly based on their large domains of applications. They play a great role in various areas ranging from catalysis,2 medicine,3 electrochemistry,4 photochromism,5 to magnetism.6 This palette of applications is intrinsically due to the combination of their added value properties (redox properties, large sizes, high negative charges, nucleophilicity...). Parallel to this domain, the organic-inorganic hybrids area has followed a similar expansion during the last 10 years. The concept of organic-inorganic hybrid materials * To whom correspondence should be addressed. E-mail: dolbecq@ chimie.uvsq.fr. Chem. Rev. 2010, 110, 6009–6048 6009

Hybrid Organic−Inorganic Polyoxometalate Compounds: From Structural Diversity to Applications

Solvothermal reactions with different solvents produced two iron trimesates [Fe2(H2O)2(BTC)4/3]Cl·4.5(DMF) (1) and [Fe4Cl(BTC)8/3]Cl2·H2O·2.5(DEF) (2) (BTC = 1,3,5-benzenetricarboxylate, DMF = N,N‘-dimethylformamide, DEF = N,N‘-diethylformamide). The framework of 1 is a (3,4)-connected net constructed from mixed-valence paddlewheel Fe2(II, III) units and BTC linkers, while the framework of 2 is a (3,8)-connected net built from mixed-valence square-planar Fe4(III, III, III, II) units and BTC linkers. The large volume inside the framework of 1 (or 2) is occupied by disordered Cl- anions and guest DMF (or DEF) molecules. The mixed-valence character of the frameworks of 1 and 2 was confirmed by Mossbauer spectroscopy studies. The active electronic property of iron cations may be the origin of the variability of the iron−organic frameworks, which are readily affected by some synthetic factors, such as solvents. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the Fe atoms in...

Mixed-valence iron(II, III) trimesates with open frameworks modulated by solvents.

Two novel organic−inorganic hybrid compounds based on Anderson-type polyoxoanions, [Cu2(bpy)2(μ-ox)][Al(OH)7Mo6O17] (1) and [Cu2(bpy)2(μ-ox)][Cr(OH)7Mo6O17] (2), have been synthesized and characterized by elemental analyses, IR, and X-ray powder diffraction. The crystal structures of 1 and 2 have been established by single-crystal X-ray diffraction, which reveals the presence of 1D chains constructed of alternating Anderson-type polyoxoanions and oxalato-bridged dinuclear copper complexes for both compounds and extensive hydrogen bonding that plays an important role in the formation of the 3D supramolecular network structures of 1 and 2. To elucidate the electronic properties and magnetic properties of the metal ions (Cu2+ or Cu2+ and Cr3+), EPR studies and magnetic susceptibility studies have been performed, respectively. The results are consistent with the structural feature of these compounds.

Organic-inorganic hybrids constructed of anderson-type polyoxoanions and oxalato-bridged dinuclear copper complexes.

A series of organic–inorganic hybrid compounds, K2H7[{Ln(PW11O39)2}{Cu2(bpy)2(μ-ox)}]·xH2O (Ln = La, x≈ 18 (1); Ln = Pr, x≈ 18 (2); Ln = Eu, x≈ 16 (3); Ln = Gd, x≈ 22 (4); Ln = Yb, x≈ 19 (5); bpy = 2,2′-bipyridine and ox = oxalate), have been isolated by the conventional solution method. Single-crystal X-ray diffraction studies reveal that compounds 1–5 are isomorphic and consist of one-dimensional chains, which are constructed by alternating bis(undecatungstophosphate) lanthanates [Ln(PW11O39)2]11− and dinuclear copper(II)–oxalate complexes [Cu2(bpy)2(μ-ox)]2+. π–π interactions of the bpy ligands from adjacent chains lead to their three-dimensional structures. An analogue of potassium K2H9[{K(PW11O39)2}{Cu2(bpy)2(μ-ox)}]·∼20.5H2O (6) has also been obtained. The syntheses and structures of these compounds are reported here. Magnetic properties of 1, 2 and 3 are discussed as well. Attempts to crystallize similar compounds containing Co(II) and Ni(II) were unsuccessful.

Organic-inorganic hybrids assembled by bis(undecatungstophosphate) lanthanates and dinuclear copper(II)-oxalate complexes.

A unique porous 3D metal–organic framework has been synthesized based on the insertion of heterogeneous pillars between 2D layers, the permanent porosity of which is confirmed by N2 adsorption isotherm measurement.

Design and construction of a microporous metal–organic framework based on the pillared-layer motif

The solvothermal reactions of nickel nitrate hexahydrate, aromatic carboxylic acids, and either 4,4′-bipyridine (bipy) or pyrazine (pyz) produced three open-framework compounds, namely, Ni(HBTC)(pyz)·3DMF 2 (BTC = 1,3,5-benzentricarboxylate, DMF = N,N′-dimethylformamide), Ni2(BTEC)(bipy)3·3DMF 3 (BTEC = 1,2,4,5-benzenetetracarboxylate), together with previously reported Ni(HBTC)(bipy)·3DMF 1. Compound 2 is the product when pyz pillars replace bipy pillars in the reaction of 1, and it is a 3D porous network where honeycomb grid layers constructed by Ni-BTC groups are interlinked by pyz pillars. When the BTEC ligand takes the place of BTC ligand in the system, compound 3 is obtained and it is a 3D connectivity with 1D channels where Ni-BTEC chains are interlinked by bipy ligands. The three compounds feature permanent porosity, which was confirmed by N2 adsorption isotherm measurement, and the architectural features of 1–3 can be ascribed to pillared-layer motifs. Furthermore, hydrogen adsorption measured at 77 K for 1 shows an excess uptake of 3.03 wt% at 20 bar. Details of the synthesis conditions, crystal structures and property measurements of each new compound are described.

Jianfang Cao

Papers

Mixed-valence iron(II, III) trimesates with open frameworks modulated by solvents.

Organic-inorganic hybrids constructed of anderson-type polyoxoanions and oxalato-bridged dinuclear copper complexes.

Organic-inorganic hybrids assembled by bis(undecatungstophosphate) lanthanates and dinuclear copper(II)-oxalate complexes.

Design and construction of a microporous metal–organic framework based on the pillared-layer motif

Rational design microporous pillared-layer frameworks: syntheses, structures and gas sorption properties