MXPA05012008A - Implementation of a strategy for achieving extraordinary levels of surface and porosity in crystals - Google Patents

Abstract

The present invention provides a metal-organic framework ("MOFâÇØ) comprising a plurality of metal clusters and a plurality of multidentate, linking ligands. Each metal of the plurality of metal clusters comprises one or more metal ions. Each ligand of the plurality of multidentate linking ligands connects adjacent metal clusters. The present invention also provides a method of forming the metalorganic framework. The method of the invention comprises combining a solution comprising one or metal ions with a multidentate linking ligand having a sufficient number of accessible sites for atomic or molecular adsorption that the surface area of the resulting metal-organic framework is greater than 2,900 M2/g.

Description

IMPLEMENTATION OF A STRATEGY TO ACHIEVE EXTRAORDINARY LEVELS OF SURFACE AND POROSITY IN CRYSTALS CROSS REFERENCE TO RELATED REQUESTS This application claims the benefit of the provisional application of E.U. Series No. 60 / 527,511, filed on December 5, 2003 and the provisional application of E.U. Series No. 60 / 469,483, filed May 9, 2003. The full description of each of these applications is incorporated herein by reference.

DECLARATION REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT The invention was produced with government support under Contract No. 9980469, granted by The National Science Foundation. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention At least in one embodiment, the present invention relates to metal-organic structures with higher levels of surface area and porosity. 2. Prior Art Porous materials have become important in a variety of chemical and physical processes including, for example, gas / liquid separation, catalysis, luminescence based detectors, gas storage and the like. Typically, each specific application requires pore size design and atomic and molecular adsorption properties to achieve the desired result. One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas. Until recently, the highest surface area for a disordered structure was that of carbon (2,030 m2 / g), and for ordered structures it was that of zeolite Y (904 m2 / g). More recently, crystals of metallic-organic structures have been reported ("MOFs") with similar or slightly larger surface areas.

Despite this progress and the critical importance of a larger surface area for many applications involving gas catalysis, separation and storage, no strategy has yet been delineated to answer the question of what is for a material the limit superior in the surface area, and how it can be achieved. The methods for designing the pore size and adsorption, involve altering the chemical composition, functionality and molecular dimensions without changing the underlying topology. (See, A. Stein, S. W. Keller and T. E. Mallouk, Science 259, 1558 (1993), and P. J. Fagan and M. D. Ward, Sci. Am. 267, 48 (1992)). Although desirable, there are few systematic procedures due to the lack of control over the molecular assembly and in particular, the inability to control the orientation of the crystal atomic groups. These difficulties must be contrasted with the synthesis of organic molecules that can be formed by well characterized and controllable stages. Typically, the insolubility of the extended solids requires that the assembly of these materials be carried out in a single step. (See, O. M. Yaghi, M. O'Keeffe and M. Kanatzidis, J. Solid State Chem. 152, 1 (2000)). Stable, porous metallic-organic structures have been previously described. Typically, an MOF includes groups of metals linked together in a periodic manner by binding ligands that increase the distance between the groups to give a network-like structure. MOFs based on the same network topology (i.e., symmetry and underlying connectivity) are described as "isorretic". Li et al., Described a metallic-organic structure (referred to as MOF-5) formed by diffusing triethylamine in a solution of zinc nitrate (II) and benzene-1,4-dicarboxylic acid (H.2BDC) in N, N -dimethyl-formamide / chlorobenzene followed by the deprotonation of H2BDC and the reaction with the Zn2 + ions (Li, Hailian, Mohamed Eddaoudi, M. O'Keeffe and OM Yaghi, "Design and synthesis of an exceptionally stable and highly porous metal- organic framework "(Design and synthesis of an exceptionally stable and highly porous metallic-organic structure), Nature, Vol. 402, pp. 276-279 (November 18, 1999)). It was found that the MOF-5 structure comprises an extended porous network having a three-dimensional intersecting channel system with a 12.9 A space between the centers of the adjacent groups. Although the MOF-5 crystal structure possesses a variety of desirable characteristics, the MOF-5 structure is formed with relatively low performance. In addition, the MOF-5 structure seems to be limited to a single benzene ring as a link between the adjacent Zn4 (0) 0_2Ce groups. The U.S. Patent Application. 20030004364 (application x364) expands and improves the work described in Li et al., By providing preparation for a variety of isorreticular organic-metal structures. Application ? 364 recognizes an improvement in requiring that the linker include a phenyl with an appended functional group. It should also be appreciated that the binding ligands in both Li et al., And in the application? 364 are charged polydentate ligands. Although application 364 provides an introduction to the design of organic metal structures, further improvement is still necessary to identify those molecular components that more effectively increase the surface area. Researchers have also attempted to formulate structures that have longer links between adjacent groups, using polytopic donor N ligands. The synthesis of open structures by the assembly of metal ions with di- and polytopic donor-N organic linkers such as 4, 4 '-bipyridine, has produced many structures of cationic structure. Although such synthesis can produce structures with various pore sizes, attempts to evacuate / exchange hosts from within the pores frequently result in the collapse of the host structure limiting the practical utility of such structures. Accordingly, there is a need in the prior art for porous structures with increased adsorption and in particular, methods for producing such structures in a systematic manner.

SUMMARY OF THE INVENTION The present invention provides a general strategy that allows the realization of a structure that has, by far, the largest surface area reported to date. In one embodiment of the present invention, there is provided a metal-organic structure ("MOF") comprising a plurality of metal groups and a plurality of multidentate linking ligands. The methodology of the present invention represents an improvement of the U.S. Patent Application. 20030004364, the complete description of which is incorporated herein by reference. Each metal of the plurality of groups of metals comprises one or more metal ions. Each ligand of the plurality of multidentate linking ligands connects the groups of adjacent metals. The plurality of multidentate linking ligands has a sufficient number of accessible sites for atomic or molecular adsorption so that the surface area is greater than 2,900 m2 / g. In another embodiment of the invention, the design, synthesis and properties of the new MOF structures and the related binding ligands are provided. In this modality, crystalline Zn40 (BTB) 2 (BTB = 1,3,5-benzenetribenzoate) is prototype, a new metal-organic structure (called MOF-177) with a surface area of 4,500 m2 / g. The MOF-177 combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of bonding polycyclic organic host-molecule attributes hitherto not made in a material. In yet another embodiment of the invention, a method for the adsorption of host species is provided.

