EP2443133A2 - Réseaux organométalliques et leurs procédés de fabrication - Google Patents

Réseaux organométalliques et leurs procédés de fabrication

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Publication number
EP2443133A2
EP2443133A2 EP10790310A EP10790310A EP2443133A2 EP 2443133 A2 EP2443133 A2 EP 2443133A2 EP 10790310 A EP10790310 A EP 10790310A EP 10790310 A EP10790310 A EP 10790310A EP 2443133 A2 EP2443133 A2 EP 2443133A2
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EP
European Patent Office
Prior art keywords
framework
organo
metal
irmof
metallic
Prior art date
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EP10790310A
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German (de)
English (en)
Other versions
EP2443133A4 (fr
Inventor
Christian J. Doonan
William Morris
Omar M. Yaghi
Bo Wang
Hexiang Deng
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University of California
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University of California
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Publication of EP2443133A2 publication Critical patent/EP2443133A2/fr
Publication of EP2443133A4 publication Critical patent/EP2443133A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the disclosure provides organometallic frameworks for gas separation, storage, and for use as sensors with chemical stability.
  • the disclosure provides chemically stable open frameworks comprising designated elements including, but not limited to, zirconium, titanium, aluminum, and magnesium ions.
  • the disclosure encompasses all open framework materials that are constructed from organic links bridged by multidentate organic or inorganic cores. Including all classes of open framework materials; covalent organic frameworks (COFs), zeolitic imidazolate frameworks (ZIFs) and metal organic frameworks (MOFs) and all possible resulting net topologies as described within the reticular chemistry structure resource
  • the disclosure provides stable frameworks utilizing these materials in industrial harsh conditions. Such material will have a variety of uses in applications such as gas storage and separation, chemical and biological sensing, molecular reorganization and catalysis.
  • the disclosure provides an organo-metallic framework comprising the general structure M-L-M, wherein M is a framework metal and wherein L is a linking moiety having an heterocyclic carbene or an imine group linked to a modifying metal.
  • the imine group comprises a chelating group.
  • the linking moiety is metallated prior to reacting with the framework metal.
  • the linking moiety comprises an N-heterocyclic carbene.
  • the framework comprises a covalent organic framework (COF) , a zeolitic imidizole framework (ZIF) , or a metal organic framework (MOF) .
  • the imine group is post-framework chelated to a metal.
  • the framework metal is selected from the group consisting of Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Au + , Zn 2+ , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ .
  • the modifying metal is selected from the group consisting of Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Au + , Zn 2+ , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ .
  • the modifying metal extends into a pore of the framework.
  • the framework comprises a guest species, however, in other embodiments, the framework lacks a guest species while remaining stable.
  • the disclosure also provides a method of making an organo-metallic framework comprising reacting an organic framework comprising an amine group with a 2- pyridinecarboxaldehyde to obtain an imine functionalized linking moiety and contacting the framework with a metal that chelates to the imine functionalized linking moiety.
  • the organo-metallic frameworks of the disclosure are usful for gas separation and catalysis. Accordingly, the disclosure provides gas sorption materials and devices comprising an organo-metallic framework of the disclosure as well as catalytic compositions and devices.
  • Figure 1 shows PXRD patterns for A, B, and C along with a simulated pattern for A (bottom) .
  • Figure 2 shows Ar gas adsorption isotherms for A (solid circles top portion of graph) , B (open circles top portion) , and C (lower line) at 87 K, with adsorption and desorption points represented by solid and open circles, respectively.
  • Figure 3 shows Pd K-edge EXAFS Fourier transforms and (inset) EXAFS spectra for C. Solid lines show the experimental data and dotted lines show the best fits using the parameters given in Table 1.
  • Figure 4 shows Pd K-edge near edge spectra of : Dichloro (N- (2-pyridylmethylene) aniline-N, N ' ) Palladium (II) (a) (Zn 4 O) 3 (BDC-C 6 H 5 N 2 PdCl 2 ) S (BTB) 4 (b) and PdCl 2 (CH 3 CN) (c) .
  • Figure 5 shows ESI mass spectrum of imine ligand fragment .
  • Figure 6A-C show structures of IRMOF-76 and -77.
  • (a) Single crystal structure of IRMOF-76 (Zn 4 O (C 23 H 15 N 2 O 4 ) 3 (X) 3 (X BF 4 , PF 6 , OH)) .
  • Figure 7 shows N 2 isotherm measurements for IRMOF-77 measured at 77 K.
  • Figure 8 shows PXRD patterns of as-synthesized IRMOF-77 (middle) , quinoline-exchanged IRMOF-77 (bottom) , and simulated PXRD pattern from single crystal X-ray structure (top) .
  • Figure 9 is an ORTEP drawing of the asymmetric unit of the IRMOF-76. All ellipsoids are displayed at the 10% probability level except for hydrogen atoms.
  • Figure 10 is an ORTEP drawing of the IRMOF-77, with a half of Zn 4 O unit and one link. All ellipsoids are displayed at the 30% probability level except for hydrogen atoms.
  • Figure 11 shows PXRD patterns of as-synthesized IRMOF-76 (black) and simulated IRMOF-15, 16 (blue and red, respectively) from single crystal X-ray structures.
