CN102574886A - Organo-metallic frameworks and methods of making same - Google Patents

Organo-metallic frameworks and methods of making same Download PDF

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CN102574886A
CN102574886A CN2010800369497A CN201080036949A CN102574886A CN 102574886 A CN102574886 A CN 102574886A CN 2010800369497 A CN2010800369497 A CN 2010800369497A CN 201080036949 A CN201080036949 A CN 201080036949A CN 102574886 A CN102574886 A CN 102574886A
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skeleton
metal
connection portion
organometallic skeletal
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克里斯蒂安·J·杜南
威廉·莫里斯
奥玛尔·M·亚纪
王博
邓鹤翔
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University of California
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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 System
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System 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
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    • 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
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    • 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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)
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
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    • 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

Abstract

The disclosure provides organic frameworks comprising increased stability.

Description

Organometallic skeletal and its method of manufacture
The cross reference of related application
The right of priority that No. the 61/247th, 351, No. the 61/218th, 891, the provisional application that the application requires to submit on June 19th, 2009 according to 35U.S.C. § 119 and the provisional application of submission on September 30th, 2009, its disclosure is incorporated herein by reference.
Statement about federal funding research
The present invention is that the fund HDTRA1-08-10023 that the fund DE-FG36-05GO15001 that authorized by Ministry of Energy and Department of Defense are authorized subsidizes.United States Government enjoys some right of the present invention.
Technical field
Disclosure book is provided for gas delivery, storage and is used as the organometallic skeletal of the transmitter with chemicalstability.
Background technology
The skeleton that is used for gas delivery, storage and purifying is very important.
Summary of the invention
Disclosure book provides the chemically stable open skeleton that comprises designed element, and said designed element includes, but is not limited to zirconium, titanium, aluminium and mg ion.Organic key compound that disclosure book is contained by multiple tooth organic or inorganic core bridge joint makes up and all next open framework materials.The open framework material that comprises all categories: covalency organic backbone (COF), zeolite imidazoles skeleton (ZIF) and metallic organic framework (MOF) and Reticular Chemistry Structure Resource ( Http:// rcsr.anu.edu.au/) the interior all possible gained network topology structure of describing.Disclosure book is provided at the stable skeleton that utilizes these materials under the industrial severe condition.During this type of material for example will be widely used in gas storage and separate, chemistry and biological sensing, molecule reconstruct and catalysis etc. use.
Disclosure book provides the organometallic skeletal that comprises universal architecture M-L-M, wherein M be the skeleton metal and wherein L have the connection portion of the modification of being connected in the heterocyclic carbene or the imine group of metal.In one embodiment, imine group comprises chelation group.In another embodiment, the connection portion is being metallized with the skeleton metal reaction before.In another embodiment, the connection portion comprises the N-heterocyclic carbene.In one embodiment, skeleton comprises covalency organic backbone (COF), zeolite imidazoles skeleton (ZIF) or metallic organic framework (MOF).In another embodiment, imine group by skeleton after chelating (post-framework chelated) in metal.In one embodiment, the skeleton metal is selected from by 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 group of forming.In another embodiment, modification is selected from by Li with metal +, 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 2+, 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 group of forming.In another embodiment, modification extends in the hole of skeleton with metal.In some embodiments, skeleton comprises guest species (guest species), but in other embodiments, skeleton lacks guest species and but still keeps stable.
Disclosure book provides the method for making organometallic skeletal mentioned above; It comprises making and comprises heterocyclic carbene and comprise through the connection portion of the connection bunch of protection and modification with metal reaction to obtain metallized connection portion; Bunch go protection and make metallized connection portion and skeleton metal reaction connecting.
Disclosure book also provides the method for making organometallic skeletal, it comprise make the organic backbone that comprises amido and the reaction of 2-pyridylaldehyde with the functionalized connection portion of acquisition imines and make skeleton and chelating in the metallic contact of the functionalized connection portion of imines.
The organometallic skeletal of disclosure book can be used for gas delivery and catalysis.Therefore, disclosure book provides the gas adsorption material and the device of the organometallic skeletal that comprises disclosure book, and catalytic composition and device.
The details of one or more embodiments of the present invention is set forth in accompanying drawing and the following embodiment.According to embodiment and accompanying drawing and according to claims, further feature of the present invention, purpose and advantage will be obvious.
Description of drawings
Fig. 1 shows the PXRD collection of illustrative plates of A, B and C and the simulation collection of illustrative plates (bottom) of A.
Fig. 2 shows A (the top solid circles part of graphic representation), B (top empty circles part) and C (following line) at the Ar of 87K gas adsorption thermo-isopleth, and wherein absorption reconciliation dot is represented by solid circles and empty circles respectively.
Fig. 3 shows Pd K-edge (edge) the EXAFS fourier transformation and (illustration) EXAFS spectrum of C.Solid line shows that experimental data and dotted line show the best-fit that uses the parameter in the table 1.
Fig. 4 show dichloro (N-(2-pyridyl methylene radical) aniline-N, N ') palladium (II) (a), (Zn 4O) 3(BDC-C 6H 5N 2PdCl 2) 3(BTB) 4(b) and PdCl 2(CH 3CN) (c) Pd K-edge proximal edge (K-edge near edge) spectrum.
Fig. 5 shows the segmental ESI mass spectrum of imine ligand.
Fig. 6 A-C shows the structure of IRMOF-76 and-77.(a) IRMOF-76 (Zn 4O (C 23H 15N 2O 4) 3(X) 3(X=BF 4, PF 6, OH)) single crystal structure.(b) IRMOF-77 (Zn that only shows with a pcu net 4O (C 28H 21I 2N 3O 4Pd) 3) single crystal structure.Atom color: tetrahedron: Zn, I, Pd, O, spheroid: N.Spheroid is represented maximum spheroid, and it will occupy cavity but not contact the Van der Waals surface, inside of IRMOF-76 and the monocrystalline skeleton (being respectively about and
Figure BDA0000136855220000032
) of IRMOF-77.For the purpose of clear, all Wasserstoffatomss, counter anion (X) and guest molecule have been omitted.(c) diagram is filled in the space of IRMOF-77.Shown and had blue and two kinds of pcu nets that interweave of golden respectively.
Fig. 7 is presented at the N of the IRMOF-77 of 77K measurement 2The thermo-isopleth measuring result.
Fig. 8 show original position synthesize the exchange of attitude (as synthesized) IRMOF-77 (centre), quinoline IRMOF-77 (bottom) the PXRD collection of illustrative plates and from the simulation PXRD collection of illustrative plates (top) of monocrystalline x-ray structure.
Fig. 9 is the ORTEP figure of the asymmetric cell of IRMOF-76.All spheroids are the probability level demonstrations with 10%, but except the Wasserstoffatoms.
Figure 10 is the ORTEP figure of IRMOF-77, has half Zn 4O unit and a connection portion.All spheroids are the probability level demonstrations with 30%, but except the Wasserstoffatoms.
Figure 11 shows the synthetic attitude IRMOF-76 (black) of original position and from the PXRD collection of illustrative plates of the Simulation with I RMOF-15,16 (being respectively blue and red) of monocrystalline x-ray structure.
Figure 12 is the TGA vestige of the synthetic attitude IRMOF-76 of original position.Huge weight loss during up to 150 ℃ is corresponding to object solvent (DMF, H 2O) loss.The decomposition of the remarkable weight loss indication material in the time of 300 to 400 ℃.
