Magnetic metal-organic frameworks.
TL;DR: The diversity of magnetic exchange interactions between nearest-neighbour moment carriers is examined, covering from dimers to oligomers and their implications in infinite chains, layers and networks, having a variety of topologies.
Abstract: The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of magnetic metal–organic frameworks, in particular those containing cobalt(II). We examine the diversity of magnetic exchange interactions between nearest-neighbour moment carriers, covering from dimers to oligomers and discuss their implications in infinite chains, layers and networks, having a variety of topologies. We progress to the different forms of short-range magnetic ordering, giving rise to single-molecule-magnets and single-chain-magnets, to long-range ordering of two- and three-dimensional networks (323 references).
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TL;DR: In this article, the authors review the research progress in metal-organic frameworks (MOFs) for CO 2 adsorption, storage, and separations that are directly related to CO 2 capture.
1,779 citations
TL;DR: This review provides an overview of the significant advances in the development of diverse MOF composites reported till now with special emphases on the synergistic effects and applications of the composites.
Abstract: Metal–organic frameworks (MOFs), also known as porous coordination polymers (PCPs), synthesized by assembling metal ions with organic ligands have recently emerged as a new class of crystalline porous materials. The amenability to design as well as fine-tunable and uniform pore structures makes them promising materials for a variety of applications. Controllable integration of MOFs and functional materials is leading to the creation of new multifunctional composites/hybrids, which exhibit new properties that are superior to those of the individual components through the collective behavior of the functional units. This is a rapidly developing interdisciplinary research area. This review provides an overview of the significant advances in the development of diverse MOF composites reported till now with special emphases on the synergistic effects and applications of the composites. The most widely used and successful strategies for composite synthesis are also presented.
1,738 citations
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TL;DR: The aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers, and the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli.
Abstract: The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
9,661 citations
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.
Abstract: A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. 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 –Br, –NH2, –OC3H7, –OC5H11, –C2H4, and –C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.
6,922 citations
TL;DR: In this article, an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxyates.
Abstract: Open metal–organic frameworks are widely regarded as promising materials for applications1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field14,15. Here we report the synthesis of a metal–organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300?°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.
6,778 citations
6,030 citations
TL;DR: In this paper, the Anderson theory of superexchange was extended to include spin-orbit coupling and the antisymmetric spin coupling suggested by Dzialoshinski from purely symmetry grounds and the symmetric pseudodipolar interaction were derived.
Abstract: A theory of anisotropic superexchange interaction is developed by extending the Anderson theory of superexchange to include spin-orbit coupling. The antisymmetric spin coupling suggested by Dzialoshinski from purely symmetry grounds and the symmetric pseudodipolar interaction are derived. Their orders of magnitudes are estimated to be ($\frac{\ensuremath{\Delta}g}{g}$) and ${(\frac{\ensuremath{\Delta}g}{g})}^{2}$ times the isotropic superexchange energy, respectively. Higher order spin couplings are also discussed. As an example of antisymmetric spin coupling the case of Cu${\mathrm{Cl}}_{2}$\ifmmode\cdot\else\textperiodcentered\fi{}2${\mathrm{H}}_{2}$O is illustrated. In Cu${\mathrm{Cl}}_{2}$\ifmmode\cdot\else\textperiodcentered\fi{}2${\mathrm{H}}_{2}$O, a spin arrangement which is different from one accepted so far is proposed. This antisymmetric interaction is shown to be responsible for weak ferromagnetism in $\ensuremath{\alpha}$-${\mathrm{Fe}}_{2}$${\mathrm{O}}_{3}$, MnC${\mathrm{O}}_{3}$, and Cr${\mathrm{F}}_{3}$. The paramagnetic susceptibility perpendicular to the trigonal axis is expected to increase very sharply near the N\'eel temperature as the temperature is lowered, as was actually observed in Cr${\mathrm{F}}_{3}$.
5,322 citations