The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)

Hybrid porous solids: past, present, future

New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal–organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework–H2 interactions, and strategies for improving storage capacity (188 references).

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Hydrogen storage in metal–organic frameworks

Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites.

2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636

Engineering Metal Organic Frameworks for Heterogeneous Catalysis

Carbon dioxide inclusion phases of a transformable 1D coordination polymer host [Rh2(O2CPh)4(pyz)]n.

Molecular-level design of efficient microporous materials containing metal carboxylates: inclusion complex formation with organic polymer, gas-occlusion properties, and catalytic activities for hydrogenation of olefins

We have detected the first example of open porous metal–organic frameworks (MOFs) that functions as an activity site for the reduction of water into hydrogen molecules in the presence of Ru(bpy)32+, MV2+, and EDTA–2Na under visible light irradiation. This activity is highly efficient: the turnover number based on MOFs and the apparent quantum yield are 8.16 and 4.82%, respectively. Furthermore, this material enables the adsorption of various gases into its pores; its hydrogen uptake capacity is 1.2 wt% at 77.4 K.

Photocatalytic hydrogen production from water using porous material [Ru2(p-BDC)2]n

Copper(II) terephthalate absorbs a large amount of gases such as N2, Ar, O2, and Xe. The maximum amounts of absorption of gases were 1.8, 1.9, 2.2, and 0.9 mole per one mole of the copper(II) salt for N2, Ar, O2, and Xe, respectively, indicating that the gases were not adsorbed on the surface but occluded within the solid. The porous structure of copper(II) terephthalate, in which the gas is occluded, is deduced from the temperature dependence of magnetic susceptibilities and the linear structure of terephthalate.

Synthesis of New Adsorbent Copper(II) Terephthalate

A three-dimensional coordination polymer was synthesized from porous copper(II) terephathlate and triethylenediamine (TED) as a pillar ligand, which has a higher porosity and higher capacity for methane adsorption than zeolites and porous coordination polymers reported previously.

Wasuke Mori

Papers

Carbon dioxide inclusion phases of a transformable 1D coordination polymer host [Rh2(O2CPh)4(pyz)]n.

Molecular-level design of efficient microporous materials containing metal carboxylates: inclusion complex formation with organic polymer, gas-occlusion properties, and catalytic activities for hydrogenation of olefins

Photocatalytic hydrogen production from water using porous material [Ru2(p-BDC)2]n

Synthesis of New Adsorbent Copper(II) Terephthalate

Design and Gas Adsorption Property of a Three-Dimensional Coordination Polymer with a Stable and Highly Porous Framwork