  • Figure 12 is a TGA trace of as-synthesized IRMOF-76.
  • the huge weight loss up to 150 0 C corresponds to the loss of guest solvents (DMF, H 2 O) .
  • a significant weight loss from 300 to 400 0 C indicates the decomposition of the material.
  • Figure 13 is a TGA trace of as-synthesized IRMOF-77.
  • the huge weight loss up to 150 0 C corresponds to the loss of guest solvents (DEF, pyridine, and H 2 O) .
  • the material loses coordinated molecules (pyridines) up to 250 0 C, and a significant weight loss from 300 to 400 0 C indicates the decomposition of the material.
  • Figure 14 is a TGA trace of activated IRMOF-77. The weight loss around 180 0 C is attributed to the partial loss of coordinated pyridine (calcd. 8.6% for full loss) .
  • Figure 15 is a TGA trace of organometallic linker Ll. The weight loss (9.7%) up to 250 0 C is in accordance with the loss of pyridine (calcd. 9.3%) to form dimer S4.
  • Figure 16 shows an activated Zr-MOF.
  • Figure 17 shows a stability test in the presence of various chemicals .
  • Figure 18 shows reactions useful for generating imines as chelators.
  • Figure 19 shows a reversible imine formation in a framework .
  • Figure 20 shows PXRD data for imines.
  • Figure 21 shows solid state NMR data for imines.
  • Figure 22A-B shows SA of imine reactions.
  • Figure 23 shows data on reversal of imine reactions.
  • Figure 24 shows ligands useful in the methods and compositions of the disclosure.
  • Metal-organic frameworks have been synthesized in the art, however, these prior MOFs lack chemical stability or suffer from low porosity and restricted cages/channels, which drastically limit their use in industry.
  • Precise control of functionality in metal complexes is commonly achieved in molecular coordination chemistry. Developing the analogous chemistry within extended crystalline structures remains a challenge because of their tendency to lose order and connectivity when subjected to chemical reactions.
  • Metal-organic frameworks (MOFs) are ideal candidates for performing coordination chemistry in extended structures because of their highly ordered nature and the flexibility with which the organic links can be modified. This is exemplified by the successful application of the isoreticular principle, where the functionality and metrics of an extended porous structure can be altered without changing its underlying topology.
  • the disclosure provides a method of generating organo-metallic frameworks via two methods.
  • a first method utilizes a post-framework synthesis reaction, wherein a reactive side-group a linking ligand serves as a metal chelator to chelate a metal into the framework.
  • the second method utilizes a pre-framework synthesis methodology wherein the linking ligand is modified to comprise a metal, wherein the metal-ligand is then reacted to form the framework.
  • the disclosure also includes compositions that result from these methods as well as devices incorporating the compositions.
  • the disclosure provides a method of generating stable organo-metallic frameworks comprising MOFs, ZIFs, or COFs using a sequence of chemical reactions.
  • One advantage of the frameworks of the disclosure is that the desired metal centers and organic links can be easily incorporated so that the porosity, functionality and channel environment can be readily adjusted and tuned for targeted functions and application .
  • the disclosure provides a precursor organic framework comprising a linking moiety having a reactive side group useful for chelating a metal.
  • the reactive side group comprises an amine group.
  • the precursor organic framework can then be reacted with a metal to form an organo-metallic framework through reaction of the framework with a post-framework reaction chelating process.
  • MOF material chosen from the vast number reported in the literature, can be subjected to a sequence of chemical reactions to make a covalently bound chelating ligand, which can subsequently be used for the complexation of Pd(II) .
  • the framework comprising the chelated metal can then be further reacted to incorporate additional functionality (e.g., space constraints, charge and the like) oto the pores of the framework.
  • This isoreticular metalation is a significant first step in harnessing the intrinsic advantages of molecular coordination chemistry for functionalization of extended solids.
  • the metal-complexed MOF can then serve as an building block for additional reactions of the chelated-metal to form further functionalized frameworks.
  • the disclosure provides an alternative method for generating organo-metallic frameworks.
  • covalently linked organometallic complexes within the pores of MOFs are generated.
  • the method metalates a reactive carbene on a linking ligand, followed by deprotecting the linking clusters and reacting the metalated linking ligand with a metal.
  • a carbene (NHC) 5 precursor is metalated (Ll, Scheme 2) and then assembled into the desired metalated MOF structure (e.g., IRMOF-77, Scheme 2) .
  • these metalated MOFs can be further modified to increase the functionality (size, charge etc.) of the pores of the framework.
  • the methods of the disclosure utilize process depicted in Scheme 3 to produce an organo- metallic MOF.
  • cluster refers to identifiable associations of 2 or more atoms. Such associations are typically established by some type of bond--ionic, covalent, Van der Waal, and the like.
  • a “linking cluster” refers to one or more reactive species capable of condensation comprising an atom capable of forming a bond between a linking moiety substructure and a metal group or between a linking moiety and another linking moiety. Examples of such species are selected from the group consisting of boron, oxygen, carbon, nitrogen, and phosphorous atoms.
  • the linking cluster may comprise one or more different reactive species capable of forming a link with a bridging oxygen atom.
