A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n
19 Feb 1999-Science (American Association for the Advancement of Science)-Vol. 283, Iss: 5405, pp 1148-1150
TL;DR: In this paper, a highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield.
Abstract: Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.
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TL;DR: Metal-organic frameworks are porous materials that have potential for applications such as gas storage and separation, as well as catalysis, and methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices.
Abstract: 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.
10,934 citations
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.
Abstract: 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.
8,013 citations
TL;DR: A critical review of the emerging field of MOF-based catalysis is presented and examples of catalysis by homogeneous catalysts incorporated as framework struts or cavity modifiers are presented.
Abstract: A critical review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated molecular species, (e) catalysis by metal-free organic struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters (66 references).
7,010 citations
TL;DR: The potential to computationally predict, with good accuracy, affinities of guests for host frameworks points to the prospect of routinely predesigning frameworks to deliver desired properties.
Abstract: 1. INTRODUCTION Among the classes of highly porous materials, metalÀorganic frameworks (MOFs) are unparalleled in their degree of tunability and structural diversity as well as their range of chemical and physical properties. MOFs are extended crystalline structures wherein metal cations or clusters of cations (\" nodes \") are connected by multitopic organic \" strut \" or \" linker \" ions or molecules. The variety of metal ions, organic linkers, and structural motifs affords an essentially infinite number of possible combinations. 1 Furthermore, the possibility for postsynthetic modification adds an additional dimension to the synthetic variability. 2 Coupled with the growing library of experimentally determined structures, the potential to computationally predict, with good accuracy, affinities of guests for host frameworks points to the prospect of routinely predesigning frameworks to deliver desired properties. 3,4 MOFs are often compared to zeolites for their large internal surface areas, extensive porosity, and high degree of crystallinity. Correspondingly, MOFs and zeolites have been utilized for many of the same applications
5,925 citations
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TL;DR: In this paper, a metal-organic framework was designed to bind aromatic guest molecules selectively, and the inclusions can be selectively readsorbed, even after the removal of included guest molecules, and they showed that the crystal lattice was thermally stable up to 350 °C.
Abstract: MICROPOROUS inorganic materials such as zeolites find widespread application in heterogeneous catalysis, adsorption and ion-exchange processes. The rigidity and stability of such frameworks allow for shape- and size-selective inclusion of organic molecules and ions1–4. Analogous microporous structures based on organic building blocks have the potential for more precise rational design, through control of the shape, size and functionalization of the pores5–8. Here we report the synthesis of a metal–organic framework designed to bind aromatic guest molecules selectively. The basic building block is a symmetric organic molecule, which binds metal ions9,10 to form layers of the metal–organic compound alternating with layers whose composition is determined by the functionalization of the starting molecules. The layers create channels in which guest aromatic molecules may be selectively bound. We show that the crystal lattice thus formed is thermally stable up to 350 °C, even after removal of included guest molecules, and that the inclusions can be selectively readsorbed.
2,094 citations
TL;DR: In this paper, a novel class of crystalline, microporous, aluminophosphate phases has been discovered that represents the first family of framework oxide molecular sieves synthesized without silica.
Abstract: A novel class of crystalline, microporous, aluminophosphate phases has been discovered that represents the first family of framework oxide molecular sieves synthesized without silica. The new family of aluminophosphate materials (AlPO/sub 4/-n)/sup 3/ currently includes about 20, three-dimensional framework structures, of which at least 14 are microporous and 6 are two-dimensional layer-type materials. The aluminophosphate materials have interesting properties for potential use in adsorptive and catalytic applications, due to both their unique surface selectivity characteristics and novel structures.
1,663 citations
TL;DR: In this paper, the authors present the synthesis, structural characterization, and gas sorption isotherm measurements for the Zn(BDC) microporous framework of crystalline Zn (BDC), 1,4benzenedicarboxylate and DMF N,N′-dimethylformamide.
Abstract: Construction of microporous metal-organic frameworks by copolymerization of organic molecules with metal ions has received widespread attention in recent years, with significant strides made toward the development of their synthetic and structural design chemistry.1 Cognizant of the fact that access to the pores and understanding the inclusion chemistry of these materials are essential to their ultimate utility, we prepared rigid frameworks that maintain their structural integrity and porosity during anion-exchange and guest sorption from solution and in the absence of guests.2-4 Although gas sorption isotherm measurements are often used to confirm and study microporosity in crystalline zeolites and related molecular sieves,5 such studies have not been established in the chemistry of open metal-organic frameworks6 thus leaving unanswered vital questions regarding the existence of permanent porosity in this class of materials. Herein, we present the synthesis, structural characterization, and gas sorption isotherm measurements for the Zn(BDC) microporous framework of crystalline Zn(BDC)‚(DMF)(H2O) (BDC ) 1,4benzenedicarboxylate and DMF ) N,N′-dimethylformamide). Slow vapor diffusion at room temperature of triethylamine (0.05 mL) and toluene (5 mL) into a DMF solution (2 mL) containing a mixture of Zn(NO3)2‚6H2O (0.073 g, 0.246 mmol) and the acid form of BDC (0.040 g, 0.241 mmol) diluted with toluene (8 mL) yields colorless prism-shaped crystals that were formulated as Zn(BDC)‚(DMF)(H2O). X-ray single-crystal analysis8 on a sample obtained from the reaction product revealed an extended open-framework structure composed of the building unit shown in Figure 1. A total of four carboxylate units of different, but symmetrically equivalent, BDC building blocks are bonded to two zinc atoms in a di-monodentate fashion. Each zinc is also linked to a terminal water ligand to form an overall arrangement that is reminiscent of the carboxylate bridged M-M bonded molecular complexes. Although the Zn-Zn distance (Zn1-Zn1A ) 2.940 (3) A) is indicative of some M-M interaction, it does not represent an actual bond.9 The structure extends into the (011) crystallographic plane by having identical Zn-Zn units linked to remaining carboxylate functionalities of BDC to yield 2-D microporous layers. These layers are held together along the a axis by hydrogen-bonding interactions between water ligands of one layer and carboxylate oxygens of an adjacent layer as illustrated in a. Stacking of the layers in the
1,013 citations