Showing papers by "Omar M. Yaghi published in 2003"
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: 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.
Abstract: Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate) with a cubic three-dimensional extended porous structure adsorbed hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. 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 we associate with hydrogen binding to zinc and the BDC linker, respectively. Preliminary studies on topologically similar isoreticular metal-organic framework-6 and -8 (IRMOF-6 and -8) having cyclobutylbenzene and naphthalene linkers, respectively, gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.
4,284 citations
TL;DR: It is shown that the definition of regular nets as those with symmetry that requires the coordination figure to be a regular polygon or polyhedron leads to five regular 3-periodic nets.
Abstract: Regular nets are defined as those with symmetry that requires the coordination figure to be a regular polygon or polyhedron. It is shown that this definition leads to five regular 3-periodic nets. There is also one quasiregular net with a quasiregular coordination figure. The natural tiling of a net and its associated essential rings are also defined, and it is shown that the natural tilings of the regular nets have the property that there is just one kind of vertex, one kind of edge, one kind of ring and one kind of tile, i.e. transitivity 1111. The quasiregular net has two kinds of natural tile and transitivity 1112.
421 citations
TL;DR: Three-periodic semiregular nets are defined as those with just one kind of vertex and one kinds of edge, but excluding the five regular and one quasire gular nets described earlier.
Abstract: Three-periodic semiregular nets are defined as those with just one kind of vertex and one kind of edge, but excluding the five regular and one quasiregular nets described earlier. Fourteen of these and their natural tilings are described and their importance in crystal chemistry is indicated.
236 citations
TL;DR: It is pointed out that the FeS2 (pyrite) net found in [Zn4O(TCA)2]·(DMF)3(H2O)3 (hereafter MOF-150) is the most regular net (and the most likely to form) for linking together triangles and octahedra and that it has some additional net properties that lead to its classification as a default net.
Abstract: A prerequisite to the design of crystalline materials is the knowledge of the possible structures that potentially may form by linking together specific molecular shapes. In this context, we recently argued that, from the large number of possible structures that could in principle be assembled from various molecular shapes, those with the highest symmetry are most likely to form in practice. Thus it is particularly important to identify these special structures since they represent the default structures for the assembly of shapes. This approach has been useful in the chemistry of extended metal–organic frameworks (MOFs) in which 3D structures assembled entirely from triangles, squares, tetrahedra, or octahedra usually form structures based on the SrSi2, NbO, diamond and primitive cubic nets, respectively. Indeed, these have the highest possible symmetry for their respective building block shapes and have become as important to crystal designers as the Platonic solids are to molecular chemists. Herein we point out that the FeS2 (pyrite) net found in [Zn4O(TCA)2]·(DMF)3(H2O)3 (hereafter MOF-150; TCA= 4,4’,4’’-Tricarboxytriphenylamine, DMF=N,N’-dimethylforamide), is the most regular net (and the most likely to form) for linking together triangles and octahedra and that it has some additional net properties that lead to its classification as a default net. We use TCA and [Zn4O(CO2)6] as secondary building units (SBUs) (Figure 1a) to provide threeand six-coordinated vertices, respectively. The SBUs are produced by employing previously determined reaction parameters to effect their formation in situ. Thus, the reaction of zinc nitrate and TCA in DMF/EtOH/H2O resulted in the formation of light brown truncated crystals, which were formulated by elemental microanalysis and single crystal X-ray diffraction studies. The structure consists of two identical interpenetrating nets, one of which is shown in Figure 1b. In this structure, the basic zinc acetate octahedral SBUs, each composed of four ZnO4 tetrahedra sharing a common corner, are linked by the tritopic TCA to form a 6,3-coordinated net shown in stylized form in Figure 1c. The two interpenetrating frameworks are depicted in Figure 1d. The underlying 6,3-coordinated framework has symmetry Pa3, and the two interpenetrating frameworks have symmetry Ia3 (as found in the crystal, Figure 1d). The topology of each framework is related to the structure of the pyrite form of FeS2; it has the same topology if the S S bonding in pyrite is ignored, so we call it the pyrite net. It has been observed, not interpenetrating, in a [Hg(TPT)3] 3+
215 citations
Patent•
27 May 2003TL;DR: In this paper, a novel class of shaped bodies containing metal-organic frameworks was proposed, which includes at least one metal ion and at least bidentate organic compound and contain at least two types of micro-and mesopores.