  • a linking cluster can comprise CO 2 H, CS 2 H, NO 2 , SO 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , Sn(SH) 4 , PO 3 H, AsO 3 H, AsO 4 H, P(SH) 3 , As(SH) 3 , CH(RSH) 2 , C(RSH) 3 , CH(RNH 2 J 2 , C(RNH 2 J 3 , CH(ROH) 2 , C(ROH) 3 , CH(RCN) 2 , C(RCN) 3 , CH(SH) 2 , C(SH) 3 , CH (NH 2 ) 2 , C(NH 2 J 3 , CH(OH) 2 , C(OH) 3 , CH(CN) 2 , and C(CN) 3 , wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 , where
  • ligans for MOFs contain carboxylic acid functional grapus .
  • the disclosure includes cycloalkyl or aryl substructures that comprise 1 to 5 rings that consist either of all carbon or a mixture of carbon, with nitrogen, oxygen, sulfur, boron, phosphorous, silicon and aluminum atoms making up the ring.
  • a "linking moiety” refers to a mono-dentate or polydentate compound that bind a transition metal or a plurality of transition metals, respectively.
  • a linking moiety comprises a substructure comprising an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, and in which a linking cluster (e.g., a multidentate function groups) are covalently bound to the substructure.
  • a linking cluster e.g., a multidentate function groups
  • a cycloalkyl or aryl substructure may comprise 1 to 5 rings that comprise either of all carbon or a mixture of carbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/or aluminum atoms making up the ring.
  • the linking moiety will comprise a substructure having one or more carboxylic acid linking clusters covalently attached.
  • the carboxylic acid cluster may be protected during certain reactions and then deprotected prior to reaction with a metal .
  • a line in a chemical formula with an atom on one end and nothing on the other end means that the formula refers to a chemical fragment that is bonded to another entity on the end without an atom attached. Sometimes for emphasis, a wavy line will intersect the line.
  • the linking moiety substructure is selected from any of the following:
  • the linking moiety has a structure:
  • linking moieties include those set forth below:
  • R 1 - R 15 is H, NH 2 , COOH, CN, NO 2 , F, Cl, Br, I, S, 0, SH, SO 3 H, PO 3 H 2 , OH, CHO, CS 2 H, SO 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , PO 3 H, AsO 3 H, AsO 4 H, P(SH) 3 , As(SH) 3 , CH(RSH) 2 , C(RSH) 3 , CH(RNH 2 J 2 , C(RNH 2 J 3 , CH(ROH) 2 , C(ROH) 3 , CH(RCN) 2 , C(RCN) 3 ,
  • Multidentate cores of the disclosure can comprise substituted or unsubstituted aromatic rings, substituted or unsubstituted heteroaromatic rings, substituted or unsubstituted nonaromatic rings, substituted or unsubstituted nonaromatic heterocyclic rings, or saturated or unsaturated, substituted or unsubstituted, hydrocarbon groups.
  • the saturated or unsaturated hydrocarbon groups may include one or more heteroatoms.
  • the multidentate core can comprise the following examples:
  • R1-R15 are each independently H, alkyl, aryl, OH, alkoxy, alkenes, alkynes, phenyl and substitutions of the foregoing, sulfur-containing groups (e.g., thioalkoxy) , silicon-containing groups, nitrogen-containing groups (e.g., amides), oxygen-containing groOups (e.g., ketones, and aldehydes) , halogen, nitro, amino, cyano, boron-containing groups, phosphorous-containing groups, carboxylic acids, or esters, Al, A2, A3, A4, A5 and A6 are each independently absent or any atom or group capable of forming a stable ring structure, and T is a tetrahedral atom (e.g., a carbon, silicon, germanium, tin and the like) or a tetrahedral group or cluster.
  • sulfur-containing groups e.g., thioalkoxy
  • Linking moieties for MOF structure that may be functionalized to include a reactive imine group for chelating a metal include those below:
  • the R group is imine functionalized to promote chelating of a post-synthesis metal .
  • Linking moieties for ZIF structures that may be functionalized to include a reactive imine group or which may be modified to form an N-heterocyclic carbene for include those below:
  • Linking moieties for COF structures that may be functionali zed to include a reactive imine group or which may be modi fied to form an N-heterocyclic carbene for include those below :
  • R1-R15 are each independently H, alkyl, aryl, OH, alkoxy, alkenes, alkynes, phenyl and substitutions of the foregoing, sulfur-containing groups (e.g., thioalkoxy) , silicon-containing groups, nitrogen-containing groups (e.g., amides), oxygen-containing groOups (e.g., ketones, and aldehydes) , halogen, nitro, amino, cyano, boron-containing groups, phosphorous-containing groups, carboxylic acids, or esters, Al, A2, A3, A4, A5 and A6 are each independently absent or any atom or group capable of forming a stable ring structure, and T is a tetrahedral atom (e.g., a carbon, silicon, germanium, tin and the like) or a tetrahedral group or cluster.
  • sulfur-containing groups e.g., thioalkoxy
  • All the aforementioned organic links that possess appropriate reactive functionalities can be chemically transformed by a suitable reactant post framework synthesis to further functionalize the pores, by modifying the organic links within the framework post-synthetically, access to functional groups that were previously inaccessible or accessible only through great difficulty and/or cost is possible and facile.