Figure 13 is the TGA vestige of the synthetic attitude IRMOF-77 of original position.Huge weight loss during up to 150 ℃ is corresponding to object solvent (DEF, pyridine and H 2O) loss.Presumably, material loses ligand molecule (pyridine) up to 250 ℃ the time, and the decomposition of the remarkable weight loss indication material 300 to 400 ℃ the time.
Figure 14 is the TGA vestige of activated state IRMOF-77.Weight loss in the time of about 180 ℃ is owing to the partial loss of coordination pyridine (be calculated as complete loss 8.6%).
Figure 15 is the TGA vestige of organo-metallic linker L1.Weight loss (9.7%) during up to 250 ℃ is consistent with the loss (calculated value 9.3%) of the pyridine that forms dimer S4.
Figure 16 shows activated state Zr-MOF.
Figure 17 is presented at the stability test under the situation that has various chemicals.
Figure 18 demonstration can be used for producing the reaction as the imines of sequestrant.
Figure 19 shows that the reversible imines forms in the skeleton.
Figure 20 shows the PXRD data of imines.
Figure 21 shows the solid state NMR data of imines.
Figure 22 A-B shows the SA of imine reaction.
Figure 23 shows the data of the reverse of imine reaction.
Figure 24 shows the part in the method and composition that can be used for disclosure book.
Embodiment
Only if context is clearly indicated, otherwise as used in this paper and the claims of enclosing, singulative " (a) ", " one (an) " and " being somebody's turn to do/said (the) " comprise a plurality of things that refer to.Therefore, comprise a plurality of said skeletons when for instance, mentioning " skeleton ", and comprise when mentioning " should/said metal " and mention the known metal of one or more one of ordinary skill in the art and its coordinator, like that.
Only if definition in addition, otherwise the implication of all scientific and technical terms used herein is identical with the common implication of understanding of disclosure book one of ordinary skill in the art.Though all can be used for describing illustrative methods and material now in the enforcement of disclosed method and composition with method as herein described and similar or equal any method and the reagent of reagent.
In addition, unless otherwise indicated, otherwise use " or " mean " and/or ".Similarly, " comprise " and " comprising " interchangeable use and do not plan to have restricted.
Should further understand; When the description of each embodiment uses a technical term " comprising "; One of ordinary skill in the art will think under some particular cases, substitutability ground use wording " basically by ... form " or " by ... form " embodiment described.
The mode that all publications that this paper mentions are quoted in full be incorporated herein be used to describe with public publication described in method, it possibly unite use with the description among this paper.Preceding text and the publication that runs through this paper discussion only since its announcement before the applying date in the application be provided.Any content among this paper should not be understood that to admit that the inventor does not have right to take the lead in this type of openly owing to formerly open.
In affiliated field, synthesized metallic organic framework (MOF), yet these previous MOF lack chemicalstability or have low porosity and the shortcoming in limited cage/duct, this has seriously limited its application in industry.
Usually realize accurate control with molecule coordination chemistry method to the functionality in the metal complex.The similar chemistry of development still has problems in extension crystalline texture, because they lose order and connectivity (connectivity) easily when the experience chemical reaction.Organometallic skeletal (MOF) is the ideal candidate of in the extension structure, carrying out coordination chemistry because they have the character of high-sequential and flexible, utilize flexible can the organic connection of modification.This illustrates through the impartial netted principle of successful Application (isoreticular principle), and wherein the functionality of extension vesicular structure can change under the situation that does not change its underlying topology structure with tolerance.
Disclosure book provides the method that produces organometallic skeletal through two kinds of methods.First method is utilized back skeleton building-up reactions (post-framework synthesis reaction), wherein reactivity side group---linking ligand---as metal chelator with metal-chelating in skeleton.Skeleton compound method (pre-framework synthesis methodology) before second method is utilized, wherein linking ligand is modified to comprise metal, and wherein metal-ligand reacts the formation skeleton then.Disclosure book also comprises from the compsn of these method generations and the device that merges said compsn.
Disclosure book provides the method for using series of chemical to produce the stable organometallic skeletal that comprises MOF, ZIF or COF.An advantage of the skeleton of disclosure book is that the metal center of expectation and organic ease of connection are mixed, and makes easily to regulate and to adjust porosity, functionality and duct environment with using to objective function.
In one embodiment of the invention, disclosure book provides the precursor organic backbone, and it comprises the connection portion, and said connection portion has the reactivity side group that can be used for chelated mineral.In one embodiment, reactivity side group comprises amido.Then, utilize back skeleton reaction process for sequestration, the precursor organic backbone can form organometallic skeletal so that pass through the reaction of skeleton with metal reaction.
The clear MOF material that is selected from numerous materials of bibliographical information of disclosure documented evidence can experience series of chemical to make covalently bound chelating ligand, and it can be used for complexing Pd (II) subsequently.The skeleton that comprises chelated mineral can further react so that extra functionality (for example space constraint, electric charge etc.) is mixed in the hole of skeleton then.
For instance, make (Zn 4O) 3(BDC-NH 2) 3(BTB) 4(A) crystal (scheme 1) reacts to form covalently bound imino-pyridine inner complex verivate (Zn with the 2-pyridylaldehyde 4O) 3-(BDC-C 6H 5N 2) 3(BTB) 4(B), itself and PdCl 2(CH 3CN) 2Reaction is to generate the MOF (Zn of metal complex 4O) 3(BDC-C 6H 5N 2PdCl 2) 3-(BTB) 4(C).These reactions can not realize under the internuncial situation of loss structure order or skeleton with its product separately.This impartial net-like metallic is being important first step aspect the intrinsic advantage of utilizing the functionalized molecule coordination chemistry of extension solid.The MOF of metal complex can be used as tectonic element (building block) then, is used for carrying out other reaction to form further functionalized skeleton with chelated mineral.
Functionalized and the subsequent metalization of scheme 1. impartial netted covalency
Figure BDA0000136855220000071
Described to be proved to be about the metallized two pieces of reports of covalency and had permanent porous material.The policies using that scheme 1 is described these defectives.The imino-pyridine moiety has been proved to be the general Fas lignand system that in known coordination environment, combines multiple transition metal.Disclosure book mixes such part through the condensation reaction (scheme 1) of amine-functionalized skeleton and 2-pyridylaldehyde.
In another embodiment of the invention, disclosure book provides the alternative method that produces organometallic skeletal.In this embodiment, produce the covalently bound organometallic complex that is arranged in the MOF hole.Said method makes the reactive carbene metallization on the linking ligand, bunch goes protection and makes metallized linking ligand and metal reaction connecting subsequently.For instance, make carbene (NHC) 5 precursor metalizations (L1, scheme 2), be then assembled in the metallization MOF structure of expectation (for example IRMOF-77, scheme 2).Disclosure book has proved that also these metallized MOF can be through further modification to increase the functionality (size, electric charge etc.) of matrix porosity.
