EP2533898A2 - Édifices organométalliques issus de métaux carbénophiles et leur procédé de fabrication - Google Patents

Édifices organométalliques issus de métaux carbénophiles et leur procédé de fabrication

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Publication number
EP2533898A2
EP2533898A2 EP11754945A EP11754945A EP2533898A2 EP 2533898 A2 EP2533898 A2 EP 2533898A2 EP 11754945 A EP11754945 A EP 11754945A EP 11754945 A EP11754945 A EP 11754945A EP 2533898 A2 EP2533898 A2 EP 2533898A2
Authority
EP
European Patent Office
Prior art keywords
framework
organo
metal
irmof
metallic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11754945A
Other languages
German (de)
English (en)
Inventor
Omar M. Yaghi
Alexander U. Czaja
Oisaki Konosuke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
University of California
Original Assignee
BASF SE
University of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE, University of California filed Critical BASF SE
Priority claimed from PCT/US2011/024671 external-priority patent/WO2011146155A2/fr
Publication of EP2533898A2 publication Critical patent/EP2533898A2/fr
Withdrawn legal-status Critical Current

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    • 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]
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    • 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
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    • 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]
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • 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
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    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
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    • B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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    • 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
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    • 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
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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
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    • 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
    • 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
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    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]

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 monodentate and/or multidentate organic or inorganic cores. Including all classes of open framework materials; covalent organic frameworks (COFs) ; zeolitic imidazolate frameworks (ZIFs); metal organic frameworks (MOFs); and all possible net topologies as described in or resulting from the reticular chemistry structure resource ( http : ( // ) rcsr . anu . edu . au/ ) .
  • the disclosure provides for chemically stable open frameworks that can be used in industry. Such frameworks can be used in a variety of applications, including, but not limited to, 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 a heterocyclic carbene linked to a modifying 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 framework metal is selected from the group including, but not limited to, Li, Na, Rb, Mg, Ca, Sr, Ba, Sc, Ti, Zr, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Ni, Pd, Pt, Cu, Au, Zn, Al, Ga, In, Si, Ge, Sn, and Bi .
  • the modifying metal is selected from the group consisting of Li, Be, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Sn, Te, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Sm, Eu, and Yb.
  • 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.
  • the disclosure provides a method of making an organo-metallic framework described above comprising reacting a linking moiety comprising a heterocyclic carbene and comprising a protected linking cluster with a modifying metal to obtain a metallated linking moiety, deprotecting the linking cluster, and then reacting the deprotected metallated linking moiety with a framework metal.
  • organo-metallic frameworks of the disclosure are useful 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. [0009] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
  • Figure 1A-C show structures of IRMOF-76 and -77.
  • Figure 2 shows N 2 isotherm measurements for IRMOF-77 measured at 77 .
  • Figure 3 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 4 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 5 is an ORTEP drawing of the IRMOF-77, with a half of Zn 4 0 unit and one link. All ellipsoids are displayed at the 30% probability level except for hydrogen atoms.
  • Figure 6 shows PXRD patterns of as-synthesized
  • IRMOF-76 black
  • simulated IRMOF-15, 16 blue and red, respectively
  • Figure 7 is a TGA trace of as-synthesized IRMOF-76.
  • the huge weight loss up to 150 °C corresponds to the loss of guest solvents (DMF, H 2 0) .
  • a significant weight loss from 300 to 400 °C indicates the decomposition of the material.
  • Figure 8 is a TGA trace of as-synthesized IRMOF-77.
  • the huge weight loss up to 150 °C corresponds to the loss of guest solvents (DEF, pyridine, and H 2 0) .
  • the material loses coordinated molecules (pyridines) up to 250 °C, and a significant weight loss from 300 to 400 °C indicates the decomposition of the material.
  • Figure 9 is a TGA trace of activated IRMOF-77. The weight loss around 180 °C is attributed to the partial loss of coordinated pyridine (calcd. 8.6% for full loss).
  • Figure 10 is a TGA ' trace of organometallic linker
  • MOFs Metal-organic frameworks
  • MOFs Metal-organic frameworks
  • the disclosure provides organo-metallic frameworks and methods 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 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 (LI, Scheme 1) and then assembled into the desired metalated MOF structure (e.g., IRMOF-77, Scheme 1). Also demonstrated by the
  • 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 2 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.