  • Post framework reactants include all known organic transformations and their respective reactants; rings of 1-20 carbons with functional groups including atoms such as N, S, O.
  • the post-framework reactant is used to generate a chelating group for the addition of a metal.
  • the disclosure includes the chelation of all metals that may chelate to and add a functional group or a combination of previously existing and newly added functional groups. All reactions that result in tethering an organometallic complex to the framework for use, for example, as a heterogenous catalyst.
  • metal and metal containing compounds that may chelate to and add functional groups or a combination of previously existing and newly added functional groups are also useful. Reaction that result in the tethering of organometallic complexes to the framework for use as, for example, a heterogeneous catalyst can be used.
  • post framework reactants include, but are not limited to, heterocyclic compounds. In one embodiment, the post framework reactant can be a saturated or unsaturated heterocycle.
  • heterocycle used alone or as a suffix or prefix, refers to a ring-containing structure or molecule having one or more multivalent heteroatoms, independently selected from N, O and S, as a part of the ring structure and including at least 3 and up to about 20 atoms in the ring(s) .
  • Heterocycle may be saturated or unsaturated, containing one or more double bonds, and heterocycle may contain more than one ring. When a heterocycle contains more than one ring, the rings may be fused or unfused. Fused rings generally refer to at least two rings share two atoms therebetween. Heterocycle may have aromatic character or may not have aromatic character.
  • heterocyclic group refers to a radical derived from a heterocycle by removing one or more hydrogens therefrom.
  • heterocyclyl used alone or as a suffix or prefix, refers a monovalent radical derived from a heterocycle by removing one hydrogen therefrom.
  • heteroaryl used alone or as a suffix or prefix, refers to a heterocyclyl having aromatic character.
  • Heterocycle includes, for example, monocyclic heterocycles such as: aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane 2, 3-dihydrofuran, 2, 5-dihydrofuran tetrahydrofuran, thiophane, piperidine, 1, 2, 3, 6-tetrahydro-pyridine, piperazine, morpholine, thiomorpholine, pyran, thiopyran, 2,3- dihydropyran, tetrahydropyran, 1, 4-dihydropyridine, 1,4- dioxane, 1,3-dioxane, dioxane, homopiperidine, 2,3,4,7- tetrahydro-lH-azepine homopiperazine, 1, 3-dio
  • heterocycle includes aromatic heterocycles (heteroaryl groups) , for example, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole, pyrazole, isothiazole, isoxazole, 1,2,3- triazole, tetrazole, 1, 2, 3-thiadiazole, 1, 2, 3-oxadiazole, 1,2,4-triazole, 1, 2, 4-thiadiazole, 1, 2, 4-oxadiazole, 1,3,4- triazole, 1, 3, 4-thiadiazole, and 1, 3, 4-oxadiazole .
  • aromatic heterocycles heteroaryl groups
  • heterocycle encompass polycyclic heterocycles, for example, indole, indoline, isoindoline, quinoline, tetrahydroquinoline, isoquinoline, tetrahydroisoquinoline, 1, 4-benzodioxan, coumarin, dihydrocoumarin, benzofuran, 2, 3-dihydrobenzofuran, isobenzofuran, chromene, chroman, isochroman, xanthene, phenoxathiin, thianthrene, indolizine, isoindole, indazole, purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine, perimidine, phenanthroline, phenazine, phenothiazine, phenoxazine, 1,2- benzisoxazole, benzothiophene, benzo
  • heterocycle includes polycyclic heterocycles wherein the ring fusion between two or more rings includes more than one bond common to both rings and more than two atoms common to both rings.
  • bridged heterocycles include quinuclidine, diazabicyclo [2.2.1 ] heptane and 7- oxabicyclo [2.2.1] heptane .
  • Heterocyclyl includes, for example, monocyclic heterocyclyls, such as: aziridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl, dioxolanyl, sulfolanyl, 2, 3-dihydrofuranyl, 2, 5-dihydrofuranyl, tetrahydrofuranyl, thiophanyl, piperidinyl, 1,2,3,6- tetrahydro-pyridinyl, piperazinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, 2, 3-dihydropyranyl, tetrahydropyranyl, 1, 4-dihydropyridinyl, 1, 4-diopyridin
  • heterocyclyl includes aromatic heterocyclyls or heteroaryl, for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, furazanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, isothiazolyl, isoxazolyl, 1, 2, 3-triazolyl, tetrazolyl, 1, 2, 3-thiadiazolyl, 1, 2, 3-oxadiazolyl, 1,2,4- triazolyl, 1, 2, 4-thiadiazolyl, 1, 2, 4-oxadiazolyl, 1,3,4- triazolyl, 1, 3, 4-thiadiazolyl, and 1,3,4 oxadiazolyl.