Scheme 2: the reducing-pitch thread of new dicarboxylicacid connector (L0, L1) synthetic with IRMOF-76,77 preparation:
aCondition: (a) CoCl 2(1mol%), NaBH 4, EtOH/THF refluxes; (b) HC (OEt) 3, thionamic acid (5mol%), MeOH, 52% (2 steps); (c) MeI, K 2CO 3, EtOH refluxes 100%; (d) Pd (PPh 3) 4(5mol%), K 2CO 3, two
Figure BDA0000136855220000082
Alkane/H 2O, 100 ℃, 62%; (e) MeI, CH 3CN refluxes 94%; (f) HBF 4OEt 2, CH 2Cl 2, 100%; (g) Zn (BF 4) 2XH 2O (3 equivalent), KPF 6(10 equivalent), DMF, 100 ℃, 36h; (h) Pd (CH 3CN) 2Cl 2, NaI, K 2CO 3, pyridine refluxes 88%; (i) TMSOTf, CH 2Cl 2(j) pyridine, CHCl 3/ MeOH; 74% (2 steps); (k) Zn (NO 3) 24H 2O (3 equivalent), DEF/ pyridine (75/1), 100 ℃, 30h.
In one embodiment, the method for disclosure book utilizes the method for describing in the scheme 3 to make organo-metallic MOF.
Figure BDA0000136855220000101
Scheme 3
Term " bunch " be meant the recognizable combination of 2 or 2 above atoms.The typically formation such as the key-ionic linkage through particular type, covalent linkage, Van der Waals force of this type of combination.
" connect bunch " be meant can condensation one or more reactive materials, it comprises can be at the atom that forms key between connection portion substructure and the metal group or between connection portion and another connection portion.The instance of said material is selected from the group that is made up of boron, oxygen, carbon, nitrogen and phosphorus atom.In some embodiments, connect bunch reactive materials that can comprise one or more abilities and bridge joint Sauerstoffatom formation key.For instance, connect and bunch can comprise CO 2H, CS 2H, NO 2, SO 3H, Si (OH) 3, Ge (OH) 3, Sn (OH) 3, Si (SH) 4, Ge (SH) 4, Sn (SH) 4, PO 3H, AsO 3H, AsO 4H, 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) 2And C (CN) 3, wherein R is the alkyl with 1 to 5 carbon atom; Or comprise 1 to 2 phenyl ring and CH (SH) 2, C (SH) 3, CH (NH 2) 2, C (NH 2) 3, CH (OH) 2, C (OH) 3, CH (CN) 2And C (CN) 3Aryl.Typically, the part of MOF contains carboxylic acid functional.Disclosure school bag is drawn together naphthenic base or the aryl substructure that comprises 1 to 5 ring, and said ring all is made up of carbon or is made up of carbon and the mixture that constitutes nitrogen, oxygen, sulphur, boron, phosphorus, silicon and the aluminium atom of ring.
" connection portion " is meant monodentate or the polydentate compound that combines a transition metal or a plurality of transition metal respectively.In general; The connection portion comprises substructure; Said substructure comprises: comprise 1 to 20 carbon atom alkyl or cycloalkyl, comprise the aryl of 1 to 5 phenyl ring or comprise alkyl or cycloalkyl or comprise the alkylamine or the arylamines of the aryl of 1 to 5 phenyl ring with 1 to 20 carbon atom, and wherein connect bunch (a for example multiple tooth functional group) and be covalently bonded in substructure.Naphthenic base or aryl substructure can comprise 1 to 5 ring, and said ring only comprises carbon or comprises carbon and the mixture that constitutes the nitrogen, oxygen, sulphur, boron, phosphorus, silicon and/or the aluminium atom that encircle.Typically, the connection portion comprises and has the substructure that one or more covalently bound carboxylic acids connect bunch.In some embodiments, carboxylic acid bunch can be protected between some reaction period, and then with metal reaction before gone protection.
As used herein, at one end have atom and do not have the straight line in the chemical formula of atom to mean at the other end, said chemical formula is meant in the chemical fragment of another entity of end bonding of linker atom not.Sometimes in order to stress that wavy line will intersect with straight line.
On the one hand, the connection portion substructure be selected from following any one:
In specific embodiments, the connection portion has following structure:
Other connection portion comprises following listed part:
Figure BDA0000136855220000123
Figure BDA0000136855220000131
R wherein 1-R 15Be H, NH 2, COOH, CN, NO 2, F, Cl, Br, I, S, O, SH, SO 3H, PO 3H 2, OH, CHO, CS 2H, SO 3H, Si (OH) 3, Ge (OH) 3, Sn (OH) 3, Si (SH) 4, Ge (SH) 4, PO 3H, AsO 3H, AsO 4H, 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,
Figure BDA0000136855220000132
X=1,2 or 3 wherein.
The multiple tooth core of disclosure book can comprise through replace or without substituted aromatic ring, through replace or without substituted hetero-aromatic ring, through replace or without substituted non-aromatic ring, through replace or without substituted non-aromatic heterocycle, or saturated or undersaturated, through replacing or without substituted alkyl.Saturated or unsaturated alkyl can comprise one or more heteroatomss.For instance, multiple tooth core can comprise following instance:
Figure BDA0000136855220000141
Wherein R1-R15 is substituent, sulfur-containing group (for example thio alkoxy), silicon-containing group, nitrogen-containing group (for example acid amides), oxy radical (for example ketone and aldehyde), halogen, nitro, amino, cyanic acid, boron-containing group, phosphorus-containing groups, carboxylic acid or the ester of H, alkyl, aryl, OH, alkoxyl group, alkylene, alkynes base, phenyl and aforementioned group independently of one another; A1, A2, A3, A4, A5 and A6 do not exist or for can forming any atom or the group of stabilizing ring structure independently of one another, and T be tetrahedron atom (for example carbon, silicon, germanium, tin etc.) or tetrahedron group or bunch.
Functionaliseding with the connection portion that comprises the reactive imine group that is used for chelated mineral of MOF structure comprises with the lower section:
Figure BDA0000136855220000151
Figure BDA0000136855220000161
Wherein R1-R15 is selected from: H, NH2, CN, OH ,=O ,=S, Cl, I, F,
Figure BDA0000136855220000162
X=1,2 or 3 wherein.In certain embodiments, the R group is functionalized to promote the chelating of synthetic back metal by imines.
Functionaliseding to comprise reactive imine group of ZIF structure maybe can be modified and comprise with the lower section with the connection portion that forms the N-heterocyclic carbene:
Figure BDA0000136855220000171
R 1-R 5
H，NH 2，COOH，CN，NO 2，F，Cl，Br，I，S，O，SH，SO 3H，PO 3H 2，OH，CHO，CS 2H，SO 3H，Si(OH) 3，Ge(OH) 3，Sn(OH) 3，Si(SH) 4，Ge(SH) 4，Sn(SH) 4，PO 3H，AsO 3H，AsO 4H，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，
Figure BDA0000136855220000172
Functionaliseding to comprise reactive imine group of COF structure maybe can be modified and comprise with the lower section with the connection portion that forms the N-heterocyclic carbene:
Figure BDA0000136855220000181
Wherein R1-R15 is substituent, sulfur-containing group (for example thio alkoxy), silicon-containing group, nitrogen-containing group (for example acid amides), oxy radical (for example ketone and aldehyde), halogen, nitro, amino, cyanic acid, boron-containing group, phosphorus-containing groups, carboxylic acid or the ester of H, alkyl, aryl, OH, alkoxyl group, alkylene, alkynes base, phenyl and aforementioned group independently of one another; A1, A2, A3, A4, A5 and A6 do not exist or for can forming any atom or the group of stabilizing ring structure independently of one another, and T be tetrahedron atom (for example carbon, silicon, germanium, tin etc.) or tetrahedron group or bunch.
