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Journal ArticleDOI

Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks.

TLDR
Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.
Abstract
Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.

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Reticular synthesis and the design of new materials

TL;DR: This work has shown that 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.
Journal ArticleDOI

Selective gas adsorption and separation in metal–organic frameworks

TL;DR: This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorbents in rigid and flexible MOFs, and primary relationships between adsorptive properties and framework features are analyzed.
Journal ArticleDOI

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage

TL;DR: Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups and can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl.
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Hydrogen Storage in Microporous Metal-Organic Frameworks

TL;DR: Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II), which are associated with hydrogen binding to zinc and the BDC linker, respectively.
References
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Journal ArticleDOI

Design and synthesis of an exceptionally stable and highly porous metal-organic framework

TL;DR: In this article, an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxyates.
Journal ArticleDOI

Interpenetrating Nets: Ordered, Periodic Entanglement.

TL;DR: A detailed and systematic examination of many interpenetrating nets of this kind is made, and implications for crystal engineering are discussed.
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Organic-Inorganic Hybrid Materials: From "Simple" Coordination Polymers to Organodiamine-Templated Molybdenum Oxides.

TL;DR: A blueprint for the design of oxide materials is provided by nature and members of the ever-expanding class of polymeric coordination complex cations, novel molybdenum oxide substructures, such as the one shown, may be prepared.
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Open-Framework Inorganic Materials.

TL;DR: Aluminosilicate zeolites such as UTD-1 belong to a family of nanoporous inorganic materials that find utility in catalysis, separation, and ion exchange.
Journal ArticleDOI

Synthetic Strategies, Structure Patterns, and Emerging Properties in the Chemistry of Modular Porous Solids†

Abstract: The designed construction of extended porous frameworks from soluble molecular building blocks represents one of the most challenging issues facing synthetic chemistry today. Recently, intense research activities directed toward the development of this field have included the assembly of inorganic metal clusters,1 coordination complexes,2 and organic molecules3 of great diversity into extended motifs that are held together either by strong metal-ligand bonding or by weaker bonding forces such as hydrogen-bonding and π-π interactions. Materials that have been produced in this way are referred to as modular since they are assembled from discrete molecules which can be modified to have well-defined function.4 The fact that the integrity of the building blocks is preserved during the synthesis and ultimately translated into the resulting assembled network offers numerous opportunities for designing frameworks with desirable topologies and architectures, thus paving the way for establishing connections between molecular and solid properties. At least three challenges have emerged in this area that must be reckoned with in order for the ideas of rational and designed synthesis of porous materials to become a reality with routine utility. First, it is difficult to control the orientation and stereochemistry of the building blocks in the solid state in order to achieve a given target molecular topology and architecture. Second, in most cases, the products of such assembly reactions are obtained as poorly crystalline or amorphous solids, thus prohibiting their full characterization by single-crystal X-ray diffraction techniques. Third, access to the pores within open structuressan aspect that is so critical to their utility as porous materialssis often prevented by either selfinterpenetration as observed for very open frameworks or strong host-guest interactions that lead to the destruction of the host framework when removal or exchange of guests is attempted. To define and investigate the parameters contributing to the assembly of materials from molecular building blocks, we have established a program aimed at constructing modular porous networks by linking inorganic metal sulfide clusters and organic molecules with transition metal ions. Our work has focused primarily on studying the issues outlined above, and this Account presents our progress toward finding viable and general solutions to these challenges. This is illustrated by some representative examples chosen from the chemistry developed in our research effort for the three building blocks shown in a-c. Their functionality, shape, size, and
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