  • heterocyclyl encompasses polycyclic heterocyclyls (including both aromatic or non-aromatic) , for example, indolyl, indolinyl, isoindolinyl, quinolinyl, tetrahydroquinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, 1, 4-benzodioxanyl, coumarinyl, dihydrocoumarinyl, benzofuranyl, 2, 3-dihydrobenzofuranyl, isobenzofuranyl, chromenyl, chromanyl, isochromanyl, xanthenyl, phenoxathiinyl, thianthrenyl, indolizinyl, isoindolyl, indazolyl, purinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl,
  • heterocyclyl includes polycyclic heterocyclyls wherein the ring fusion between two or more rings includes more than one bond common to both rings and more than two atoms common to both rings.
  • bridged heterocycles include quinuclidinyl, diazabicyclo [2.2.1 ] heptyl; and 7-oxabicyclo [2.2.1 ] heptyl .
  • Metal ions that can be used in the synthesis of frameworks of the disclosure include Li + , Na + , Rb + , Mg 2+ , Ca 2+ ,
  • Metal ions can be introduced into open frameworks, MOFs, ZIFs and COFs, via complexation with the functionalized organic linkers (e.g., imine or N-heterocyclic carbene) in framework backbones or by simple ion exchange. Therefore, any metal ions from the periodic table can be introduced.
  • the preparation of the frameworks of the disclosure can be carried out in either an aqueous or non-aqueous system.
  • the solvent may be polar or non-polar as the case may be .
  • the solvent can comprise the templating agent or the optional ligand containing a monodentate functional group.
  • non-aqueous solvents examples include n-alkanes, such as pentane, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, cyanobenzene, aniline, naphthalene, naphthas, n-alcohols such as methanol, ethanol, n-propanol, isopropanol, acetone, 1,3, - dichloroethane, methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N-methylpyrollidone, dimethylacetamide, diethylformamide, thiophene, pyridine, ethanolamine, triethylamine, ethlenediamine, and the like.
  • n-alkanes such as pentane, hexane, benzene, toluene,
  • Templating agents can be used in the methods of the disclosure. Templating agents employed in the disclosure are added to the reaction mixture for the purpose of occupying the pores in the resulting crystalline base frameworks. In some variations of the disclosure, space-filling agents, adsorbed chemical species and guest species increase the surface area of the metal-organic framework.
  • Suitable space-filling agents include, for example, a component selected from the group consisting of: (i) alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (ii) aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings; (iii) alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (iv) aryl phosphonium salts, having from 1 to 5 phenyl rings; (v) alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (vi) aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings; (vii) aliphatic alcohols,
  • Crystallization can be carried out by leaving the solution at room temperature or in isothermal oven for up to 300 °C; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and/or transferring the solution to a closed vessel and heating to a predetermined temperature.
  • the device includes a sorbent comprising a framework provided herein or obtained by the methods of the disclosure.
  • the uptake can be reversible or non-reversible.
  • the sorbent is included in discrete sorptive particles.
  • the sorptive particles may be embedded into or fixed to a solid liquid- and/or gas-permeable three- dimensional support.
  • the sorptive particles have pores for the reversible uptake or storage of liquids or gases and wherein the sorptive particles can reversibly adsorb or absorb the liquid or gas.
  • a device provided herein comprises a storage unit for the storage of chemical species such as ammonia, carbon dioxide, carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen, argon, organic dyes, polycyclic organic molecules, and combinations thereof.
  • chemical species such as ammonia, carbon dioxide, carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen, argon, organic dyes, polycyclic organic molecules, and combinations thereof.
  • methods for the sorptive uptake of a chemical species includes contacting the chemical species with a sorbent that comprises a framework provided herein.
  • the uptake of the chemical species may include storage of the chemical species.
  • the chemical species is stored under conditions suitable for use as an energy source.
  • methods for the sorptive uptake of a chemical species which includes contacting the chemical species with a device provided described herein.
  • Natural gas is an important fuel gas and it is used extensively as a basic raw material in the petrochemical and other chemical process industries.
  • the composition of natural gas varies widely from field to field.
  • Many natural gas reservoirs contain relatively low percentages of hydrocarbons (less than 40%, for example) and high percentages of acid gases, principally carbon dioxide, but also hydrogen sulfide, carbonyl sulfide, carbon disulfide and various mercaptans.
  • Removal of acid gases from natural gas produced in remote locations is desirable to provide conditioned or sweet, dry natural gas either for delivery to a pipeline, natural gas liquids recovery, helium recovery, conversion to liquefied natural gas (LNG), or for subsequent nitrogen rejection.
  • LNG liquefied natural gas
  • CO2 is corrosive in the presence of water, and it can form dry ice, hydrates and can cause freeze-up problems in pipelines and in cryogenic equipment often used in processing natural gas. Also, by not contributing to the heating value, CO 2 merely adds to the cost of gas transmission.
  • Natural gas is typically treated in high volumes, making even slight differences in capital and operating costs of the treating unit significant factors in the selection of process technology. Some natural gas resources are now uneconomical to produce because of processing costs. There is a continuing need for improved natural gas treating processes that have high reliability and represent simplicity of operation.
  • XAS Data collection XAS measurements were conducted at the Stanford Synchrotron Radiation Laboratory (SSRL) with the SPEAR storage ring containing between 80 and 100 mA at 3.0 GeV. Pd Kedge data were collected on the structural molecular biology XAS beamline 7-3 operating with a wiggler field of 2 T. A Si (220) double-crystal monochromator was used. Beamline 7-3 is equipped with a rhodium-coated vertical collimating mirror upstream of the monochromator, and a downstream bent- cylindrical focusing mirror (also rhodium-coated) . Harmonic rejection was accomplished by detuning the intensity of the incident radiation at the end of the scan by 50%.