The organic connector with appropriate reaction property functional group that all are above-mentioned can carry out chemical conversion through suitable reactant back skeleton is synthetic; With through at the intraskeletal organic connector of synthetic post-modification and further functionalized hole, thus make near before can't near or can only be under great difficulty and/or cost approaching functional group become maybe and easy.The back skeleton reactant comprises all known organic transformation and its corresponding reactant; Have and comprise the for example ring of 1-20 carbon of N, S, the equiatomic functional group of O.In specific embodiments, the back skeleton reactant is used to produce chelation group to add metal.Disclosure school bag is drawn together all metals of chelating, but said metal chelating and the combination of adding functional group or preexist and the new functional group that adds.Can use cause organometallic complex be connected with skeleton with as heterogeneous catalyst for example responded.
In addition, but chelating with to add functional group or preexist suitable equally with the metal and the containing metal compound of the combination of the new functional group that adds.Can use and cause organometallic complex to be connected with skeleton to be used as the for example reaction of heterogeneous catalyst.The instance of back skeleton reactant includes, but is not limited to heterogeneous ring compound.In one embodiment, the back skeleton reactant can be saturated or unsaturated heterocycle.Use separately or be meant structure or the molecule that contains ring as the term " heterocycle " that suffix or prefix are used; It has one or more parts that independently are selected from the multivalence heteroatoms of N, O and S as ring structure, and in one or more rings, comprise at least 3 with can reach about 20 atoms.
Heterocycle can be saturated or undersaturated, contains one or more pairs of keys, and heterocycle can contain the ring more than.When heterocycle contained more than one ring, said ring can condense or uncondensed.Condensed ring generally is meant at least two rings sharing two atoms each other.Heterocycle can have the aromatic series characteristic or can not have the aromatic series characteristic.Use separately or be meant through removing one or more hydrogen derived from the heterocyclic group as term " heterocyclic group ", " heterocyclic moiety ", " heterocycle (heterocyclic) " or " heterocycle (heterocyclo) " that suffix or prefix are used.Use separately or be meant through removing a hydrogen derived from the heterocyclic monoradical as the term " heterocyclic radical " that suffix or prefix are used.Use separately or be meant heterocyclic radical with aromatic series characteristic as the term " heteroaryl " that suffix or prefix are used.Heterocycle comprises for example monocyclic heterocycles; For example: Soluol XC 100, oxyethane, thiirane, azetidine, trimethylene oxide, Thietane, tetramethyleneimine, pyrroline, imidazolidine, pyrazolidine, pyrazoline, dioxolane, tetramethylene sulfone, 2; 3-dihydrofuran-, 2; 5-dihydrofuran-, THF, thiotetrole, piperidines, 1; 2; 3; 6-tetrahydropyridine, piperazine, morpholine, thiomorpholine, pyrans, sulfo-pyrans, 2,3-dihydropyrane, tetrahydropyrans, 1,4-dihydropyridine, 1; 4-two
Figure BDA0000136855220000191
alkane, 1; 3-two
Figure BDA0000136855220000192
alkane, two
Figure BDA0000136855220000193
alkane, high piperidines, 2,3,4; 7-tetrahydrochysene-1H-azepine
Figure BDA0000136855220000194
high piperazine, 1; 3-Dioxepane, 4,7-dihydro-1,3-dioxane heptene and epoxy hexane.In addition; Heterocycle comprises heteroaromatic (heteroaryl); For example pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furans, furazan, pyrroles, imidazoles, thiazole,
Figure BDA0000136855220000195
azoles, pyrazoles, isothiazole, different azoles, 1,2,3-triazoles, tetrazolium, 1; 2; 3-thiadiazoles, 1,2,3-
Figure BDA0000136855220000202
diazole, 1; 2; 4-triazole, 1,2,4-thiadiazoles, 1; 2; 4-
Figure BDA0000136855220000203
diazole, 1,3,4-triazole, 1; 3; 4-thiadiazoles and 1,3,4-
Figure BDA0000136855220000204
diazole.
In addition; Heterocycle is contained many ring heterocycles; For example indoles, indoline, isoindoline, quinoline, tetrahydroquinoline, isoquinoline 99.9, tetrahydroisoquinoline, 1; 4-benzo two
Figure BDA0000136855220000205
alkane, tonka bean camphor, melilotine, cumarone, 2; 3-Dihydrobenzofuranes, isobenzofuran, chromene, chroman, heterochromatic full, xanthene, fen
Figure BDA0000136855220000206
thiophene, thianthrene, indolizine, isoindole, indazole, purine, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, phenanthridines, pyridine pah, phenanthroline, azophenlyene, thiodiphenylamine, fen
Figure BDA0000136855220000207
piperazine, 1,2-benzisoxa
Figure BDA0000136855220000208
azoles, thionaphthene, benzo
Figure BDA0000136855220000209
azoles, benzothiazole, benzoglyoxaline, benzotriazole, Thioxanthine, carbazole, carboline, acridine, double pyrrolizidine pyridine and quinolizine pyridine.
Except above-described many ring heterocycles, heterocycle comprises that also the ring between two or more rings wherein condenses the many rings heterocycles that comprise two common above atoms of common above key of two rings and two rings.This type of bridge joint heterocyclic instance comprises rubane, diazabicyclo [2.2.1] heptane and 7-oxabicyclo [2.2.1] heptane.
Heterocyclic radical comprises for example monocyclic heterocycles base; For example: '-aziridino, Oxyranyle, thiirane base, azetidinyl, oxetanyl, Thietane base, pyrrolidyl, pyrrolinyl, imidazolidyl, pyrazolidyl, pyrazolinyl, dioxolanyl, tetramethylene sulfone base, 2; 3-dihydrofuran-base, 2; 5-dihydrofuran-base, tetrahydrofuran base, thiophene alkyl, piperidyl, 1; 2; 3; 6-tetrahydro pyridyl, piperazinyl, morpholinyl, thio-morpholinyl, pyranyl, sulfo-pyranyl, 2; 3-dihydro pyranyl, THP trtrahydropyranyl, 1; 4-dihydropyridine base, 1,4-two
Figure BDA00001368552200002010
alkyl, 1,3-two
Figure BDA00001368552200002011
alkyl, two
Figure BDA00001368552200002012
alkyl, homopiperidinyl, 2; 3; 4,7-tetrahydrochysene-1H-azepine
Figure BDA00001368552200002013
base, high piperazinyl, 1,3-Dioxepane base, 4; 7-dihydro-1,3-dioxane heptenyl and cyclohexene oxide groups.
In addition; Heterocyclic radical comprises aromatic heterocycle or heteroaryl; For example pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, thienyl, furyl, furazan base, pyrryl, imidazolyl, thiazolyl,
Figure BDA00001368552200002014
azoles base, pyrazolyl, isothiazolyl, different
Figure BDA00001368552200002015
azoles base, 1; 2; 3-triazolyl, tetrazyl, 1,2,3-thiadiazolyl group, 1; 2; 3-
Figure BDA00001368552200002016
di azoly, 1,2,4-triazolyl, 1; 2; 4-thiadiazolyl group, 1,2,4-
Figure BDA00001368552200002017
di azoly, 1; 3; 4-triazolyl, 1,3,4-thiadiazolyl group and 1; 3,4-
Figure BDA00001368552200002018
di azoly.