  • reactive species include, but are not limited to, boron, sulfur, oxygen, carbon, nitrogen, and phosphorous atoms.
  • a linking cluster can comprise C0 2 H, CS 2 H, N0 2 , S0 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , Sn(SH) 4 , P0 3 H, As0 3 H, As0 4 H, P(SH) 3 , As(SH) 3 , CH(RSH) 2 , C(RSH) 3 , CH(RNH 2 ) 2 , C(RNH 2 ) 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 ) 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
  • ligands for MOFs contain carboxylic acid functional groups.
  • 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/or aluminum atoms making up the ring.
  • a "linking moiety” refers to a mono-dentate or ' polydentate compound that binds a metal or a plurality of metals, respectively through a linking cluster.
  • a linking moiet 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 group) is covalently bound to the substructure.
  • a linking cluster e.g., a multidentate function group
  • the substructure comprises a hetrocyclic carbene that can be functionalized with a carbeneophilic metal.
  • 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.
  • 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.
  • Carbonophilic refers to those metals that have been found to bind to persistent carbenes. Moreover, as used herein in this application, “carbenophilic” and “modifying metal” are equivalent and are used interchangeably.
  • linking moieties may be used that can be functionalized with an heterocyclic carbene.
  • a linking moieties useful in the methods and compositions of the disclosure will comprise a general formula I or II:
  • thioalkoxy silicon-containing group, nitrogen-containing group (e.g., amide, cyano, nitro, azide, and amino), oxygen-containing group (e.g., ketone, aldehyde, ester, ether, carboxylic acid, and acyl halide) , boron-containing group, phosphorous-containing group, a tin containing group, an arsenic containing group, a germanium containing group or halogen ; R 5 and R 6 are each independently selected from the group consisting of an alkyl containing 1 to 6 carbons, and H; R 2 and R 3 are selected from the group consisting of H, alkyl, aryl, alkoxy, alkenes, alkynes, phenyl and substitutions of the foregoing, sulfur-containing group (e.g., thioalkoxy) , silicon-containing groups, nitrogen-containing groups (e.g., amide, amino, nitro, azide, and cyano),
  • ⁇ and Y 2 are independently either a nitrogen, sulfur, oxygen, phosphorous, or silicon;
  • M c represents a modifying metal, which may further comprise a functionalizing moiety.
  • the MOF comprises the general structure M-L-M, wherein M comprise a transition metal and L comprising a linking moiety having the general structure :
  • the disclosure provides a metal organic framework
  • the HC-precursor comprises the general structure :
  • the MOF comprises the general structure M-L-M, wherein M is a transition metal and wherein L is a linking moiety having a HC-precursor with a general formula:
  • 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.
  • 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.
  • post framework reactants include, but are not limited to, heterocyclic compounds.
  • the post framework reactant can be a saturated or unsaturated
  • heterocycle used alone or as a suffix or prefix, refers to a ring-containing structure or molecule having one or more multivalent heteroatoms as part of the ring structure and including at least 3 and up to about 20 atoms in the ring(s).
  • Heterocycles 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. Heterocycles may have aromatic character or may not have aromatic character. The terms
  • 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
  • heterocycle includes aromatic heterocycles (heteroaryl groups), for example, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole, pyrazole, isothiazole, isoxazole,
  • heterocycle encompass polycyclic
  • heterocycles for example, indole, indoline, isoindoline,
  • tetrahydroisoquinoline 1 , 4-benzodioxan, coumarin, dihydrocoumarin, benzofuran, 2, 3-dihydrobenzofuran, isobenzofuran, chromene, chroman, isochr man, xanthene, phenoxathiin, thianthrene,
  • indolizine isoindole, indazole, purine, phthalazine,
  • phenothiazine phenoxazine, 1 , 2-benzisoxazole, benzothiophene, benzoxazole, benzthiazole, benzimidazole, benztriazole,
  • 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,
  • heterocyclyl includes aromatic
  • heterocyclyls or heteroaryl for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, furazanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, isothiazolyl ,
  • heterocyclyl encompasses polycyclic heterocyclyls (including both aromatic or non-aromatic) , for example, indolyl, indolinyl, isoindolinyl, quinolinyl,
  • phenanthridinyl perimidinyl, phenanthrolinyl , phenazinyl, phenothiazinyl , phenoxazinyl , 1 , 2-benzisoxazolyl , benzothiophenyl , benzoxazolyl , benzthiazolyl , benzimidazolyl , benztriazolyl , thioxanthinyl, carbazolyl, carbolinyl, acridinyl, pyrolizidinyl, and quinolizidinyl .
  • 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 .
  • 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
  • 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. Reactions that result in the tethering of organometallic complexes to the framework for use as, for example, a heterogeneous catalyst can be used.
  • Metal ions that can be used in the synthesis of frameworks of the disclosure include Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ ,
  • Metal ions can be introduced into open frameworks, MOFs,
  • any metal ions from the periodic table can be introduced.
  • the functionalized organic linkers e.g., N-heterocyclic carbene
  • 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,
  • 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,
  • 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.
  • 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 including, but not limited to: (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
  • aryl ammonium salts having from 1 to 5 phenyl rings;