  • SSRL Stanford Synchrotron Radiation Laboratory
  • Incident and transmitted X-ray intensities were monitored using argon or nitrogen-filled ionization chambers.
  • X-ray absorption was measured in transmittance mode. During data collection, samples were maintained at a temperature of approximately 1OK using an Oxford instruments liquid helium flow cryostat. For each sample, three scans were accumulated, and the energy was calibrated by reference to the absorption of a Pd foil measured simultaneously with each scan, assuming a lowest energy inflection point of 24349.0 eV.
  • the energy threshold of the extended X-ray absorption fine structure (EXAFS) oscillations was assumed to be 24370 eV.
  • F is defined as where the summations are over all data points included in the refinement .
  • Powder X-ray data were collected using a Bruker D8-Discover ⁇ -2 ⁇ diffractometer in reflectance Bragg-Brentano geometry employing Ni filtered Cu Ka line focused radiation at 1600 W (40 kV, 40 mA) power and equipped with a Vantec Line detector. Radiation was focused using parallel focusing Gobel mirrors. The system was also outfitted with an antiscattering shield that prevents incident diffuse radiation from hitting the detector, preventing the normally large background at 2 ⁇ ⁇ 3. Samples were mounted on zero background sample holders by dropping powders from a wide-blade spatula and then leveling the sample with a razor blade. Samples were prepared by dissolving small amounts of the material in methanol followed by sonication for 10 min .
  • Iminopyridine moieties have proved to be a versatile ligand system for binding a variety of transition metals in known coordination environments.
  • the disclosure demonstrates incorporation of such a moiety into A through condensation of the amine-functionalized framework and 2- pyridinecarboxaldehyde (Scheme 1) .
  • the isoreticular functionalized MOF B was synthesized by adding 1.5 equiv of 2- pyridinecarboxaldehyde to A in anhydrous toluene and allowing the reaction to proceed for 5 days, during which the needleshaped crystals changed color from clear to yellow to give a product having a composition that coincided well with the expected formula, thus indicating quantitative conversion.
  • Powder X-ray diffraction (PXRD) studies showed that B maintained crystallinity and possessed the same underlying topology as A subsequent to the covalent transformation.
  • the presence of the iminopyridine unit was confirmed by mass spectrometry of digested samples of B, which showed a parent ion peak at m/z 269 ([M - H]-) attributable to the ligand fragment .
  • Isoreticular metalation was achieved by adding 1.5 equiv of PdCl 2 (CH 3 CN) 2 to B in anhydrous CH2C12, whereupon the yellow crystalline material became dark-purple within several minutes. After 12 h, the material was washed three times with 10 mL portions of CH 2 Cl 2 ; the crystals were then immersed in dry CH 2 Cl 2 , and the solvent was refreshed every 24 h for 3 days to yield C. Again, the PXRD pattern of C ( Figure 1) confirmed that it retained crystallinity and possessed a framework topology identical to those of A and B. Removal of guest species from the pores was achieved by evacuating the crystals at 80 °C for 12 h.
  • the EXAFS data analysis provides a quantitative structural description of the Pd coordination environment within the MOF and clearly demonstrates that Pd is bound to the framework via the iminopyridine moiety. Furthermore, analysis of the X-ray absorption near-edge structure (XANES) spectrum indicated that the major chemical form of Pd within the framework of C was consistent with an iminopyridine-bound moiety and not the starting material, PdCl 2 (CH 3 CN) 2 .
  • XANES X-ray absorption near-edge structure
  • Recycle delays betweens scans varied between 10 and 30 s, depending upon the compound as determined by observing no apparent loss in the signal intensity from one scan to the next.
  • the 13 C chemical shifts are given relative to tetramethylsilane as zero ppm calibrated using the methyne carbon signal of adamantane assigned to 29.46 ppm as a secondary reference.
  • FT-IR spectra were collected on a Shimazu FT-IR Spectrometer. Electrospray ionization mass spectra (ESI-MS), matrix-assisted laser desorption ionization mass spectra
  • MALDI-MS MALDI-MS
  • CI/GC-MS chemical ionization mass spectra with gas chromatography
  • Sl Starting material (1) was prepared following the reported procedure. 1 Reduction of 1 was performed following the published procedures 1 ' 2 with slight modification in the work-up process. To a 2000 mL flask were added 1 (20.5 g, 70 mmol) , CoCl 2 (91 mg, 0.7 mmol), THF (200 mL) and EtOH (450 mL) . The mixture was refluxed. NaBH 4 (2.65 g, 70 mmol for each portion) was added three times (total 8.0 g) every hour. After consumption of 1 was confirmed by TLC analysis, the mixture was cooled to room temperature. After addition of water (300 mL) and vigorous stirring for 10 min, gummy precipitate was filtered off using Celite.