In addition; Heterocyclic radical is contained many ring heterocyclic radicals (comprising aromatic series or non-aromatic); For example indyl, indolinyl, isoindoline base, quinolyl, tetrahydric quinoline group, isoquinolyl, tetrahydro isoquinolyl, 1; 4-benzo two
Figure BDA00001368552200002019
alkyl, tonka bean camphor base, melilotine base, benzofuryl, 2; 3-dihydro benzo furyl, isobenzofuran-base, chromenyl, chromanyl, different chromanyl, oxa-anthryl, fen thiophene base, thianthrenyl, indolizinyl, pseudoindoyl, indazolyl, purine radicals, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridyl, phenanthridinyl, pyridine base, phenanthroline base, phenazinyl, phenothiazinyl, fen
Figure BDA0000136855220000212
piperazine base, 1 pah, 2-benzisoxa
Figure BDA0000136855220000213
azoles base, benzothienyl, benzo
Figure BDA0000136855220000214
azoles base, benzothiazolyl, benzimidazolyl-, benzotriazole base, Thioxanthine base, carbazyl, carbolinyl, acridyl, double pyrrolizidine pyridine base and quinolizine pyridine base.
Except above-described many ring heterocyclic radicals, heterocyclic radical comprises that also the ring between two or more rings wherein condenses the many rings heterocyclic radicals that comprise two common above atoms of common above key of two rings and two rings.The instance of this type of bridge joint heterocyclic radical comprises quinuclidinyl, diazabicyclo [2.2.1] heptyl and 7-oxabicyclo [2.2.1] heptyl.
Spendable metals ion comprises Li in the skeleton of disclosure book synthetic +, 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+With its combination, and corresponding metal salt counter anion.
Metals ion can through with the skeleton main chain in (for example imines or the N-heterocyclic carbene) complexing of functionalized organic linker or introduces among opening skeleton, MOF, ZIF and the COF through simple ion exchange.Therefore, can introduce any metals ion in the periodictable.
The skeleton of disclosure book can prepare in water-based or non-aqueous system.Depend on the circumstances, solvent can be polarity or non-polar solvent.Solvent can comprise template (templating agent) or the optional part that contains monodentate functional group.The instance of non-aqueous solvent comprises NPH (for example pentane, hexane), benzene,toluene,xylene, chlorobenzene, oil of mirbane, cyanobenzene, aniline, naphthalene, petroleum naphtha, n-alkanol (for example methyl alcohol, ethanol, n-propyl alcohol), Virahol, acetone, 1,3-ethylene dichloride, methylene dichloride, chloroform, tetracol phenixin, THF, N, methyl-sulphoxide, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, DEF, thiophene, pyridine, thanomin, triethylamine, quadrol etc.One of ordinary skill in the art confirm appropriate solvent based on initial reactant easily, and it is most important not think that solvent is chosen in the material that obtains disclosure book.
Template can be used in the method for disclosure book.Used template is added in the reaction mixture in the disclosure book, is used for occupying the hole of gained crystallization basic skeleton.In some variants of disclosure book, gap weighting agent, the chemical substance that is adsorbed and guest species increase the surface-area of metallic organic framework.Suitable gap weighting agent comprises the component that for example is selected from by the following group of forming: (i) alkylamine and its corresponding alkylammonium salt, contain straight chain, side chain or cyclic aliphatic base and have 1 to 20 carbon atom; (ii) arylamines and its corresponding aryl ammonium salt have 1 to 5 phenyl ring; (iii) alkyl
Figure BDA0000136855220000221
salt contains straight chain, side chain or cyclic aliphatic base and has 1 to 20 carbon atom; (iv) Fang Ji Phosphonium salt has 1 to 5 phenyl ring; (v) alkyl organic acid and its corresponding salt contain straight chain, side chain or cyclic aliphatic base and have 1 to 20 carbon atom; (vi) aryl organic acid and its corresponding salt have 1 to 5 phenyl ring; (vii) fatty alcohol contains straight chain, side chain or cyclic aliphatic base and has 1 to 20 carbon atom; Or (viii) aryl alcohol has 1 to 5 phenyl ring.
Crystallization can be carried out as follows: make solution left standstill at room temperature or in the isothermal baking oven up to 300 ℃ (isothermal oven); Diluted alkaline is joined in the solution with the beginning crystallization; Diluted alkaline is diffused in the solution with the beginning crystallization; And/or solution transferred in the closed container and be heated to preset temperature.
The device that is used for adsorptivity picked-up chemical substance also is provided.Said device comprises sorbent material, the skeleton that said sorbent material comprises that this paper provides or the method through disclosure book obtains.Picked-up can be a reversible or irreversible.Aspect some, in sorbent material is included in the form of dispersive granule for absorbing.The three-dimensional carrier of the permeable and/or gas-permeable of solid-liquid can imbedded or be fixed in to granule for absorbing.Aspect some, granule for absorbing has and is used for absorbing or the hole of storing liquid or gas reversiblely, and wherein granule for absorbing adsorbs reversiblely or absorbs liquid or gas.
In some embodiments; The device that this paper provided comprises and is used to store chemical substance, for example ammonia, carbonic acid gas, carbon monoxide, hydrogen, amine, methane, oxygen, argon gas, nitrogen, argon gas, organic dye, encircle the storage element of organic molecule and its combination more.
The method that is used for adsorptivity picked-up chemical substance also is provided.Said method comprises makes chemical substance contact with the sorbent material that comprises the skeleton that this paper provides.The picked-up of chemical substance can comprise the storage chemical substance.Aspect some, chemical substance is stored in and is fit to it as under the condition of the energy.
The method that is used for adsorptivity picked-up chemical substance also is provided, and it comprises that the device that makes chemical substance and this paper provide and describe contacts.
Sweet natural gas is important fuel gas, and extensive as basic material in petroleum chemistry and other CPI.The composition of Sweet natural gas extensively changes between each gas field.Many gas reservoir contain the hydrocarbon (for example less than 40%) of relatively low per-cent and the acid gas of high per-cent, mainly are carbonic acid gas, but also can be hydrogen sulfide, nitric sulfid, dithiocarbonic anhydride and various mercaptan.Need to remove the acid gas in the Sweet natural gas of making in the side area,, be used to be transported to pipeline, reclaim natural gas liquids, reclaim helium, be converted into natural gas liquids (LNG), or be used for denitrogenation subsequently so that the dry type Sweet natural gas through adjusting or desulfurization is provided.CO 2Existing under the situation of water is corrosive, and it can form dry ice, hydrate and can in pipeline and in the normally used cyrogenic equipment of natural gas processing, cause frozen problem.In addition, because to not contribution of calorific value, CO 2Only can increase the cost of gas transmission.
An importance of any gas conditioning method all is an economy.Sweet natural gas is typically handled under heavy body, even this causes the difference of capital and running cost of processing unit very little, in the selection of processing technology, also can become very important factor.Because tooling cost, some natural gas sources are used at present making and are uneconomical.Demand for the modified form gas conditioning method with high reliability and simplified control property is continuing always.
In addition, as the main source of current artificial carbonic acid gas, the carbonic acid gas in the power station stack gases is usually through cooling and pressurised exhaust gas or through letting smog remove through the fluidized-bed of amine aqueous solution, and these two kinds of methods all cost are very high and efficient is not high.Seek based on the carbonic acid gas chemisorption on oxide surface or other method in porous silicate, carbon and the film of being adsorbed on be used as absorbing the means of carbonic acid gas.Yet; In order to let effective adsorption medium in co 2 removal, have the long life; It should have two characteristics concurrently: (i) periodic structure; Wherein the picked-up of carbonic acid gas and release are completely reversibilities and (ii) flexible, can utilize it to realize that chemical functionalization and molecular level fine setting are to obtain best picked-up ability.