In this embodiment, an MOF is contacted with a host species in such a way that at least a portion of the host species is adsorbed.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an illustration showing the surface area of graphite fragments. (a) A graphene sheet extracted from the graphite structure has a Connolly surface area of 2.965 m2 / g when calculated with the Cerius modeling software (see Nijkamp, MG, Raaymakers, JE van Dillen, AJ &de Jong, KP hydrogen storage using physiosorption material requirements Appl. Phys. A 72, 619-623 (2001)); (b) A series of 6-poly-p-linked rings can be extracted from that sheet, thereby increasing the surface area to 5,683 m2 / g; (c) The excision of the 6-member rings 1, 3, 5-linked to a central ring, elevates the surface area to 6,200 m2 / g; (d) The surface area reaches a maximum of 7.745 m2 / g when the graphene sheet completely decomposes into isolated 6-member rings; Figure 2 provides the structure of MOF-177. (a) A unit of BTB linked to three units of Ozn4 (H atoms are omitted). The tetrahedra of Zn04 are shown in gray and the atoms of 0, C are shown as spheres in light gray and black, respectively. (b) The structure projected as [001] is illustrated similarly. For clarity, only about half of the repeating unit of axis c is shown. (c) A fragment of the structure radiating from a central OZn4; 6-member rings are shown as gray hexagons; Figure 3 illustrates the concatenation of rings in meshing networks with their dual structures. The networks are shown enlarged with triangles in the coordinated 3 vertices and with octahedrons in the coordinated vertices 6, (a) A pair of identical rings in the pyr autodual network of the MOF-150; (b) A ring of six members of the network qom of the MOF-177 concatenated with a ring of the dual network. Please note in the latter, that the pairs of coordinated vertexes 3 are directly linked as are the pairs of the coordinated vertices 6; Figure 4 is a diagram of the sorption isotherm of nitrogen gas at 78 K for MOF-177 (filled circles, sorption, open circles desorption); P / P0 is the ratio of the gas pressure (P) to the saturation pressure (P0), with P0 = 746 torr; Figure 5 is an illustration demonstrating the inclusion of organic polycyclic hosts. The observation of colorless crystals that turn dark red provided an optical evidence for the adsorption of C60 in the unique crystals of MOF-177. (a) Analytical evidence was provided by comparing the Raman spectrum of a cut glass (D) and a complete crystal (C) for the C60 volume (A) and an evacuated MOF (B); (b) The ability of the crystals of MOF-177 to adsorb large hosts was quantified for the Orange Astrazon, Nile Red, and Reichardt dye. These incorporated 16, 2 and 1 molecules per unit cell respectively. Cutting the crystals to expose their inner core proved that for Orange "Astrazon and Nile Red, uniform adsorption was achieved throughout the entire crystal while for Reichardt's dye, adsorption was restricted mainly to the edges of the crystal The sphere and ray patterns of the molecules are superimposed on a sphere with a diameter of 11 A which is adapted to the pores of the MOF-177; Figure 6 provides x-ray structures of a single crystal of the MOF -5 (A), IRMOF-6 (B) and the IRMOF-8 (C) illustrated for a single cube fragment of their respective extended three-dimensional cubic structures.

At each of the corners there is a group [OZn4 (C02) 6] of an oxygen centered Zn4 tetrahedron bridged by six carb? Xylates of an organic linker (Zn04, gray tetrahedron, 0, gray spheres, C, black spheres).