  • S2 To a 1000 mL flask were added 4- methoxyphenylboronic acid (20.5 g, 113 mmol) , pinacol (14.0 g, 118 mmol) and THF (500 mL) . The mixture was heated to reflux, stirred for 2 h, and then cooled to room temperature. The solution is filtered over short pad basic aluminum oxide and the solvent was evaporated to give S2 as a white powder (26.0 g, 85% yield) .
  • [00112] 4 The stirred solution of 2 (1.93 g, 6.67 mmol) , 3 (4.67 g, 15.35 mmol), Pd(PPh 3 J 4 (385 mg, 0.33 mmol) and K 2 CO 3 (2.76 g, 20 mmol) in 50 mL of 1,4-dioxane and 12 mL of water was heated to 100 0 C under nitrogen atmosphere. Stirring was continued overnight, and then the mixture was cooled to room temperature. Water was added and organic compounds were extracted with ethyl acetate three times . The combined organic layer was washed with brine and dried over Na 2 SO 4 . The extract was filtered through short pad basic aluminum oxide and evaporated.
  • LO To a solution of 5 (2.1 g, 3.35 mmol) in dichloromethane (35 mL) was added HBF 4 -OEt 2 (2.26 mL, 16.5 mmol) . The mixture was stirred for 2 h at room temperature. After dilution with diethyl ether the precipitates were filtered and washed with thoroughly with dichloromethane and diethyl ether. Toluene was added to the powder and evaporated. This is repeated twice to remove residual water as an azeotropic mixture. After drying in vacuo at 50 0 C, LO was obtained as gray powder (1.7 g, 100% yield) .
  • L2 To a suspension of Ll (-80 mg) in 5 mL chloroform was added quinoline (0.2 mL) . The mixture was stirred for 1 h at room temperature. Volatiles were evaporated and the residue was suspended in chloroform and filtered off to collect L2 as an orange powder, which was used as a reference compound for digestion studies.
  • IRMOF-76 A solid mixture of LO (47 mg, 0.1 mmol) , Zn (BF 4 ) 2 hydrate (72 mg, 0.3 mmol), KPF 6 (186 mg, 1 mmol) was dissolved in N, ⁇ f-dimethylformamide (DMF, 15 mL) in a capped vial. The reaction was heated to 100 0 C for 24-48 h yielding block crystals on the wall of the vial. The vial was then removed from the oven and allowed to cool to room temperature naturally. After opening and removal of mother liquor from the mixture, colorless crystals were collected and rinsed with DMF
  • IRMOF-77 A solid mixture of Ll (16.6 mg, 0.02 mmol) and Zn (NO 3 ) 2 • 6H 2 O (18 mg, 0.06 mmol) was dissolved in N, N- diethylformamide (DEF, 1.5 mL) and pyridine (0.02 mL) in a capped vial. The reaction was heated to 100 0 C for 24-36 h yielding block crystals on the bottom of the vial. The vial was then removed from the oven and allowed to cool to room temperature naturally. After opening and removal of mother liquor from the mixture, light orange crystals were collected and rinsed with DEF (3 x 4 mL) . Powder and single X-ray diffractions for this material were measured immediately. [00129] Any impurities were separated using the difference in the crystal densities. After decanting the mother liquor, DMF and CHBr 3 (1:2 ratio) were added to crystals. Floating orange crystals were collected and used.
  • IRMOF-77 was activated on a Tousimis Samdri PVT-3D critical point dryer. Prior to drying, the solvated MOF samples were soaked in dry acetone, replacing the soaking solution for three days, during which the activation solvent was decanted and freshly replenished three times. Acetone-exchanged samples were placed in the chamber and acetone was completely exchanged with liquid CO 2 over a period of 2.5 h. During this time the liquid CO 2 was renewed every 30 min . After the final exchange the chamber was heated up around 40 0 C, which brought the chamber pressure to around
  • IRMOF-77 40.36 (methyl) , 125.97*, 130.47*, 140.86 (pyridine), 154.10 (NHC carbon), 175.37 (CO 2 Zn) .
  • MOF 39.63 (methyl), 128.81*, 140.19*, 146.19 (quinoline) , 152.86 (NHC carbon), 174.38 (CO 2 Zn) .
  • Link L2 40.14 and 43.43 (non-equivalent methyl), 128.16*, 143.14*, 146.32 (quinoline), 153.59 (NHC carbon), 173.42 (CO 2 H)
  • IRMOF-76 A colorless block-shaped crystal (0.60 * 0.60 x 0.40 mm) of IRMOF-76 was placed in a 1.0 mm diameter borosilicate capillary containing a small amount of mother liquor to prevent desolvation during data collection.
  • the structure has been reported to display the framework of IRMOF-76 as isolated in the crystalline form.
  • the structure is a primitive cubic framework.
  • SQUEEZE 5 routine of A. Spek has been performed.
  • atomic co-ordinates for the "non-SQUEEZE" structures are also presented. No absorption correction was performed.
  • IRMOF-77 A light orange block-shaped crystal (0.30 x 0.30 x 0.20 mm) of IRMOF-77 was placed in a 0.4 mm diameter borosilicate capillary containing a small amount of mother liquor to prevent desolvation during data collection.
  • the structure was solved by direct method and refined using the SHELXTL 97 software suite. Atoms were located from iterative examination of difference F-maps following least squares refinements of the earlier models.