Abstract: The present invention relates to a novel class of shaped bodies containing metal-organic frameworks. Said metal-organic frameworks comprise at least one metal ion and at least one at least bidentate organic compound and contain at least one type of micro- and mesopores or micro- or mesopores. Said shaped bodies comprise at least one metal-organic framework material and may optionally contain further substances, in particular at least one supporting material.
205 citations
118 citations
TL;DR: The CdSO4 and quartz nets are described as tilings of generalized tetrahedra [62·82] and quartz dual net is a self dual which explains its propensity to occur selfinterpenetrating in crystalline frameworks as discussed by the authors.
113 citations
Patent•
22 Oct 2003TL;DR: In this article, a process for the preparation of polyalkylene carbonate, an alternating copolymer, obtainable from the ring opening of an alkene oxide or a carbon dioxide or any substance delivering carbon oxide, in the presence of at least one catalyst containing a metal-organic framework material, wherein said framework material comprises pores and a metal ion and an at least bidentate organic compound, the bidentates being coordinately bound to the metal ion.
Abstract: The present invention relates to a process for the preparation of polyalkylene carbonate, an alternating copolymer, obtainable from the ring opening of an alkene oxide or an alkene oxide precursor in the presence of carbon dioxide or any substance delivering carbon oxide, in the presence of at least one catalyst containing a metal-organic framework material, wherein said framework material comprises pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion.
94 citations
Patent•
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TL;DR: In this paper, a non-cylindrical geometry container for uptaking, or storing, or releasing, or uptaking and storing, storing, and releasing at least one gas is presented.
Abstract: The present invention relates to a container such as a container having non-cylindrical geometry, for uptaking, or storing, or releasing, or uptaking and storing, or uptaking and releasing, or storing and releasing, or uptaking, storing and releasing at least one gas, comprising at least one opening for allowing the at least one gas to enter and exit or at least one opening for allowing the at least one gas to enter and at least one opening for allowing the at least one gas to exit said container, and a gas-tight mechanism capable of storing the at least one gas under a pressure of from 1 to 750 bar, especially preferably from 50 to 80 bar, inside the container, said container further comprising a metallo-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound which is bound to said metal ion, as well as to a storage system and a fuel cell comprising said container, and to a method of using said container or said fuel cell for supplying power to power plants, cars, trucks, busses, cell phones, and laptops.
75 citations
TL;DR: This report illustrates the utility of a simple molecule, N(C( 3)N(3))(3)Cl(6), in answering the question of whether triazine based C(3]N(4) phases are layered or instead they adopt 3D structures.
Abstract: The successful synthesis and structural characterization of molecules that represent segments of extended solids is a valuable strategy for learning metric and stereochemical characteristics of those solids. This approach has been useful in cases in which the solids are particularly difficult to crystallize and thus their atomic connectivity and overall structures become difficult to deduce with X-ray diffraction techniques. One such class of materials is the covalently linked CxNy extended solids, where molecular analogues remain largely absent. In particular, structures of C3N4 solids are controversial. This report illustrates the utility of a simple molecule, N(C3N3)3Cl6, in answering the question of whether triazine based C3N4 phases are layered or instead they adopt 3D structures. Here, we present density functional calculations that clearly demonstrate the lower stability of graphitic C3N4 relative to 3D analogues.
TL;DR: In this paper, three new germanate solids were synthesized under hydrothermal conditions using 1,4-diaminobutane (DAB), DAPe, and DACH as bases.