The large spheres represent the largest spherical volume that would fit into the cavities without intersecting the van der aals surface of the structure atoms. The hydrogen atoms have been omitted. Figure 7 provides the sorption isotherm of the hydrogen gas for MOF-5 at 298 K; and Figure 8 provides the INS spectrum (T = 10 K) for hydrogen adsorbed to MOF-5 with charges of 4 H2 (upper), 8 H (medium), and 24 H2 (lower) per unit of formula [ Zn40 (BDC) 3] obtained in the QENS spectrometer in IPNS, Argonne National Laboratory. In each case, the spectrum of the host-free MOF-5 sample (blank) was subtracted. The very light after subtraction close to 4 meV arises from a peak in that region of the blank sample, which can not be removed by heating under vacuum. Assignments are based on the use of a potential model and isotype shifts were observed from a D2 spectrum in the MOF-5. The peaks in 10.3 and 12.1 meV are assigned to transitions 0-1 for the two main link sites (I and II, marked in the spectrum). Other tentative assignments are 4.4 meV (1-2, site II), 15.5 meV (0-2, site II), 7.5 meV (1-2, site I), 17.5 meV (0-2, site I) and 14.5 meV (H2 solid). The regions of the MOF-5 corresponding to sites I and II are shown schematically in the upper right corner.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Reference will now be made in detail to the presently preferred compositions or embodiments and methods of the invention, which constitute the best modes of practicing the invention currently known to the inventors. As used herein "link ligand" means a chemical species (including molecules and neutral ions) that coordinates to two or more metals resulting in an increase in their separation and the definition of regions or channels of vacuum in the structure that is produced. Examples include 4,4'-bipyridine (a neutral molecule, multiple donor N) and benzene-1,4-dicarboxylate (a polycarboxylate anion). As used herein, "ligand without link" means a chemical species that coordinates to a metal but does not act as a linker. The ligand without bond can still connect metals, but this is typically through a unique coordination functionality and consequently does not lead to a large separation. Examples include: water, hydroxide, halides, and coordination solvents such as alcohols, formamides, ethers, nitriles, dimethylsulfoxide and amines. As used herein, "host" means any chemical species that resides within the vacuum regions of an open-structure solid that is not considered integral to the structure. Examples include: solvent molecules that fill the vacuum regions during the synthetic process, other molecules that are exchanged by the solvent such as during immersion (through diffusion), or after evacuation of the solvent molecules, such as gases in an absorption experiment. As used herein, "kind of load balance" means a loaded host species that balances the load of the structure. Very often, this species is strongly bound to the structure, i.e., through hydrogen bonds. This can be decomposed to evacuation to leave a smaller loaded species (see below), or exchanged for an equivalently charged species, but typically can not be removed from the pore of an organic-metal structure without collapsing it. As used in this"space filling agent" means a host species that fills the vacuum regions of an open structure during synthesis. Materials exhibiting permanent porosity remain intact after removing the space filler through heating and / or evacuation. Examples include: solvent molecules or molecular species of charge balance. The latter can decompose on heating, so that their gaseous products are easily evacuated and a smaller kind of charge balance remains in the pore (i.e. protons). Sometimes the space fillers are referred to as quenching agents. The conceptual basis of the present invention can be appreciated by considering a graphene sheet (Figure la). The excision of the progressively smaller fragments from this sheet and the calculation of their Connolly surface areas (see Examples), show that the exposure of the latent edges of the six-member rings leads to a significant increase in surface area specific. In this way, the surface area of a single infinite sheet is 2,965 m2 / g (calculating both sides, see the Examples). For units consisting of infinite chains of 6-poly-p-linked member rings (Figure Ib), the surface area at least doubles (5,683 m / g). alternatively, if the graphene sheet is divided into two units of three 6-membered rings that are 1.3, 5-linked to a central ring (Figure 1), the surface area is similarly high (6,200 m2 / g) . Finally, the exposure of all the latent edges to give isolated rings of 6 members (Figure Id) leads to an upper limit value of 7.745 m2 / g. This analysis does not take into account the hydrogen atoms that would end the fragments in the MOFs, although that would result in even larger surface areas for these fragments. As described below, exposing the latent edges serves as a guide to design structures with exceptional surface areas, and helps identify the reasons why zeolites are unlikely targets for this purpose. Within a typical zeolite structure such as faujasite, the host molecules can only access the adsorption sites in the pore walls leaving the space inside each of the sodalite cells and the edges of the MOM rings (M it is a metal atom) of six completely inaccessible members, which leads to relatively low surface areas. In this way, structures with fused rings should be avoided in order to maximize exposed surfaces and ring edges. In one embodiment, the present invention provides a metal-organic structure comprising a plurality of metal groups and a plurality of multidentate linking ligands. Each metal of the plurality of groups of metals comprises one or more metal ions. In addition, the metal group includes one or more non-binding ligands. Each ligand of the plurality of multidentate linking ligands connects groups of adjacent metals. Typically, the plurality of multidentate linking ligands has a number of accessible sites for atomic or molecular adsorption so that the surface area per gram of material is greater than 2,900 m2 / g. Specifically, the multidentate ligand has a sufficient number of edges available for atomic or molecular adsorption so that the surface area per gram of material is greater than 2,900 m2 / g. "Borders" as used herein means a region within the pore volume in proximity to a chemical bond (single, double triple, aromatic- or coordination) where the adsorption of a host species may occur. For example, such edges include regions near the exposed atom-to-atom bonds in an aromatic or non-aromatic group. Exposed means that it is not a bond that occurs in the position where the rings merge with each other. Although there are different methods to determine the surface area, a particularly useful method is the Langmuir method of surface area. In variations of the invention, the plurality of multidentate linking ligands has a sufficient number of accessible sites (i.e. borders), for atomic or molecular adsorption so that the surface area per gram of material is greater than 3,000 m2 / g. In other variations, the plurality of multidentate linking ligands has a sufficient number of accessible sites (i.e. borders) for atomic or molecular adsorption so that the surface area per gram of material is greater than about 3,500 m2 / g. In yet another variation, the plurality of multidentate linking ligands has a sufficient number of accessible sites (i.e. borders) for atomic or molecular adsorption so that the surface area per gram of material is greater than about 4,000 m2 / g. The upper limit for the surface area will typically be approximately 10,000 m2 / g. More typically, the upper limit for the surface area will be approximately 8,000 m2 / g. The metal ions used in the MOFs of the present invention comprise one or more ions selected from the group consisting of metal ions from Group 1 to 16 of the Periodic Table of IUPAC Elements (including actinides and lanthanides). Specific examples of the metal ions used in the MOFs of the present invention, comprise one or more ions selected from the group consisting of Li +, Na +, K +, Rb +, Be3 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Sc3 +, Y3 +, Ti4 + , Zr4 +, Hf4 +, V4 + and V3 +, V2 +, Nb3 +, Ta3 +, Cr3 +, Mo3 +, 3+, Mn3 +, Mn2 +, Re3 +, Re2 +, Fe3 +, Fe2 +, Ru3 +, Ru2 +, 0s3 +, 0s2 +, Co3 +, Co2 +, Rh2 +, Rh + , Ir2 +, Ir +, Ni2 +, Ni \ Pd2 +, Pd +, Pt +, Pt +, Cu2 +, Cu +, Ag +, Au +, Zn2 +, Cd2 +, Hg +, Al3 +, Ga3 +, In3 +, Tl3 +, Si4 +, Si2 +, Ge4 +, Ge2 +, Sn4 +, Sn2 + , Pb4 +, Pb2 +, As5 +, As3 +, As +, Sb5 +, Sb3 +, Sb +, Bi5 +, Bi3 +, Bi +, and combinations thereof. Of these, Co2 +, Cu2 +, and Zn2 + are preferred because of their ability to form predetermined groups in the synthesis mixture. A particularly useful metal group is described by the formula MmXn wherein M is a metal ion, X is selected from the group consisting of anions and a non-metallic atom from Group 14 to Group 17, m is an integer from 1 to 10, and n is a selected number for balancing the charge of the metal group so that the metal group has a predetermined electric charge. Examples of the metal M ion, include, Mg2 +, Ca2 +, Sr2 +, Ba2, V2 +, V3 +, V4 +, V5 +, Mn2 +, Re2 +, Fe2 +, Ru3 +, Ru2 +, Os2 +, Co2 +, Rh2 +, Ir2 +, Ni2 +, Pd2 +, Pt2 +, Cu2 + , Zn2 +, Cd2 +, Hg2 +, Si2 +, Ge2 +, Sn2 +, and Pb2 +. More specific examples of X are the anions of O, N, and S. Accordingly, a representative metal group has X as 0 with n equal to 4 (e.g., Zn40). The MOFs of the present invention may further include a metal group that includes one or more non-binding ligands. Useful non-binding ligands include, for example, a ligand selected from the group consisting of O 2", sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, sulfur, hydrogen sulfate, selenide, selenate, hydrogen selenate, telluride, telurate, hydrogen telurate, nitride, phosphide, arsenide, arsenate, hydrogen arsenate, arsenate dihydrogen, antimony, antimonate, hydrogen antimonate, dihydrogen antimonate, fluoride, boride, borate, hydrogen borate, perchlorate, chlorite, hypochlorite, perbromate, bromite, hypobromite, periodate, iodite, hypoiodite; and mixtures thereof. The MOFs of the present invention also include a multidentate linking ligand. Typically, the multidentate linking ligand will be a charged linkage ligand. Such charged binding ligands will include functional anionic groups such as carboxylate (C0 ~), sulfate (S03 ~) and the like. Typically, each of the multidentate linking ligands will include two or more functional groups charged in this manner. The multidentate ligand may be a bidentate ligand or a tridentate ligand (functional groups greater than three are also within the scope of the invention). Accordingly, an example of a useful multidentate ligand may contain 2, 3, or more carboxylate groups. The multidentate linking ligand will typically have more than 16 atoms that are incorporated into aromatic rings or non-aromatic rings. In other variations, the multidentate linking ligand has more than 20 atoms that are incorporated into aromatic rings or non-aromatic rings. In each of these variations, the upper limit to the number of atoms incorporated in aromatic or non-aromatic rings is typically about 60 atoms. Alternatively, the multidentate ligand may be described by the number of edges contained in the aromatic or non-aromatic rings. For example, multidentate ligands typically have at least 16 edges in the aromatic or non-aromatic rings. In other variations, the multidentate ligands have at least 18 edges in the aromatic or non-aromatic rings. In yet other variations, multidentate ligands typically have at least 24 edges in the aromatic or non-aromatic rings. In each of these variations, the upper limit to the number of edges in the aromatic or non-aromatic rings is typically about 60. A preferred multidentate linking ligand is described by the formula I: i; And, substituted variations of formula I. The substituted variations will include components with the hydrogen atoms in the rings replaced by groups such as an alkyl, an alkoxy, a halogen, a nitro, a cyano, an aryl, aralkyl and the like. An example of an organic-metal structure of this embodiment has the formula Zn0 (BTB) 3 * (DEF) x, where x represents the number of coordinated N, N-diethylformamide ("DEF") molecules. This number is typically from 0 to about 25. Another preferred multidentate linking ligand is described by formula II: II and substituted variations of formula II. The substituted variations will include components with the hydrogen atoms in the rings replaced by groups such as an alkyl, an alkoxy, a halogen, a nitro, a cyano, an aryl, aralkyl and the like. An example of an organic-metal structure of this embodiment has the formula Zn04 (DCBP) * (DEF) X, where x is an integer representing the number of coordinated diethylformamide molecules. Again this number is typically from 0 to about 25. In another embodiment of the present invention, a metal-organic structure is provided. The metal-organic structure of this embodiment comprises a plurality of groups of metals and one or more multidentate linking ligands having the formula III: (C34Ha204N4Zn) neither; and substituted variations of formula III. The substituted variations will include components with the hydrogen atoms in the rings replaced by groups such as an alkyl, an alkoxy, a halogen, a nitro, a cyano, an aryl, aralkyl and the like. An example of an organic-metal structure of this embodiment has the formula Zn04 (C34H1204N4Zn) 3 * (DEF) X, (also represented as Zn40 [Zn (BCPP)] 3 * (DEF) X), where x represents the number of coordinated N, N-diethylformamide ("DEF") molecules. In another embodiment of the invention, the metal-organic structures described above include a host species. The presence of such a host species can advantageously increase the surface area of the metal-organic structures. Suitable host species include, for example, organic molecules with a molecular weight less than 100 g / mol, organic molecules with a molecular weight less than 300 g / mol, organic molecules with a molecular weight less than 600 g / mol, organic molecules with a molecular weight greater than 600 g / mol, organic molecules containing at least one aromatic ring, polycyclic aromatic hydrocarbons, and metal complexes having the formula MmXn wherein M is a metal ion, X is selected from the group consisting of from an anion from Group 14 to Group 17, m is an integer from 1 to 10, and n is a number selected to balance the charge of the metal group so that the metal group has a predetermined electric charge; and combinations thereof. The host species is introduced into the metal-organic structure by contacting the structure with the host species. In a variation of this mode, the host species is an adsorbed chemical species. Examples of such species include ammonia, carbon dioxide, carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen, argon, organic dyes, organic polycyclic molecules, and combinations thereof. Again, these chemical species are introduced into the metallic-organic structure by contacting the structure with the chemical species. In another embodiment of the invention, a method is provided for adsorbing a host species with MOF-5 (a structure with inorganic [Ozn4] 6+ groups attached to an octahedron array of [02C-C6H4-C02] 2"groups ( 1,4-benzenedicarboxylate, BDC)) or related structures In this method, these structures are contacted with the host species (or chemical species) as described above.The related structures include those structures that have [Ozn] 6 groups + inorganics bound with multidentate ligands including 1 or 2 substituted or unsubstituted aromatic ring groups (ie, phenyl, phenylene, mesitylene, etc.). In a variation of the invention, the metal-organic structures described above may include an interpenetrating metal-organic structure that increases the surface area of the metal-organic structure. Although the structures of the invention can advantageously exclude such interpenetration, there are circumstances in which the inclusion of an interpenetration structure can be used to increase the surface area. In another embodiment of the present invention, a method for forming a metal-organic structure is provided. The method of this embodiment comprises combining a solution comprising a solvent and one or more ions selected from the group consisting of metal ions from Group 1 to 16 of the Periodic Table of IUPAC Elements. (including actinides and lanthanides) with a multidentate binding ligand. The multidentate ligand is selected such that the surface area of the metal-organic structure has the above-described surface area and adsorption properties. Examples of metal ions that can be used are selected from the group consisting of Li +, Na +, K +, Rb +, Be3 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Sc3 +, Y3 +, Ti4 +, Zr4 +, Hf4 +, V4 +, V3 +, V2 +, Nb3 + , Ta3 +, Cr3 +, Mo3 +, W3 +, Mn3 +, Mn2 +, Re3 +, Re2 +, Fe3 +, Fe2 +, Ru3 +, Ru2 +, 0s3 +, 0s2 +, Co3 +, Co2 +, Rh2 +, Rh +, Ir2 +, Ir +, Ni2 +, Ni +, Pd2 +, Pd +, Pt2 + , Pt +, Cu2 +, Cu +, Cu +, Ag +, Au +, Zn2 +, Cd2 +, Hg2 +, Al3 +, Ga3 +, In3 +, Tl3 +, Si4 +, Si2 +, Ge4 +, Ge2 +, Sn +, Sn2 +, Pb4 +, Pb2 +, As5 +, As3 +, As +, Sb5 +, Sb3 + , Sb +, Bi5 +, Bi3 +, Bi +, and combinations thereof. The preferred multidentate linking ligands are the same as described above. Suitable solvents include, for example, ammonia, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine, N, N-dimethylformamide, N, N-diethylformamide, and mixtures thereof. In a variation of this modality (without considering the adsorption properties of the structures), a metallic-organic structure is formed by combining a solution comprising a solvent and one or more ions selected from the group consisting of metal ions from Group 1 to 16 of the Periodic Table IUPAC elements (including actinides and lanthanides) with a ligand selected from the ligands represented by the formulas I, II or III as described above. The solution used in the method of the invention may also include a space filler. Suitable space fillers include, for example, a component selected from the group consisting of: a. alkylamines and their corresponding alkyl ammonium salts, containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; b. arylamines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings; c. alkyl phosphonium salts, containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; d. aryl phosphonium salts having from 1 to 5 phenyl rings; and. organic alkyl acids and their corresponding salts containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; .f. organic aryl acids and their corresponding salts having from 1 to 5 phenyl rings; g. aliphatic alcohols containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; h. aryl alcohols having from 1 to 5 phenyl rings; i. inorganic anions of the group consisting of sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, O2 -, sulfur diphosphate, hydrogen sulfate, selenide, selenate, hydrogen selenate, telluride, telurate, hydrogen telurate, nitride, phosphide, arsenide, arsenate, hydrogen arsenate, dihydrogen arsenate, antimony, antimonate, hydrogen antimonate, antimonate of dihydrogen, fluoride, boride, borate, hydrogen borate, perchlorate, chlorite, hypochlorite, perbromate, bromite, hypobromite, periodate, iodite, hypoiodite and the corresponding acids and salts of said inorganic anions; j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine , trifluoromethylsulphonic acid, N, N-dimethylformamide, N, N-diethylformamide, dimethylsulfoxide, chloroform, bromoform, dibromo-methane, iodoform, diiodomethane, halogenated organic solvents, N, N-dimethylacetamide, N, N-diethylacetamide, l-methyl-2-pyrrolidinone, amide solvents, methylpyridine, dimethylpyridine, diethylether and mixtures thereof. It should be recognized that these space fillers can remain within the organic-metal structures until they are removed. The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and the scope of the claims. These ideas were implemented using reticular chemistry reactions established to bind the carboxylate derivative of the type shown in Figure LE (BTB, a triangular unit) with basic groups of zinc (II) carboxylate (Zn0 (C02) 6, (a octahedron unit) (Figure 2a) in MOF-177. Block-shaped crystals of MOF-177 were produced (see Methods), heating a mixture of H3BTB and Zn (N03) 2 * 6H_0 in N, N-diethylformamide (DEF) at 100 ° C. The crystals were formulated by elemental analysis as Zn40 (BTB) * (DEF) 15 (H20) 3 (Calculated Analysis: C, 56.96; H, 7.46; N, 7.73. Found: C, 56.90; H, 7.54; N, 7.67). An X-ray diffraction study (see Methods and Support Information) in a crystal isolated from the reaction mixture confirmed this formulation. A composition of the remarkably open three-dimensional structure of Zn40 (BTB) was also revealed, in which each basic zinc acetate group is bonded to six units of BTB (Figure 2b).