Proposed many being used for, and on technical scale, it has been implemented from the method for air flow recovery or removal carbonic acid gas.Said method can extensively change, but relates generally to solvent absorbing, absorption on porous adsorbent, distills or diffuse through these several kinds of forms of semi-permeable membranes.
Following examples are intended to explanation but do not limit disclosure book.Though the embodiment that said embodiment representative possibly be used, but still substitutability ground uses known other program of one of ordinary skill in the art.
Embodiment
Embodiment 1: the metallization of synthetic back
Unless otherwise indicated, otherwise all reagent all obtain and need not to be further purified and can use from commercial source (Alfa Aesar, Cambridge isotope laboratories, Sigma Aldrich), and all operations all carries out under argon gas atmosphere.The yield of being reported is not through optimizing.Elemental microanalysis is to carry out at the chemistry of University of California, Los Angeles and department of biochemistry.
(Zn 4O) 3(BDC-C 6H 5N 2) 3(BTB) 4(Zn 4O) 3(BDC-C 6H 5N 2PdCl 2) 3(BTB) 4Synthetic
(Zn 4O) 3(BDC-C 6H 5N 2) 3(BTN) 4Synthesis program. with 200mg (Zn 4O) 3(BDC-NH 2) 3(BTB) 4Be placed in the 20ml vial, immerse in the 10ml dry toluene.In bottle, add 0.3ml 2-pyridylaldehyde and under noiseless, left standstill 5 days.The yellow crystals that obtains is used CH 2Cl 2Washing and vacuum-drying obtain (Zn 4O) 3(BDC-C 6H 5N 2) 3(BTB) 4(0.190g, 87%).
(Zn 4O) 3(BDC-C 6H 5N 2PdCl 2) 3(BTB) 4Synthesis program. with 100mg (Zn 4O) 3(BDC-C 6H 5N 2) 3(BTB) 4Be placed in the 20ml bottle, immerse the anhydrous CH of 10ml 2Cl 2In.Add 0.20g PdCl 2(CH 3CN) 2, cause yellow crystals to become mulberry.Reaction mixture left standstill 12 hours under noiseless, and after this mulberry crystal is used CH 2Cl 2Washing is also dry, obtains (Zn 4O) 3(BDCC 6H 5N 2PdCl 2) 3(BTB) 4(0.098g, 85%).
The synthesis program of model compound dichloro (N-(2-pyridyl methylene radical) aniline-N, N ') palladium (II). use PdCl 2(CH 3CN) 2Acetone soln 2.0g (E)-N-((pyridine-2-yl) methylene radical) aniline was handled 2 hours.Orange powder dichloro (N-(2-pyridyl methylene radical) aniline-N, the N ') palladium (II) that obtains (1.45g) is filtered, and is air-dry and need not to be further purified and can use.
XAS data gathering .XAS measurement is to utilize in synchrotron radiation laboratory, Stamford (SSRL) to contain 80 to 100mA SPEAR energy storage ring and under 3.0GeV, carry out.Pd K MARG is to go up collection at the structural molecular biology XAS light beam line 7-3 of (wiggler field) operation that waves with 2T.Use Si (220) double-crystal monochromator.Light beam line 7-3 has been equipped with the vertical collimation mirror of the rhodium coating that is positioned at the monochromator upper reaches and the press-bending-cylindrical focusing mirror in downstream (also by the rhodium coating).Harmonic wave suppresses through the intensity detuning 50% of incident radiation being realized when the end of scan.The intensity of incident X-rays and Transmission X ray is used the ionization chamber monitoring that is filled with argon gas or nitrogen.X ray is absorbed under the transmission mode and measures.During data gathering, sample uses Oxford instrument liquid helium streaming cryostat to be maintained under the temperature of about 10K.For each sample, accumulate three scannings, and reference calibrates energy with the absorption that each scans simultaneously-measured Pd paper tinsel, suppose that wherein the minimum energy flex point is 24349.0eV.The energy threshold of extended X-ray absorption fine structure (EXAFS) vibration is assumed that 24370eV.
XAS data analysis .EXAFS vibration χ (k) uses the EXAFSPAK computer package, uses ab initio calculation mutually theoretical and with the amplitude function of the 8.25th edition calculating of program FEFF, through the fitting of a curve quantitative analysis.Not to data carry out smoothly, filtration or relating operation.
Table 1:EXAFS curve fitting parameter a.
Figure BDA0000136855220000251
aLigancy N, interatomic distance
Figure BDA0000136855220000252
The Debye-Waller factor
Figure BDA0000136855220000253
With threshold energy displacement E0 (eV).Value in the bracket is the estimated standard deviation (precision) from the diagonal element acquisition of covariance matrix.Accuracy will be more much bigger with numeral and Debye-Waller factor than these values.The summation of summation all data points of being in the refine to be comprised wherein that the error of fitting function F is defined as
Figure BDA0000136855220000254
.
XANES measures. and Fig. 4 is Pd model compound, PdCl relatively 2(CH 3CN) 2(Zn 4O) 3(BDC-C 6H 5N 2PdCl 2) 3(BTB) 4The proximal edge district.This piles up graphic representation and has given prominence to model complex compound and (Zn 4O) 3(BDC-C 6H 5N 2PdCl 2) 3(BTB) 4Between similarity, show that palladium all is in the closely similar chemistry and electronic environment under two kinds of situation.
Powder x-ray diffraction. the powder X-ray ray data is to use Bruker D8-Discover θ-2 θ diffractometer to collect for how much with reflectivity Bragg-Brentano; Wherein use 1600W (40kV, 40mA) power down and be equipped with Vantec straight-line detection device through the radiation of the filtering Cu K of Ni α line focus.Radiation uses parallel focusing Gobel mirror to focus on.Said system also is equipped with anti-scattering cover, and it stops the incident diffusion radiation to arrive detector, thereby stops 2 θ＜3 time common very big background.Through leaf spatula (wide-blade spatula) powder that drips leniently, shakeout sample with blade then, sample is placed on the zero background specimen holder.Sample is through being dissolved in small quantity of material in the methyl alcohol, and supersound process prepared in 10 minutes subsequently.Filtering precipitate is then collected data then.
Mass spectroscopy. with (Zn 4O) 3(BDC-C 6H 5N 2) 3(BTB) 4Sample dissolution and is carried out ESI-MS (referring to for example Fig. 5) under negative ion mode in MeOH.
Gas adsorption is measured. and low pressure Ar adsorption isothermal line is by volume measured on Autosorb-1 analyser (Quantachrome Instruments).Liquid argon is bathed (87K) and is used to measure.Used Ar and He gas are the UHP levels.According to the Ar adsorption isothermal line, calculated the BET surface-area (useable surface area) and the total pore volume (table 2) of every kind of material.The pore volume of every kind of material is from Dubinin-Radushkevich (DR) model assessment, supposes wherein that adsorbate is in a liquid state and adsorbs to relate to the hole filling process.In order to estimate the pore size distribution of MOF,, use the non local density functional theory (NLDFT) that realizes hybrid core to analyze the Ar thermo-isopleth of Ar absorption under the 87K based on the zeolite that contains the cylindrical pore/silica model.
The summary of the porosity measurement of table 2:MOF.