  • alkyl phosphonium salts containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
  • aryl phosphonium salts having from 1 to 5 phenyl rings;
  • alkyl organic acids and their corresponding salts containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
  • aryl organic acids and their corresponding salts having from 1 to 5 phenyl rings;
  • aliphatic alcohols containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; or
  • aryl alcohols having from 1 to 5 phenyl rings .
  • 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.
  • the method 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.
  • Also provided are 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
  • C02 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, C0 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.
  • Cross-polarization with MAS (CP/MAS) was used to acquire at 75.47 MHz ( 13 C) .
  • the 1 and 13 C ninety-degree pulse widths were both 4 ⁇ .
  • the CP contact time was 1.5 ms .
  • High power two-pulse phase modulation (TPPM) 1 H decoupling was applied during data
  • the decoupling frequency corresponded to 72 kHz.
  • the MAS sample spinning rate was 10 kHz.
  • 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.
  • Electrospray ionization mass spectra (ESI-MS)
  • MALDI-MS matrix-assisted laser desorption ionization mass spectra
  • CI/GC-MS chemical ionization mass spectra with gas chromatography
  • ICP Inductively coupled plasma
  • 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) .
  • S3 A solution of 5 (1.87 g, 3 mmol) , Pd (CH 3 CN) 2 C1 2 . (900 mg, 3.3 mmol), Nal (750 mg, 6 mmol), and K2CO3 (2.07 g, 15 mmol) in 30 mL of pyridine was heated to reflux and stirred overnight. After cooling the mixture to room temperature, all volatiles were evaporated. The obtained residue was dissolved in chloroform (200 mL) and water (100 mL) . The separated organic layer was washed with 5% CuS0 4 aq. (30 mL, twice) and brine (30 mL) , and then dried over Na 2 SO ! i . The extract was filtered over short pad silica gel and ⁇ washed thoroughly with hexane/acetone (2/1). The combined organic solutions were evaporated to give S3 as an orange powder (2.5 g, 88% yield) .
  • L2 To a suspension of LI ( ⁇ 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 L0 (47 mg, 0.1 mmol),
  • IRMOF-77 A solid mixture of LI (16.6 mg, 0.02 mmol) and
  • IRMOF-77 was activated on a
  • IRMOF-77 40.36 (methyl ) , 125.97*, 130.47*, 140.86 (pyridine),
  • IRMOF-77 were immersed in 4% v/v quinoline/DMF solution in a 20-mL vial, capped, and let stand for one day.
  • the quinoline solution was decanted and the crystals were rinsed with DMF (3 x 4 mL) after which the PXRD pattern was immediately measured. After exchange with chloroform for one day, the solvent was evacuated overnight at room temperature. Solid state CP/MAS NMR spectra were recorded using the dried compound.
  • MOF 39.63 (methyl), 128.81*, 140.19*, 146.19 (quinoline), 152.86 (NHC carbon), 174.38 (C0 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 (C0 2 H)
  • IRMOF-76 A colorless block-shaped crystal (0.60 ⁇ 0.60 x 0.40 mm) of IPMOF-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.
  • IBMOF-77 A light orange block-shaped crystal (0.30 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 capillary was flame sealed and mounted on a SMART APEXII three circle
  • 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.
  • Crystal size 0.60 0.60 0.40 mm 3
  • Theta range for data collection 1.78-40.06°
  • Powder X-ray diffraction (PXRD) data were collected using a Bruker D8-Discover ⁇ -2 ⁇ diffTactometer in reflectance Bragg- Brentano geometry.
  • Cu Ko ⁇ i radiation ( ⁇ 1.5406 A; 1600 W, 40 kV, 40 mA) was focused using a planar Gobel Mirror riding the Ka line.
  • 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 .
  • 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 (0.922 g cm “3 ), calculated pore volume (0.57 cm 3 g "1 ) corresponds to 0.53 cm 3 cm “3 .
  • DR Dubinin-Raduskavich
  • 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) .
  • 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.
  • L0 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 The synthesis of ⁇ IRMOF-76 was carried out using a mixture of three equivalents of Zn (BF 4 ) 2 -xH 2 0, ten equivalents of KPF 6 and L0 in N, W-dimethylformamide (DMF) . The mixture was heated at 100 °C for 36 h, whereupon colorless crystals of IRMOF-76
  • IRMOF-76 Single crystal X-ray diffraction analysis revealed that IRMOF-76 is isoreticular with MOF-5. Here, Zn0 units are connected to six L0 links to form a cubic framework of pcu topology ( Figure la) .
  • 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 ( -carboxylphenyl ) -1, 3-dimethylbenzimidazole-2- ylidene] (pyridyl) palladium(II ) iodide (LI, Scheme 2) was used, which is potentially attractive as a catalyst homologous to known homogeneous catalyst systems.
  • LI 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 C0 3 ) , and an iodide source (Nal) .
  • Deprotection of the tert-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.
  • the pyridine co-ligand was removed to form dimeric complexes. Adding pyridine as a ligand was necessary to produce LI possessing a monomeric NHC-PdI 2 (py) moiety.
  • 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 lb) .
  • 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 lc) , 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 LI.
  • the pore aperture is ca. 5 A x 10 A. All immobilized Pd(II) centers protrude into the pores without blocking each other.
  • IRMOF-76 and 77 demonstrate the successful application of the methods of the disclosure to immobilize Pd(II)-NHC organometallic complex in MOFs without losing the MOF' s porosity and its structural order.

Abstract

La présente invention porte sur des structures organiques qui comportent une plus grande stabilité.
EP11754945A 2010-02-12 2011-02-12 Édifices organométalliques issus de métaux carbénophiles et leur procédé de fabrication Withdrawn EP2533898A2 (fr)

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