In this structure there are 72 exposed edges (48 C-C, 12 C-0, and 12 Zn-0) and only 4 fused edges (Zn-0) per formula unit (Figure 2c). Notably, the structure of M0F-177 is completely constructed of six-member C6H4, C5H3 and 0Zn2C02 rings. There are two sites in the structure that are furthest away from any atom in the structure. The positions 0,0,0 and 0,0,1 / 2, have the carbon atom closest to 7.5 Á and the six positions at%, 0, 0 etc., have the carbon atom closest to 7.1 Á. Allowing a radius van der aals of the carbon atom of 1.7 Á, these accommodate spheres of a diameter of 12.8 and 10.8 Á, respectively, without touching any of the atoms of the structure. The latter are connected to produce continuous sinuous channels along 7a, 0.2, 0, 1/2, z. And Z . { see Figure 2c). In the material thus prepared, the cavities are occupied by at least 15 guests of DEF and 3 of H20 per unit of formula. The space occupied by the single guests is 81% of the cell volume. Indeed, gas adsorption studies indicate that this space is accessible to incoming host species and that the structure maintains its integrity in the absence of the guests. The. Evidence of host mobility and stability of the structure initially comes from a gravimetric thermal analysis study. A crystalline sample (2.9460 mg) was heated to a constant ratio of 5 ° C / min in air from 25-600 ° C. Two stages of weight loss were observed: the first corresponding to 47.85% occurred between 50 and 100 ° C, which can be attributed to the loss of host molecules (calculated 48.17%), while the second weight loss of 22.01% above 350 ° C is due to the decomposition of the structure. The lack of any weight loss between 100 and 350 ° C indicated that the structure is thermally stable in air at these temperatures. The comparison of the powder diffraction patterns of the X-rays of the MOF-177 thus synthesized, with samples of the material that has completely evacuated pores, shows that the periodicity and the structure of the structure are still preserved, confirming also the architectural stability of the structure in the absence of guests. To determine the capacity of this material to the gases, the adsorption isotherm of N2 (gr) was measured in samples of the MOF-177 where the pores were completely evacuated. The isotherm revealed a type I reversible behavior and showed no hysteresis when desorbing the pore gas (Figure 4). The accessible vacuum space is completely saturated with N2 molecules at relatively low pressures (P / Po ~ 0.2) with an adsorption of the total weight of 1.288 mg of N2 per gram of the completely evacuated structure which correlates with an estimated total number of N molecules of 52.7 per formula unit, and 422 per unit cell. When using the Dubinin-Raduskhvich equation, a pore volume of 1.59 cm3 / g (0.69 cm3 / cm3) was obtained. For a monolayer cover of N2, it was found that the Langmuir surface area was 4,500 m2 / g. It does not make sense that this surface area is determined with the same level of precision as that achieved for more established materials and that the pores of the MOF-177 are still found in the microporous regime (pore size diameter <20 Á) . However, the pore volume and surface area of the MOF-177 are well beyond those observed for the more porous crystalline zeolites and the porous carbon and significantly exceed the previous record for the crystalline MOF material (2,900 m2). / g and 0.59 cm3 / cm3 for MOF-5). The underlying topology of the MOF-177 is a network (6,3) coordinated with the center of the octahedron cluster of OZn4 (C02) as the site of coordination six and the BTB unit center as the site of the coordination 3. The structure of this network plays an important role in determining the pore size, obviating the formation of interpenetration structures as described above. The network (6, 3) coordinated more regular ("failure") is the one called by the structure of pyrite (pyr). However, two such networks can be interpenetrated in such a way that all the rings of one structure are penetrated by the links of the other (fully catenated) and vice versa, and indeed the MOF-150 based on this topology is presented as a pair of interpenetration networks (Figure 3). It is said that the second network that is completely linked to a given network is twice that network and if a network and its double have the same structure (as in the case of pyr) it is said to be self-dual. Although self-duality is a rare property of networks, it also occurs in network failure structures with a coordination of 3-4 and 6-, and in this way it is found that the interpenetration of two (or more) Copies of identical networks is a common obstacle for the synthesis of large pore materials. The present invention provides an effective strategy to avoid interpenetration (if desired) to use networks in which the structure of the double is very different. The underlying network MOF-177 (Figure 2b), which is called qom, is related to the pyr network: in that last coordinate sites 6 are arranged as centers of the spheres in the nearest cubic package (ie, in a lattice) cubic centered on the surface), in qom the corresponding arrangement is that of the closest hexagonal packing. However, the dual network, although it is also (6.3) coordinated, is very different, and since some of the edges link sites of the same coordination (Figure 3b), it is not a viable candidate for an MOF. Similarly, since qom is very different from its double, two such networks can not interpenetrate efficiently. Of course, the strategy to avoid the pyr network must be identified in the first instance. It can be demonstrated by simple geometric arguments that to avoid the formation of the pyr network (as in the MOF-150), when linking the octahedron OZn4 (C02) 6, aromatic tricarboxylates such as BTB known to have coplanar carboxylates should be used. in the MOFs. Given the exceptional stability, porosity and large pores of MOF-177, the ability to adsorb large organic molecules was tested. Traditionally, inclusion in porous materials has been achieved either through the in situ synthesis of the host, the synthesis of the structure to retain the host or the direct incorporation by absorption. The last two methods are not very suitable to produce new materials for separation. Moreover, in all these methods the use of polycrystalline materials raises the problem that the inclusion takes place in inter-crystalline regions instead of directly in the pores. This problem is avoided using monocrystalline samples of MOF-177 in all studies. Initial studies demonstrated the easy adsorption of bromobenzene, 1-bromonaphthalene, 2-bromonaphthalene, and 9-bromoanthracene from the solution (see Methods). However, it was difficult to directly determine the uniformity of distribution of these guests in the crystals. Accordingly, the inclusion of colored organic molecules in the unique crystals of MOF-177 was evaluated in order to be able to visually verify host incorporation directly. The crystals of MOF-177 were placed in a C60 toluene solution. After several days the configuration and integrity of the crystals remained intact and a change of color to deep red provided the optical evidence of the inclusion of C6o in the structure (Figure 5a). In order to test the presence of C6o, a complex of MOF-177-C6o was analyzed by Raman spectroscopy.