Figure BDA0000136855220000261
For porosity measurement, with (the Zn of the synthetic attitude of original position 4O) 3(BDC-C 6H 5N 2) 3(BTB) 4Immerse in the acetone and kept 24 hours, during to activation solvent makeup three times.In Tousimis Samdri PVT-3D critical evaporator, use supercritical CO 2The emptying sample.The sample that in brief, will contain acetone is placed in the compartment and uses liquid CO 2Exchange acetone.To contain sample and liquid CO then 2Compartment be heated to about 40 ℃ and under super critical condition (typically 1300psi), kept 1 hour.CO 2Under about 40 ℃, slowly discharge (about 1 hour), obtain porous material from air chamber.
The imino-pyridine moiety has been proved to be the general Fas lignand system that in known coordination environment, combines multiple transition metal.Disclosure book mixes A through the condensation reaction (scheme 1) of amine-functionalized skeleton and 2-pyridylaldehyde with said part.Through joining 1.5 equivalent 2-pyridylaldehydes in the dry toluene that contains A and letting reaction carry out synthetic impartial netted functionalized MOF B over 5 days; The color of needle-like crystal is from transparent yellowing during this time; Had and the product of the very consistent composition of expection chemical formula, so indicated Quantitative yield.Powder x-ray diffraction (PXRD) research (Fig. 1) shows that B keeps crystallinity and after the covalency conversion, has the underlying topology structure identical with A.The unitary existence of imino-pyrimidine is through being confirmed that by the mass spectroscopy of digestion B sample said mass spectroscopy shows the parent ion peak under the m/z 269 ([M-H]-), is attributable to the part fragment.
Through with 1.5 equivalent PdCl 2(CH 3CN) 2Join the anhydrous CH that contains B 2Cl 2In realize impartial net-like metallic, wherein the yellow crystal material becomes mulberry in several minutes.After 12 hours, with a CH of 10mL 2Cl 2With material washing 3 times; Then crystal is immersed dry CH 2Cl 2In, solvent of renewal in per 24 hours continues 3 days, obtains C.The PXRD collection of illustrative plates (Fig. 1) of C has reconfirmed that it keeps crystallinity and has the skeleton topology identical with A and B.From the hole, remove guest species through keeping 12 hours at 80 ℃ of following emptying crystal.Skeleton to the no guest species of C carries out ultimate analysis, obtains molecular formula C 50H 28N 2O 13Zn 4PdCl 2, its Pd/Zn ratio is 1: 4, the quantitative metallization in this and imino-pyridine site is consistent.
Analyze the porosity of B and C through obtaining 87K Ar thermo-isopleth (Fig. 2).Notably, two kinds of materials are all kept porosity after two chemical transformation subsequently.In addition, A-C is observed analogue; Yet, in the thermo-isopleth of C, there is slight hysteresis phenomenon, there is defective in this hint, possibly be to be caused by the series of chemical of on crystal, carrying out.
In order to confirm Pd and the complexing of imino-pyridine unit and accurately to confirm intraskeletal Pd coordination environment, the C sample is carried out Pd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis.Fig. 3 shows EXAFS fourier transformation and the curve fitting analysis result of C.Data analysis indication exists 2.276 (2) and two Pd-Cl and two Pd-N parts of
Figure BDA0000136855220000271
respectively.The investigation of Cambridge structural database shows that these two distances are consistent with the crystallographic data of similar Pd compound.In addition; For the optimum data match; Two kinds of Pd-C under needing
Figure BDA0000136855220000272
interact, and it belongs to the part main chain.The EXAFS data analysis provides the D-M (Determiner-Measure) construction of the Pd coordination environment in the MOF to describe, and has clearly proved that Pd is incorporated into skeleton through the imino-pyridine moiety.In addition, the analysis of x ray absorption near edge structure (XANES) spectrographic is shown, the part of the main chemical species of the intraskeletal Pd of C and combination imino-pyridine consistent and with starting substance PdCl 2(CH 3CN) 2Inconsistent.
Embodiment 2: metallization before synthetic
Linker (L0-L2) is only and if IRMOF-76,77 synthetic and analytical data. point out in addition, otherwise chemical is to buy and in statu quo use from commercial supplier.Anhydrous solvent is to obtain from EMDChemicals
Figure BDA0000136855220000273
system.Thin-layer chromatography (TLC) is to use the sheet glass (Whatman LK6F) that coating in advance contains the silica gel 60 of fluorescent indicators to carry out.Sheet glass is by UV light (254nm) and iodine/silica gel inspection.Column chromatography is to use silica gel 60F (230-400 order) to carry out. 1H, 13C with 19F solution NMR spectrum is recorded on Bruker ARX400 (400MHz) or AV600 (600MHz) spectrograph.Residual solvent is used as 1H with 13The internal standard substance of C NMR.Trifluoroacetic acid (δ=-76.5ppm) be used as 19The external standard of F NMR.Chemical shift is enumerated with ppm based on the δ scale, and coupling constant is with hertz (Hz) record.Below abbreviation is used to represent multiplicity: s, and is unimodal; D, doublet; T, triplet; Q, quartet; B, broad peak; M, multiplet or overlapping peaks.
13C CP/MAS solid state NMR spectrum is on Bruker DSX-300 spectrograph, to collect, and said spectrograph uses standard Bruker evil spirit angle rotation (MAS) probe with 4mm (external diameter) zirconium white rotor.Cross polarization and MAS (CP/MAS) be used for 75.47MHz ( 13C) survey down. 1H with 13 C 90 degree PWs all are 4 μ s.CP duration of contact is 1.5ms.Superpower two pulse PM (TPPM) 1The H decoupling zero is used in data acquisition period.The decoupling zero frequency is corresponding to 72kHz.MAS sample SR is 10kHz.Do not determine that by observing significantly sacrificing depend on compound, the recycling delay between the scanning is between 10s and 30s for the strength of signal that scans next scanning from. 13The C chemical shift is to provide with respect to TMS, and TMS uses to be appointed as 29.46ppm and to be 0ppm as the methine carbon signal calibration of the diamantane of secondary reference.
FT-IR spectrum is collected on Shimazu FT-IR spectrograph.Electrospray ionization mass spectrometry (ESI-MS), substance assistant laser desorpted ionized mass spectrum (MALDI-MS) and chemical ionization mass spectrometry-gc (CI/GC-MS) are that carry out the molecule experimental center (Molecular Instrumentation Center) in University of California, Los Angeles.
Elemental microanalysis is on Thermo Flash EA1112 burning CHNS analyser, to carry out.The analyses of IRMOF-76 and 77 inductively coupled plasma (ICP) are to carry out through Intertek QTI.
Figure BDA0000136855220000281
S1: according to the program of being reported 1Preparation starting substance (1).According to the open program that in treating processes, has minor alteration 1,2Carry out 1 reduction.In the 2000mL flask, add 1 (20.5g, 70mmol), CoCl 2(91mg, 0.7mmol), THF (200mL) and EtOH (450mL).Mixture is refluxed.Per hour three times (8.0g altogether) adds NaBH 4(every part of 2.65g, 70mmol).After being consumed, with the mixture cool to room temperature through TLC analysis confirmation 1.After adding entry (300mL) and fully stirring 10 minutes, use Celite to leach gelatinous precipitate.Evaporation organic solvent and with dichloromethane extraction product three times.Organic layer water and the brine wash that merges also used Na 2SO 4Dry.Leach extract, evaporation, and with short pad silica gel chromatography (eluent: hexane/acetone=5/1) purification of crude mixture.Evaporate the solution that merges, obtain the diamines of orange solids shape.