Abstract: Three new germanate solids, ASU-19, ASU-20-DAPe, and ASU-20-DACH, have been synthesized under hydrothermal conditions using respectively 1,4-diaminobutane (DAB), 1,5-diaminopentane (DAPe), and 1,4-diaminocyclohexane (DACH) as bases. The structures of ASU-19 and ASU-20-DACH have been characterized by single-crystal X-ray diffraction: ASU-19, Ge 14 O 29 X 4 .[GeOX 2 ].[H 2 DAB] 3 .3.8H 2 O (X = F or OH), space group P1, a = 11.4191(5), b = 12.0525(6), c = 18.1847(8), a = 90.704(1)°, β = 92.635(1)°, γ = 91.389(1)°, V = 2499.1(2) A 3 ; ASU-20-DACH: Ge 7 O 14 X 3 .[H 2 DACH] 1.5 .2H 2 O, space group C2/c, a = 15.9525(11), b = 17.5476(12), c = 19.0027(13) A, β = 109.446(1)°, and V = 5015.9(6) A 3 . The structure of ASU-20-DAPe, Ge 7 O 14 X 3 .[H 2 DAPe] 1.5 .H 2 O, has been determined from X-ray powder diffraction data: space group C2/c, a = 16.3180(5), b = 16.6125(4), c = 17.8898(6) A, β = 99.684-(2)°, V = 4780.5(3) A 3 . All three structures are based on the assembly of the same cluster Ge 7 (O,OH,F) 19 . The two ASU-20 structures consist of a slab of four-connected clusters. In ASU-19, the same layers are connected pairwise through a GeO 2 X 2 spacer, generating a slab structure, with slab thickness ca. 20 A. The existence of the same layer in the presence of three different organic bases shows the adaptability of the structures to molecules differing in size, shape, and symmetry.
TL;DR: Six new zirconogermanates have been prepared under hydrothermal conditions using amines as bases and the structural relationships between ASU-25 and its inorganic counterpart are described.
Abstract: Six new zirconogermanates have been prepared under hydrothermal conditions using amines as bases. There are four new structure types (ASU-n) with a common motif of ZrGe5. ASU-23 is a layered structure: ZrGe3O8(OH)F·[C10H26N4]·H2O, space group P21/n, a = 6.7957(8) A, b = 12.700(1) A, c = 24.293(3) A, β = 97.936(2)°, V = 2076.4(4) A3. ASU-24 is a pillared layered structure: Zr3Ge6O18(OH2,F)4F2·[C6H18N2]·[C6H17N2]2·2H2O, space group P21/n, a = 7.4249(3) A, b = 25.198(1) A, c = 11.3483(5) A, β = 90.995(1)°, V = 2122.9(2) A3. This material has the lowest framework density (FD) of any oxide material that we are aware of (FD = 8.48 metal atoms/nm3). Two other materials form three-dimensional open-frameworks, ASU-25: ZrGe3O9·[C3H12N2], space group P1121/a, a = 13.1994(4) A, b = 7.6828(2) A, c = 11.2373(3) A, γ = 91.233(3)°, V = 1139.29(5) A3. The other is ASU-26: ZrGe3O9·[C2H10N2], space group Pn, a = 13.7611(3) A, b = 7.7294(2) A, c = 11.2331(3) A, β = 104.793(1)°, V = 1155.21(4) A3. ASU-25 is related to the...
Patent•
27 May 2003TL;DR: In this paper, a process for the reaction of at least one organic compound with one oxygen-delivering substance, for example a hydroperoxide, in the presence of a metal-organic framework material comprising pores and a metal ion and an at least bidentate organic compound being coordinately bound to the metal ion is described.
Abstract: The present invention relates to a process for the reaction of at least one organic compound with one oxygen-delivering substance, for example a hydroperoxide, in the presence of at least one catalyst containing a metal-organic framework material comprising pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. Further, the present invention is directed to the products being obtainable by the process according to the invention.
TL;DR: The structural basis for complex oxides of the early transition metals in their highest oxidation states is not well understood on the atomic-molecular size scale, and as a result, these properties are difficult or impossible to control chemically as mentioned in this paper.