This vibratory spectrum was compared with the spectrum of the C6o load and with that of the evacuated MOF-177. The encapsulated fullerene complex exhibited bands in the same positions as the deosolvated MOF-177. However, the fullerene bands were enlarged and observed in positions slightly displaced from the Cso load indicating the interaction with the structure (Figure 5a). Inclusion uniformity was achieved by cutting a single crystal into three parts, thus exposing the inner core, and verifying that the middle portion was uniformly colored and that the Raman spectrum exhibited bands for both the structure and the host (Figure 5a) . In order to quantify the ability of MOF-177 to accommodate large polycyclic organic molecules, three dyes were selected, Orange Astrazon R, Nile Red and Reichardt dye. Saturated solutions of these compounds were used to color the crystals. The examination of a section from the center of the crystal was used to calibrate the uniformity of the colorant distribution (Figure 5b). In the cases of the Orange Astrazon R and the Red of the Nile, the cuts were colored uniformly indicating the free movement of the dye in the crystals. In the case of Reichardt's dye, this very large molecule only penetrated the outer part of the crystal. The maximum adsorption of these three dyes in the MOF-177 was determined as described in the methods section. Orange Astrazon R achieved more than 40% by weight in the crystals corresponding to 16 colored molecules in each unit cell. On average, two red Nile molecules entered each unit cell. Reichardt's dye, the largest of the three dyes studied, was the least effective when entering the crystal with only 1 molecule entering each unit cell on average. These results, taken with the diffusion experiments, clearly demonstrate the potential for size selectivity in a regime currently inaccessible with conventional porous materials. In summary, the present invention provides in one embodiment a general strategy based on exposed edges to achieve ultra porous crystals that have the highest capacity for gas storage. The importance of using non-dual networks to achieve non-interpenetration structures and therefore large, fully accessible pores has also been demonstrated. The MOF-177 is unique because it combines a high surface area with an ordered pore structure of an extra-large diameter, which, as illustrated by the inclusion of the dye, allows the binding of large organic molecules such as petroleum fragments. and drug molecules.