  • Hydrogen atoms were placed in calculated positions and included as riding atoms with isotropic displacement parameters 1.2-1.5 times U eq of the attached C atoms.
  • the structures were examined using the Adsym subroutine of PLATON to assure that no additional symmetry could be applied to the models.
  • the structure has been reported to display the framework of IRMOF-77 as isolated in the crystalline form.
  • the structure is a two-fold interpenetrating cubic framework.
  • SQUEEZE routine of A. Spek has been performed.
  • atomic co-ordinates for the "non- SQUEEZE" structures are also presented.
  • the structure reported after SQUEEZE does not include any solvents. No absorption correction was performed.
  • Powder X-ray diffraction (PXRD) data were collected using a Bruker D8-Discover ⁇ -2 ⁇ diffractometer in reflectance Bragg-Brentano geometry.
  • a 0.6 mm divergence slit was used for all measurements.
  • Diffracted radiation was detected using a Vantec line detector (Bruker AXS, 6° 2 ⁇ sampling width) equipped with a Ni monochromator .
  • TGA Thermal Gravimetric Analysis
  • the pore volume was determined using the Dubinin-Raduskavich (DR) method with the assumption that the adsorbate is in the liquid state and the adsorption involves a pore-filling process. Given the bulk density of IRMOF-77
  • This example targeted a structure based on the well- known primitive cubic MOF-5 and utilized a linear ditopic carboxylate link that could accommodate an NHC-metal complex or its precursor.
  • the disclosure demonstrates a convergent synthetic route for new links utilizing cross-coupling reactions as the key step to combine the imidazolium core with the carboxylate modules (Scheme 2, above) .
  • Scheme 2, above the carboxylate modules
  • LO dimethylbenzimidazium tetrafluoroborate
  • the module possessing a tert-butyl ester as a masked carboxylic acid was selected because of improved solubility and feasible late- stage unmasking of carboxylic acid.
  • Treatment with an excess of methyl iodide produced 5, possessing the N, N'- dimethylbenzimidazolium moiety.
  • LO was then obtained by deprotection of two tert-butyl esters using HBF 4 concomitant with counteranion substitution from I " to BF 4 " . All conversions were feasible on a gram scale.
  • IRMOF-76 is a non-interpenetrated cationic MOF possessing imidazolium moieties (NHC precursors) on each link.
  • the ICP analysis and 19 F NMR spectrum of digested IRMOF-76 reveal that both BF 4 " and PF 6 " are included as counter- anions of the imidazolium moieties.
  • a strategy using a link possessing a metal-NHC complex was developed.
  • the metal-NHC bond is generally stable even under mild acidic conditions, and chemoselective NHC- coordination avoids undesired reactions with metal sources in the construction of secondary building units (SBUs) , which, in many cases, relies on oxygen-metal coordination.
  • SBUs secondary building units
  • [4, 7-bis (4-carboxylphenyl) - 1, 3-dimethylbenzimidazole-2-ylidene] (pyridyl) palladium (II) iodide (Ll, Scheme 2) was used, which is potentially attractive as a catalyst homologous to known homogeneous catalyst systems.
  • Ll was prepared from intermediate 5 (Scheme 2) .
  • the benzimidazolium moiety of 5 was converted to the NHC-PdI 2 (py) complex when refluxed in pyridine with a Pd(II) source, a base (K 2 CO 3 ), and an iodide source (NaI) .
  • Deprotection of the fcerfc- butyl esters was achieved with trimethylsilyl trifluoromethanesulfonate (TMSOTf) .
  • TMSOTf trimethylsilyl trifluoromethanesulfonate
  • the covalently formed Pd(II)-NHC bond was surprisingly stable even under the strongly Lewis acidic conditions for deprotection. However, the pyridine co-ligand was removed to form dimeric complexes.
  • IRMOF-77 was conducted using Zn (NO 3 ) 2 ' 6H 2 O of three equivalents to Ll in a solvent mixture of N, ZV-diethylformamide (DEF) and pyridine (75/1) . The mixture was heated at 100 0 C for 30 h, whereupon orange crystals of IRMOF-77 (Zn 4 O(C 28 H 21 I 2 N 3 O 4 Pd) 3 ) were obtained.
  • X-ray single crystal structure analysis reveals that IRMOF-77 is also isoreticular with MOF-5.
  • the X-ray crystal structure verifies the presence of the NHC-PdI 2 (py) moiety ( Figure 6b) .
  • the Zn ions used for the construction of the framework are not involved in binding with the metal-NHC moiety.
  • Measured elemental compositions in accordance with the expected values confirm the absence of undesired metal exchange on NHC.
  • NHC- Pd(II) moieties are positioned on every face of the cubic cage within the framework.
  • Two interwoven frameworks were formed with ca. 7 A offset distance ( Figure 6c), presumably to mitigate the interference of the metal-NHC moieties with each other, with 4.06 A shortest distances between two methyl carbons from two frameworks.
  • the catenation is different from that of IRMOF-15, whose link length is the same as Ll. Due to the interwoven nature of the structure, the pore aperture is ca .

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Abstract

La présente invention concerne des structures organiques qui comportent une plus grande stabilité.
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