Omar M. Yaghi

Reticular synthesis and the design of new materials

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.

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

Open metal–organic frameworks are widely regarded as promising materials for applications 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 field. 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.

The Chemistry and Applications of Metal-Organic Frameworks

Background Metal-organic frameworks (MOFs) are made by linking inorganic and organic units by strong bonds (reticular synthesis). The flexibility with which the constituents’ geometry, size, and functionality can be varied has led to more than 20,000 different MOFs being reported and studied within the past decade. The organic units are ditopic or polytopic organic carboxylates (and other similar negatively charged molecules), which, when linked to metal-containing units, yield architecturally robust crystalline MOF structures with a typical porosity of greater than 50% of the MOF crystal volume. The surface area values of such MOFs typically range from 1000 to 10,000 m2/g, thus exceeding those of traditional porous materials such as zeolites and carbons. To date, MOFs with permanent porosity are more extensive in their variety and multiplicity than any other class of porous materials. These aspects have made MOFs ideal candidates for storage of fuels (hydrogen and methane), capture of carbon dioxide, and catalysis applications, to mention a few. Metal-organic framework (MOF) structures are amenable to expansion and incorporation of multiple functional groups within their interiors. (A) The isoreticular expansion of MOFs maintains the network’s topology by using an expanded version of the parent organic linker. Examples of catalysis in MOFs are shown in the large space created by IRMOF-74-XI; Me is a methyl group. (B) Conceptual illustration of a multivariate MOF (MTV-MOF) whose pores are decorated by heterogeneous mixtures of functionalities that arrange in specific sequences. (Background) Optical image of zeolitic imidazolate framework (ZIF) crystals. Advances The ability to vary the size and nature of MOF structures without changing their underlying topology gave rise to the isoreticular principle and its application in making MOFs with the largest pore aperture (98 Å) and lowest density (0.13 g/cm3). This has allowed for the selective inclusion of large molecules (e.g., vitamin B12) and proteins (e.g., green fluorescent protein) and the exploitation of the pores as reaction vessels. Along these lines, the thermal and chemical stability of many MOFs has made them amenable to postsynthetic covalent organic and metal-complex functionalization. These capabilities enable substantial enhancement of gas storage in MOFs and have led to their extensive study in the catalysis of organic reactions, activation of small molecules (hydrogen, methane, and water), gas separation, biomedical imaging, and proton, electron, and ion conduction. At present, methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices. Outlook The precise control over the assembly of MOFs is expected to propel this field further into new realms of synthetic chemistry in which far more sophisticated materials may be accessed. For example, materials can be envisaged as having (i) compartments linked together to operate separately, yet function synergistically; (ii) dexterity to carry out parallel operations; (iii) ability to count, sort, and code information; and (iv) capability of dynamics with high fidelity. Efforts in this direction are already being undertaken through the introduction of a large number of different functional groups within the pores of MOFs. This yields multivariate frameworks in which the varying arrangement of functionalities gives rise to materials that offer a synergistic combination of properties. Future work will involve the assembly of chemical structures from many different types of building unit, such that the structures’ function is dictated by the heterogeneity of the specific arrangement of their constituents. Strategies for Metal-Organic Frameworks Metal-organic frameworks are porous materials that can exhibit very high surface areas that have potential for applications such as gas storage and separation, as well as catalysis. Furukawa et al. (1230444) review the structures devised so far and discuss the design strategies that allow families of materials to be synthesized and modified with similar framework topology but vary in pore size and type of functional groups present on the linkers. 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.

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture

A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390°C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold ∼83 liters of CO2 at 273 kelvin under ambient pressure.

Ultrahigh Porosity in Metal-Organic Frameworks

Network Approaches to Highly Porous Materials Metal-organic frameworks (MOFs), in which inorganic centers are bridged by organic linkers, can achieve very high porosity for gas absorption. However, as the materials develop larger void spaces, there is also more room for growing interpenetrating networks—filling the open spaces not with gas molecules but with more MOFs. Furukawa et al. (p. 424, published online 1 July) describe the synthesis of a MOF in which zinc centers are bridged with long, highly conjugated organic linkers, but in which the overall symmetry of the networks created prevents formation of interpenetrating networks. Extremely high surface areas and storage capacities for hydrogen, carbon dioxide, and methane were observed. The large surface areas of these materials would correspond to that of dispersed nanocubes just 3 to 6 nanometers wide. Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4′,4″-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4′,44″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4′,44″-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4′-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

A route to high surface area, porosity and inclusion of large molecules in crystals

One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas. Such materials are of critical importance to many applications involving catalysis, separation and gas storage. The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g-1 (ref. 2). Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g-1 (ref. 3). But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g-1 (refs 4–7). Despite this, no method of determining the upper limit in surface area for a material has yet been found. Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date. We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g-1. This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules—attributes not previously combined in one material.

Porous, Crystalline, Covalent Organic Frameworks

Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6·(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P63/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500° to 600°C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).

Metal−Organic Frameworks with Exceptionally High Capacity for Storage of Carbon Dioxide at Room Temperature

Metal-organic frameworks (MOFs) show high CO2 storage capacity at room temperature. Gravimetric CO2 isotherms for MOF-2, MOF-505, Cu3(BTC)2, MOF-74, IRMOFs-11, -3, -6, and -1, and MOF-177 are reported up to 42 bar. Type I isotherms are found in all cases except for MOFs based on Zn4O(O2C)6 clusters, which reveal a sigmoidal isotherm (having a step). The various pressures of the isotherm steps correlate with increasing pore size, which indicates potential for gas separations. The amine functionality of the IRMOF-3 pore shows evidence of relatively increased affinity for CO2. Capacities qualitatively scale with surface area and range from 3.2 mmol/g for MOF-2 to 33.5 mmol/g (320 cm3(STP)/cm3, 147 wt %) for MOF-177, the highest CO2 capacity of any porous material reported.

Deconstructing the Crystal Structures of Metal–Organic Frameworks and Related Materials into Their Underlying Nets

Deconstructing the Crystal Structures of Metal Organic Frameworks and Related Materials into Their Underlying Nets Michael O’Keeffe* and Omar M. Yaghi* Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States Center for Reticular Chemistry, Center for Global Mentoring, Department of Chemistry and Biochemistry, University of California Los Angeles, 607 Charles E. Young Dr. East, Los Angeles, California 90095, United States Graduate School of EEWS, Korea Advanced Institute of Science and Technology, Daejeon, Korea