Adsorption properties of MOF-5 and related structures The adsorption properties of the MOF-5 (Figure 6A) in which groups are united [Ozn4] 6+ to an octahedron arrangement of groups [02C-C6H-C02] 2"(1, 4-benzenedicarboxylate, BDC) to form a robust and highly porous cubic structure.The motif of the MOF-5 structure and the Related compounds provide ideal platforms on which to adsorb gases, because the linkers are isolated from each other and accessible from all sides to adsorb molecules.The nature similar to the scaffolding of MOF-5 and its derivatives leads to apparent surface areas extraordinarily high (2500 to 3000 m2g) for these structures.On a practical level, the preparation of the MOFs is simple, not expensive and high performance.For example, the formation reaction for MOF-5 is 4Zn2 + + 3H2BDC + 80H "+ 3Zn40) BDC) 3? 7H20. The MOF family also has a high thermal stability (300 ° to 400 ° C). The MOF-5 and the metallic-organic isorreticular structure 6 (IRMOF-6) (Figure 6B) give capacity for other materials in the adsorption of methane at room temperature. Agree with this, the capacity for storage of hydrogen was determined. The adsorption of hydrogen gas was measured by MOF-5 at 78 K by introducing small amounts of H2 into a chamber containing the free form of the host material and monitoring the change in weight as a function of increased doses of H2. The measured adsorption isotherm shows a type I behavior, in which saturation is reached at low pressures followed by a pseudo platform at a higher H2 pressure with a maximum adsorption of 13.2 mg H2 per gram of MOF-5. The precise observed adsorption of H2 at a lower pressure indicates favorable adsorption interactions between the MOF-5 structure and the H2 molecules. It should be noted that, similar to the reversible adsorption of organic gases and vapors (N2, Ar, C02, CHC13, CC14, C6H6 and C6H_2) in MOF-5, the adsorbed H2 molecules can also be reversibly desorbed from the pores reducing the pressure. The adsorption of H2 was evaluated under conditions that mimic a typical application environment, that is, ambient temperature and pressures considered safe for the mobile fuel supply. A different adsorption apparatus was constructed in which a 10 g sample of a free host MOF-5 was loaded with H2 up to 20 bar and the change in weight was monitored as a function of adsorption and H2 release. The MOF-5 showed a substantial adsorption of H2 that increased linearly with the pressure, giving 1.0% weight at 20 bar (Figure 7). These findings demonstrate the potential of MOFs for H2 storage applications. It is expected that the isothermy at room temperature is approximately linear because the material is notoriously sub saturated with H2 in the range of pressure explored and, in principle, at higher pressures can adsorb more H2 at least up to the amount observed at 78K . To understand the H2 adsorption properties of MOF-5 and thus potentially control the characteristics of the H2 bond, INS spectroscopy of the rotation transitions of the adsorbed hydrogen molecules was carried out. The neutrons are dispersed in a non-elastic manner much more strongly by hydrogen than by any other element, which facilitates the observation of a rotating tunnel separation from the earth-balance state of the H2 molecule. This separation is similar to the ortho-para transition for free H2 and this mode is forbidden in optical spectroscopy. This separation is an extremely sensitive measurement of the surface area of rotation of the energy potential, a feature that has made it possible to determine fine details of hydrogen adsorption by INS in a wide variety of materials, including zeolites, nickel-phosphate nano-porous VSB-5 and carbon nanotubes. The INS spectra for MOF-5 are shown in Figure 8 for three H2 load levels corresponding to 4, 8 and 24 H2 per formula unit. First, the observed peaks are much more accurate than those found for H2 in zeolites, VSB-5 and carbon materials. Thus, the adsorption sites for H2 in MOF-5 are well defined compared to those in zeolites, in which the molecule has a variety of nearby binding sites available in energy. Second, spectrum richness immediately leads to the suggestion that more than one type of binding site is present in MOF-5 although rotational transitions other than 0-1 can be observed. Some progress can be made in the allocation of peaks with the use of a model for the rotation potential. For reasons of simplicity, the eigenvalues of energy are used for H2 rotations with two angular degrees of freedom in a double-minimum potential. In this way, peaks in 10.3 and 12.1 meV can be assigned to transitions 0-1 for the two sites. These are subsequently referred to as I and II, assigning the remaining peaks to transitions 0-2 and 1-2. These assignments are verified by comparing the INS spectrum of 4 D2 molecules per formula unit and scaling the rotation energy level diagram by the respective rotation constants of H2 and D2. It is found that the rotation barriers associated with sites I and II are 0.40 and 0.24 kcal mol 1, respectively. Inferences about the nature of link sites can also be produced based on the dependency of the INS spectrum on the H2 charge. Since the percentage load increases from 4 to 8 H2 per unit of the formula, the intensity of the band of 12.1 meV (site II) is doubled, while that of the band of 10.3 meV (site I) remains constant. Site I can be associated with Zn and site II with BDC linkers. In addition, the increases in the load (24 H2 per unit of the formula) (Figure 8, lower panel), show that the line at 12.1 meV is divided into four lines, which are associated with four slightly different sites with the BDC linker. This result suggests that additional increases in adsorption capacity could be achieved for these types of materials through the use of larger linkers. Indeed, a small peak close to 14.5 meV is observed in this high load corresponding to a small amount of solid H2 (for which the transition is presented '0-1 essentially in the value of free rotation of 14.7 meV), indicative of a saturation coverage in the MOF-5. The rotation barrier for the binding site near Zn is somewhat higher than those in the BDC, as can be expected, but also significantly lower than that for the Zn2 + cation with extra structure in zeolite ZnNaA, for which the rotation transition to 8 meV. Several factors contribute to this difference, including the different degrees of accessibility of the Zn and the strong electrostatic field in the super cell of zeolite. The barriers found for the MOF-5 are notoriously higher (0.40 and 0.24 kcal mol 1) than those found in carbons, including single wall nanotubes, in which it is 0.025 kcal mol 1. In addition, the rotation band in that case has a width of almost 2.5 meV compared to 0.5 meV in our case. This value corroborates the much lower mobility (and thus the stronger interaction) for H2 in the MOF-5 than in carbons. The results of INS for hydrogen in MOF-5 point to the importance of organic linkers to determine the levels of H2 adsorption. Accordingly, by using the same experimental procedure and the details outlined above for the measurements of ambient temperature in the MOF-5, the adsorption of H2 was determined in IRMOF-6 and IRMOF-8 (Figure 6, B and C) . Here, the specific adsorption of H2 is approximately doubled and quadrupled, respectively, for IRMOF-6 and -8 in relation to that found for MOF-5 at the same temperature (environment) and pressure (10 bar). Specifically, for IRMOF-8, H2 adsorption under these conditions is 20 mg H2 per gram (2.0% weight) - a capacity well above those found for "active" carbon (0.1% weight) (CECA , France) and "graphitic" carbon (0.3% weight). The percent adsorption found for MOF-5, IRMOF-6 and IRMOF-8 at room temperature and at 10 bar is equivalent to 1.9, 4.2, and 9.1 H2 per unit of the formula respectively. The capacity of these structures for hydrogen at room temperature is comparable with the highest capacity achieved for carbon nanotubes at cryogenic temperatures, although the capacity of these materials is very sensitive to the preparation conditions and seems to saturate at lower pressures.

METHODS 1. Synthesis Synthesis of Zn40 (BTB) 2 * 15 DEF 3 H20 (MOF-177): A solution of N, N-diethylformamide (DEF) containing 4,4 ', 4"-benzene-1, 3, 5 acid -triil-tribenzoic (H3BTB; 0.005 g, 1.14xl0 ~ 5 mol) and zinc nitrate hexahydrate (Zn (N03) 2 * 6H20 (0.020 g, 6.72xl0"5 mol) was placed in a Pyrex tube (10 mm x 8 mm outer diameter x inner diameter, 150 mm length) The sealed tube was heated at a ratio of 2.0 ° C / min to 100 °, kept at 100 ° C for 23 hours, and cooled to a 0.2 ° ratio C / min to room temperature Yellow crystals were formed in the form of a block of MOF-177 and isolated by washing with DEF (4x2 ml) and briefly drying in the air (ca 1 min) (0.005 g, 32% based on the binder). Calculated Analysis for C_29H_o_N? 5? 3iZn4 = Zn40 (BTB) 2 * (15 DEF) (3H20): C, 56. 96; H, 7 46; N, 7.73. Found: C, 56.90; H, 7.54; N, 7.67. FT-IR (KBr, 4000 ~ 400 cm "1: 1643 (s), 1607 (s), 1591 (s), 1546 (m), 1406 (s), 1300 (s), 1263 (s), 1213 (s), 1180 (w), 1105 (w), 1017 (w), 857 (w), 809 (w), 980 (s), 708 (w), 669 (w).

Synthesis of Zn4Q (BTB) 2 (MOF-178): A solution of 750 ml of N, N-dimethylformamide of 4,4 ', 4"-benzene-1,3,5-triyl-tribenzoic acid (H3BTB) was prepared (3.0 g, 6.8 mmol) and zinc nitrate hexahydrate (18.0 g, 60.5 mmol) and distributed in 30 equal portions in 60 ml glass jars The packages were then heated for 16 hours in an oven at 100 ° C, after which the pale yellow needles of the MOF-178 were harvested by filtration and rinsed with N, N-dimethylformamide followed by chloroform, immersion of the product in chloroform (60 ml) for more than 3 days, followed by evacuation. for 12 hours (25 degrees C, <1 mTorr) produced the activated material Zn0 (BTB) 2 (FW 1154 g / mol, yield 3.2 g, 81%) Similar results were observed when using other glass containers. using anhydrous acetonitrile as the exchange host, with little effect on the surface area of the final product.

Synthesis of Zn4Q [ZnX (BCPP)] 3 (MOF-180): Zinc nitrate hexahydrate was dissolved Zn (N03) 2 * 6H20 (3 mg, 0.01001 mmol) in 1.2 ml of DMF. 5, 15-bis (4-carboxyphenyl) zinc (II) orphyrin (H2BCPP) (1 g, 0.00164 mmol) was dissolved in 0.2 ml of DMF. Both solutions were placed in a tube that was subsequently evacuated / sealed and heated to 105 ° C at a rate of 5 ° C / min and maintained for 24 hours. The reaction tube was then cooled to a ratio of 0.2 ° C / min. Dark purple cubic crystals of MOF-180 were formed.