Abstract: Complex oxides of the early transition metals in their highest oxidation states display a remarkable variety of properties, including catalytic [1], electrooptic [2], high-K dielectric [3], electromechanical [4], ferroelectric [5], and charge density wave [6] behavior The structural basis for this behavior, although understood in general terms, is not well understood on the atomic-molecular size scale, and as a result, these properties are difficult or impossible to control chemically A first step toward addressing this problem is clear definition of structure and bonding in these materials, the subject of this Chapter
TL;DR: In this article, the same layers are connected pairwise through a GeO2X2 spacer, generating a slab structure, with slab thickness ca. 20 Å. The existence of the same layer in the presence of three different organic bases shows the adaptability of the structures to molecules differing in size, shape, and symmetry.
Abstract: Three new germanate solids, ASU-19, ASU-20-DAPe, and ASU-20-DACH, have been synthesized under hydrothermal conditions using respectively 1,4-diaminobutane (DAB), 1,5-diaminopentane (DAPe), and 1,4-diaminocyclohexane (DACH) as bases. The structures of ASU-19 and ASU-20-DACH have been characterized by single-crystal X-ray diffraction: ASU-19, Ge14O29X4‚[GeOX2]‚[H2DAB]3‚3.8H2O (X) F or OH), space group P1h, a) 11.4191(5), b ) 12.0525(6), c ) 18.1847(8) Å, R ) 90.704(1)°, ! ) 92.635(1)°, γ ) 91.389(1)°, V ) 2499.1(2) Å3; ASU-20-DACH: Ge7O14X3‚[H2DACH]1.5‚2H2O, space group C2/c, a ) 15.9525(11), b ) 17.5476(12), c ) 19.0027(13) Å, ! ) 109.446(1)°, and V ) 5015.9(6) Å3. The structure of ASU-20-DAPe, Ge7O14X3‚[H2DAPe]1.5‚H2O, has been determined from X-ray powder diffraction data: space group C2/c, a ) 16.3180(5), b ) 16.6125(4), c ) 17.8898(6) Å, ! ) 99.684(2)°, V ) 4780.5(3) Å3. All three structures are based on the assembly of the same cluster Ge7(O,OH,F)19. The two ASU-20 structures consist of a slab of four-connected clusters. In ASU-19, the same layers are connected pairwise through a GeO2X2 spacer, generating a slab structure, with slab thickness ca. 20 Å. The existence of the same layer in the presence of three different organic bases shows the adaptability of the structures to molecules differing in size, shape, and symmetry.
TL;DR: In this article, six new zirconogermanates have been prepared under hydrothermal conditions using amines as bases and four new structure types (ASU-n) with a common motif of ZrGe5.
Abstract: Six new zirconogermanates have been prepared under hydrothermal conditions using amines as bases. There are four new structure types (ASU-n) with a common motif of ZrGe5. ASU-23 is a layered structure: ZrGe3O8(OH)F·[C10H26N4]·H2O, space group P21/n, a = 6.7957(8) A, b = 12.700(1) A, c = 24.293(3) A, β = 97.936(2)°, V = 2076.4(4) A3. ASU-24 is a pillared layered structure: Zr3Ge6O18(OH2,F)4F2·[C6H18N2]·[C6H17N2]2·2H2O, space group P21/n, a = 7.4249(3) A, b = 25.198(1) A, c = 11.3483(5) A, β = 90.995(1)°, V = 2122.9(2) A3. This material has the lowest framework density (FD) of any oxide material that we are aware of (FD = 8.48 metal atoms/nm3). Two other materials form three-dimensional open-frameworks, ASU-25: ZrGe3O9·[C3H12N2], space group P1121/a, a = 13.1994(4) A, b = 7.6828(2) A, c = 11.2373(3) A, γ = 91.233(3)°, V = 1139.29(5) A3. The other is ASU-26: ZrGe3O9·[C2H10N2], space group Pn, a = 13.7611(3) A, b = 7.7294(2) A, c = 11.2331(3) A, β = 104.793(1)°, V = 1155.21(4) A3. ASU-25 is related to the...