Synthesis of Zn4Q (BBC) 3 * (host) x (MOF-190); Zinc nitrate tetrahydrate [Zn (N03) 2 * 4H20] and 0.022 g of 1, 3, 5- (4 '-carboxy-4, 4'-biphenyl) benzene (0.033 mmol) were dissolved in 10 ml of N, N -dimethylformamide (DMF) in a scintillation vial and heated at 85 ° C for 24 hours. Colorless crystals were formed in block form on the walls of the vial and mechanically collected. The topology of the MOF-190 is the same as that of MOF-177.

Synthesis of Zn4Q (C26H1804) 3 * (DEF) __4 (H20)? 3.5 (IRMOF-17); S-6,6'-Dichloro-2,2 '-dietoxy-1,1' -bnaphthalene-4,4' -dicarboxylate (DCBP) (21 mg, 0.044 mmol) and Zn (N03) 2 * 4H20 ( 46 mg, 0.176 mmol) in DEF (4 ml) in a 20 ml scintillation vial. Cubic colorless crystals (10 mg, 0.003 mmol, 20%) were formed after heating the mixture at 100 ° C for 24 hours. Analysis' Calculated (%) for Zn40 (DCBP) 3 * (DEF) _4 (H20) 13.5; C, 51.84; H, 6.91; N, 5.72.

Found: C, 51.56; H, 6.07; N, 5.73. FT-IR (KBr 4000-500 cm "1): 3446 (br), 3102 (w), 3071 (w), 2980 (m), 2937 (w), 2881 (w), 1667 (s), 1646 ( s), 1572 (s), 1495 (w), 1447 (m), 1400 (m), 1321 (m), 1263 (m), 1222 (m), 1118 (m), 1087 (m), 909 ( w), 826 (w), 801 (w), 766 (w), 511 (w). Calculated Analysis (%) for Zn40 (C26H180) 3 * (DEF) 0.75 (H2O) 10 (chlorobenzene exchange product) : C, 48.48; H, 4.09; N, 0.52, Found: C, 48.35; H, 3.01; N, 0.62. 2. Surface area calculations Surface areas for faujasite and fragments of these structures were obtained through the Connolly Surface method, as implemented by the Cerius program. 3. Crystallographic studies on the MOF-177 The crystal (0.30 x 0.30 x 0.28 mm3) of Zn40 (BTB) 2 * (DEF) 15 (H20) 3 was sealed in a glass capillary and mounted on a Bruker SMART APEX CCD equipped diffractometer with a normal Mo-target X-ray focusing tube (? = 0.71073 Á) operated at 2000 W of energy (50 kV, 40 mA). The intensities of the X-rays were measured at 273 (2) K. A total of 1800 structures were collected with a scan width of 0.3 ° in? with an exposure time of 30 s / structure. The structures were integrated with the SAINT software package with a narrow structure algorithm. The integration of the data using trigonal unit cell produced a total of 173,392 reflections up to a maximum 2T value of 41.68 ° of which 12,530 were independent and 5233 were greater than 2s (J). The final cell constants were refined with 5049 reflections with 4.395 < 2T < 41,661. the analysis of the data showed an imperceptible decrease during the data collection. The correction to adsorption was applied using SADABS. The structure was dissolved by direct methods and the subsequent Fourier difference syntheses and refined with the SHELXTL software package (version 6.10), using the trigonal space group P31c (No. 163), = 37.072 (2) A, c = 30.033 (2) A with Z = 8 for the formula based on the elemental analysis. There were two independent Zn40 groups centered on the Wyckoff positions, 2 d and 6 h; the first of these was disordered on two possible orientations. The final refinement of the total matrix of smaller squares in F2 converged to Rl = 0.1538 (F> 4s (F)) and wR2 = 0.4639 (all data) with GOF = 1.397. Additional details are presented as Support Information. 4. Bromoarene diffusion The crystals were transferred from their mother liquor (DMF) to heptane. After 30 minutes, the heptane was removed and fresh heptane was added once more. This process was repeated three times in order to ensure the total displacement of the DMF molecules of the porous structure. The excess heptane was then removed and 1 ml of a heptane solution containing 0.007 M of each of the four bromoarenes was added. The crystals remained immersed in this solution for 90 minutes. The concentration of each bromoarene in the supernatant liquid was monitored by gas chromatography. The disappearance of the material indicates the adsorption of bromoarenos by the crystals of MOF-177.

. Quantification of dye adsorption The crystals of MOF-177 (3-5 mg) were placed in 0.15 ml of a saturated solution of dye in CH2C12.

Over a period of six days, the supernatant solution was removed, and replaced with fresh dye solution twenty times. After the sixth day of inclusion, the crystals were removed from the solution and rinsed three times with CH2C12. Individual crystals with a microgram scale were accurately weighed and absorbed in 40 to 60 μl of 0.1 N NaOH in methanol. This solution was transferred quantitatively to a 2 ml volumetric flask and methanol was added to obtain an accurate dilution. The analysis of UV-vis absorbency of the resulting solutions allowed the determination of the concentrations of the dyes and therefore of the amount of dye included in the structure of the MOF-177. Although the embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. On the contrary, the words used in the specification are words of description instead of limitation, and it is understood that various changes can be made without departing from the spirit and scope of the invention.

Claims (37)

1. CLAIMS 1. A metal-organic structure (MOF) comprising: a plurality of groups of metals, each of the groups of metals comprising one or more metal ions; and a plurality of charged multidentate linking ligands that connect the groups of adjacent metals, the plurality of multidentate linking ligands having a sufficient number of accessible sites for atomic or molecular adsorption so that the surface area of the metal-organic structure is greater than approximately 2,900 m2 / g.
2. 2. The metal-organic structure of claim 1 further comprising at least one ligand without linkage.
3. 3. The metal-organic structure of claim 1 wherein each metal group comprises 3 or more metal ions.
4. 4. The metal-organic structure of claim 1 wherein the plurality of multidentate linking ligands has a sufficient number of accessible sites for atomic or molecular adsorption so that the surface area is greater than 3,000 m2 / g.
5. The metal-organic structure of claim 1 wherein the plurality of multidentate linking ligands has a sufficient number of accessible sites for atomic or molecular adsorption so that the surface area is greater than about 3,500 m2 / g.
6. 6. The metal-organic structure of claim 1 wherein the plurality of multidentate linking ligands has a sufficient number of accessible sites for atomic or molecular adsorption so that the surface area is greater than about 4,000 m2 / g.
7. The metal-organic structure of claim 1 wherein each ligand of the plurality of multidentate ligands includes 2 or more carboxylates.
8. The metal-organic structure of claim 1 wherein the metal ion selected from the group consisting of Group 1 through 16 of metals of the Periodic Table of the IUPAC Elements including actinides and lanthanides, and combinations thereof.
9. The metal-organic structure of claim 1 wherein the metal ion is selected from the group consisting of Li +, Na +, K +, Rb +, Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Sc3 +, Y3 +, Ti +, Zr4 +, Hf4 +, V4 +, V3 +, V2 +, Nb3 +, Ta3 +, Cr3 + Mo3 +, W3 +, Mn3 +, Mn2 +, Re3 +,, Re2 +, Fe3 +, Fe2 +, Ru3 +, Ru2 +, 0s3 + Os2 +, Co3 +, Co2 +, Rh2 +, Rh +, Ir +, Ir +, Ni2 +, Ni +, Pd2 +, Pd +, Pt2 +, Pt +, Cu2 +, Cu +, Ag +, Ag +, Au +, Zn2 +, Cd2 +, Hg2 +, Al3 +, Ga3 +, In3 +, Tl3 +, Si4 +, Si2 +, Ge4 +, Ge2 +, Sn4 +, Sn2 +, Pb +, Pb2 +, As5 +, As3 +, As +, Sb5 +, Sb3 +, Sb +, Bi5 +, Bi3 +, Bi +, and combinations thereof.
10. 10. The metal-organic structure of claim 1 wherein the metal group has the formula MmXn wherein M is a metal ion, X is selected from the group consisting of an anion from Group 14 to Group 17, m is an integer of 1 to 10, and n is a selected number for balancing the charge of the metal group so that the metal group has a predetermined electric charge.
11. The metal-organic structure of claim 10 wherein X is selected from the group consisting of 0, / N, and S.
12. The metal-organic structure of claim 10 wherein X is O and m is 4.
13. 13 The metal-organic structure of claim 10 wherein M is selected from the group consisting of Mg2 +, Ca2 +, Sr2 +, Ba2 +, V2 +, V3 +, V4 +, V5 +, Mn2 +, Re2 +, Fe2 +, Fe3 +, Ru3 +, Ru2 +, Os2 +, Co2 +, Rh2 +, Ir2 +, Ni2 +, Pd2 +, Pt2 +, Cu2 +, Zn2 +, Cd2 +, Hg2 +, Si2 +, Ge2 +, Sn2 +, and Pb2 +.
14. 14. The metallic-organic structure of claim 10 wherein the metal group has the formula Zn40.
15. 15. The metal-organic structure of claim 1 wherein the ligand without linkage is selected from the group consisting of O2", sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate , phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, sulfur, hydrogen sulfate, selenide, selenate, hydrogen selenate, telluride, telurate, hydrogen telurate, nitride, phosphide, arsenide, arsenate, arsenate of hydrogen, dihydrogen arsenate, antimony, antimonate, hydrogen antimonate, dihydrogen antimonate, fluoride, boride, borate, hydrogen borate, perchlorate, chlorite, hypochlorite, perbromate, bromite, hypobromite, periodate, iodite, hypoiodite; and mixtures thereof.
16. 16. The metal-organic structure of claim 1 further comprising a host species.
17. 17. The metallic-organic structure of claim 16 wherein the host species increases the surface area of the metal-organic structure.
18. 18. The metal-organic structure of claim 16 wherein the host species is selected from the group consisting of organic molecules with a molecular weight less than 100 g / mol, organic molecules with a molecular weight less than 300 g / mol, molecules organic compounds with a molecular weight of less than 600 g / mol, organic molecules with a molecular weight greater than 600 g / mol, organic molecules containing at least one aromatic ring, polycyclic aromatic hydrocarbons, and metal complexes having the formula MmXn wherein M is a metal ion, X is selected from the group consisting of an anion from Group 14 to Group 17, m is an integer from 1 to 10, and n is a selected number to balance the charge of the metal group so that the group Metallic has a predetermined electric charge; and combinations thereof.
19. 19. The metal-organic structure of claim 1 further comprising an interpenetrating metal-organic structure that increases the surface area of the metal-organic structure.
20. The metal-organic structure of claim 1 wherein the multidentate linking ligand has more than 16 atoms that are incorporated into aromatic rings or non-aromatic rings.
21. 21. The metal-organic structure of claim 1 wherein the multidentate linking ligand has more than 20 atoms that are incorporated into aromatic rings or non-aromatic rings.
22. 22. The metal-organic structure of claim 1 further comprising an adsorbed chemical species.
23. 23. The metallic-organic structure of claim 20 wherein the adsorbed chemical species is selected from the group consisting of ammonia, carbon dioxide, carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen, argon, organic dyes , organic polycyclic molecules, and combinations thereof.
24. 24. A metal-organic structure (MOF) comprising: a plurality of groups of metals, each metal group comprising one or more metal ions; and at least one multidentate linking ligand having the formula I: i; or, substituted variations of formula I.
25. 25. A metallic-organic structure (MOF) comprising: a plurality of groups of metals, each metal group comprising one or more metal ions; and at least one multidentate linking ligand having the formula II: ii; or, substituted variations of formula II.
26. 26. A metal-organic structure (MOF) comprising: a plurality of groups of metals, each metal group comprising one or more metal ions; and at least one multidentate linking ligand having the formula III: (C34H1204N4Zn) III. or, substituted variations of formula III.
27. 27. A method for forming a metal-organic structure (MOF), the method comprising: combining a solution comprising a solvent and metal ions selected from the group consisting of Group 1 to 16 metals including actinides and lanthanides, and combinations of the same with a multidentate binding ligand, the multidentate ligand being selected in such a way that the surface area of the metal-organic structure is greater than 2,900 m2 / g.
28. The method of claim 27 wherein each ligand of the plurality of multidentate ligands includes 2 or more carboxylates.
29. 29. The method of claim 27 wherein the multidentate linking ligand has more than 16 atoms that are incorporated into aromatic rings or non-aromatic rings.
30. 30. The method of claim 27 wherein the multidentate linking ligand is described by the formula I: I; or, substituted variations of formula I.
31. 31. The method of claim 27 wherein the multidentate linking ligand is described by formula II: II; or, substituted variations of formula I.
32. 32. The method of claim 27 wherein the solvent comprises a component selected from ammonia, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1, 2-Dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine, N, N-dimethylformamide, N-diethylformamide, methanol, ethanol, propanol, alcohols, dimethylsulfoxide, chloroform, bromoform, dibromomethane, iodoform, diiodomethane, halogenated organic solvents, N, N- dimethylacetamide, N, N-diethylacetamide, l-methyl-2-pyrrolidinone, amide solvents, methylpyridine, dimethylpyridine, diethylether and mixtures thereof.
33. 33. The method of claim 27 wherein the solution further comprises a space filler.
34. 34. The method of claim 27 wherein the space filler is selected from the group consisting of: a. alkylamines and their corresponding alkyl ammonium salts, containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; b. arylamines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings; c. alkyl phosphonium salts, containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; d. aryl phosphonium salts having from 1 to 5 phenyl rings; and. organic alkyl acids and their corresponding salts containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; F. organic aryl acids and their corresponding salts having from 1 to 5 phenyl rings; g. aliphatic alcohols containing linear, branched or cyclic aliphatic groups having from 1 to 20 carbon atoms; h. aryl alcohols having from 1 to 5 phenyl rings; i. inorganic anions of the group consisting of sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, O2", sulfur diphosphate, hydrogen sulfate, selenide, selenate, hydrogen selenate, telluride, telurate, hydrogen telurate, nitride, phosphide, arsenide, arsenate, hydrogen arsenate, dihydrogen arsenate, antimony, antimonate, hydrogen antimonate, antimonate of dihydrogen, fluoride, boride, borate, hydrogen borate, perchlorate, chlorite, hypochlorite, perbromate, bromite, hypobromite, periodate, iodite, hypoiodite and the corresponding acids and salts of said inorganic anions; j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, triethylamine, trifluoromethylsulfonic acid, N, N-dimethylformamide, N, N-diethylformamide, dimethyl sulfoxide, chloroform, bromoform, dibromomethane, iodoform, diiodomethane, halogenated organic solvents, N, N-dimethylacetamide, N, N-diethylacetamide, l-methyl-2-pyrrolidinone , amide solvents, methylpyridine, dimethylpyridine, diethylether and mixtures thereof.
35. 35. The method of claim 27 further comprising contacting the metal-organic structure with a host species so that the host species is at least partially incorporated into the metal-organic structure.
36. 36. A method for forming a metal-organic structure (MOF), the method comprising: combining a solution comprising a solvent and metal ions selected from the group consisting of metals from Group 1 to 16 of the Periodic Table of Elements IUPAC with a multidentate binding ligand having the formula III: (C34H? 204N4Zn) III; or substituted variations of formula I.
37. 37. A method for adsorbing a host species with a metal-organic structure, the method comprising: contacting a metal-organic structure with a host species, the metal-organic structure having inorganic groups of [0Zn4] d + bound with multidentate ligands which include 1 or 2 groups of substituted or unsubstituted aromatic rings.