The diamines that obtains directly is used for next step.Add HC (OEt) in the diamines in being dissolved in MeOH (350mL) 3(13.9mL, 84mmol) and thionamic acid (340mg, 3.5mmol).With mixture stirred overnight and formation powder precipitation thing.Evaporating solvent is also with ether cleaning and removing residual thing.Dry under air, obtain the S1 (10.1g, 52% yield, 2 steps) of yellow powder shape.
1H NMR (400MHz, DMSO-d 6): δ=7.35 (s, 2H), 8.36 (s, 1H), 13.2 (brs, 1H); 13C NMR (100MHz, DMSO-d 6): δ=113.75,126.21,132.75,144.05; IR (KBr, cm -1) v=630,792,912,956,1163,1217,1259,1284,1340,1381,1433,1489,1616,2823,3062; CI/GC-MS [M] +C 7H 4Br 2N 2 +M/z=276; Ultimate analysis: C 7H 4Br 2N 2Calculated value: C, 30.47; H, 1.46; N, 10.15%, experimental value: C, 30.21; H, 1.64; N, 10.94%.
Figure BDA0000136855220000291
2: in the 1000mL flask, add S1 (19.7g, 71.4mmol), K 2CO 3(29.6g, 214mmol) and EtOH (500mL).The reflux mixture.(8.8mL 142.8mmol), and keeps mixture and refluxed 1 hour in hot mixt, dropwise to add MeI.After being consumed, with the mixture cool to room temperature through TLC analysis confirmation S2.Add entry (200mL) and evaporate after the EtOH collection powdery precipitate, water and hexane/Et 2O (1/1) washing, drying obtains 2 (21.0g, 100% yields) of brown powder shape.
1H NMR (400MHz, DMSO-d 6): δ=4.05 (s, 3H), 7.34 (s, 2H), 8.32 (s, 1H); 13C NMR (100MHz, DMSO-d 6): δ=34.51,102.75,112.82,126.14,128.05,132.44,143.80,147.96; IR (KBr, cm -1) v=524,623,719,781,918,1058,1105,1186,1219,1273,1301,1332,1390,1465,1500,1604,1816,2940,3086; CI/GC-MS [M] +C 8H 6Br 2N 2 +M/z=290; Ultimate analysis: C 8H 6Br 2N 2Calculated value C, 33.14; H, 2.09; N, 9.66%, experimental value C, 31.92; H, 2.13; N, 9.50%.
Figure BDA0000136855220000301
S2: in the 1000mL flask, add 4-anisole ylboronic acid (20.5g, 113mmol), tetramethyl ethylene ketone (14.0g, 118mmol) and THF (500mL).Mixture heating up to refluxing, was stirred 2 hours, then cool to room temperature.With short pad alkali alumina filtering solution, and the S2 (26.0g, 85% yield) of evaporating solvent to obtain white powder.
1H NMR (400MHz, CDCl 3): δ=1.34 (s, 12H), 3.83 (s, 3H), 7.86 (d, J=6.7Hz, 2H), 8.01 (d, J=6.7Hz, 2H). 13C NMR (100MHz, CDCl 3): δ=24.88,52.13,84.16,128.59,132.32,134.66,167.12; IR (KBr, cm -1) v=486,520,576,651,709,771,806,856,1018,1109,1140,1278,1373,1508,1562,1614,1724 (s), 1950,2985 (s); CI/GC-MS [M] +C 14H 19BO 4 +M/z=262; Ultimate analysis: C 14H 19BO 4Calculated value C, 64.15; H, 7.31%, experimental value C, 64.81; H, 7.30%.
Figure BDA0000136855220000302
3: according to open program 3Carry out transesterify.Under nitrogen atmosphere through 30 fens clockwise through the S2 that stirs (13.2g, 50mmol) dropwise add in the solution in the 500mL anhydrous diethyl ether t-BuOK (28.0g, 250mmol).Continue to stir 2 hours.Suspension-s is poured in the water (1000mL).After separating organic layer, with ethyl acetate extraction compound three times.The organic layer that merges is used Na 2SO 4Drying leaches and evaporates, and obtains 3 (12.2g, 80% yields) of white powder.3 need not to be further purified and promptly are used for next step.
1H NMR (400MHz, CDCl 3): δ=1.35 (s, 12H), 1.63 (s, 9H), 7.85 (d, J=6.7Hz, 2H), 7.96 (d, J=6.7Hz, 2H); 13C NMR (100MHz, CDCl 3): δ=24.87,28.19,81.08,84.09,128.42,134.25,134.52,165.80; IR (KBr, cm -1) v=522,578,651,709,777,815,854,960,1016,1116,1141,1170,1296,1359,1508,1560,1612,1705 (s), 1957,1981 (s); CI/GC-MS [M-(CH 2=C (CH 3) 2)] +C 13H 18BO 4 +M/z=249. ultimate analysis: C 17H 25BO 4Calculated value C, 67.12; H, 8.28%, experimental value C, 67.60; H, 8.23%.
Figure BDA0000136855220000311
4: under nitrogen atmosphere will through stir 2 (1.93g, 6.67mmol), 3 (4.67g, 15.35mmol), Pd (PPh 3) 4(385mg, 0.33mmol) and K 2CO 3(2.76g, 20mmol) in 50mL 1,4-two
Figure BDA0000136855220000312
Solution in alkane and the 12mL water is heated to 100 ℃.Continue stirred overnight, then with the mixture cool to room temperature.Add entry and with ethyl acetate extraction organic cpds three times.The organic layer that merges is with brine wash and use Na 2SO 4Dry.Extract filters and evaporation through too short pad alkali alumina.The resistates that obtains is with hexane/Et 2O (2/1) washes, and obtains 4 (2.0g, 62% yields) of brown powder shape.
1H NMR (400MHz, CDCl 3): δ=1.62 (s, 9H), 1.64 (s, 9H), 3.42 (s, 3H), 7.23 (d, J=7.6Hz, 1H), 7.49 (d, J=7.6Hz, 1H), 7.52 (d, J=8.1Hz, 2H), 7.87 (s, 1H), 8.05-8.16 (m, 6H); 13C NMR (100MHz, CDCl 3): δ=28.26,34.50,80.79,81.38,121.52,125.04,125.99,129.10,129.59,129.80,130.79,131.51,131.68,132.38,142.32,142.40,145.54,165.45,165.87; IR (KBr, cm -1) v=509,592,630,661,704,731,769,825,848,867,1018,1118,1168,1294,1369,1471,1500,1608,1708 (s), 2978 (s); CI/GC-MS
Figure BDA0000136855220000313
Figure BDA0000136855220000314
Ultimate analysis: C 30H 32N 2O 4Calculated value C, 74.36; H, 6.66; N, 5.78%, experimental value: C, 73.05; H, 6.50; N, 6.06%.
5: with 4 (570mg, 1.17mmol) and MeI (0.73mL, 11.7mmol) solution in the 12mL acetonitrile is heated to and refluxes and stirred overnight.After the mixture cool to room temperature, the evaporation volatile matter.The resistates that obtains obtains 5 (689mg, 94% yields) of brown powder shape with hexane/ethyl acetate (2/1) flushing.
1H NMR (400MHz, CDCl 3): δ=1.61 (s, 18H), 3.87 (s, 6H), 7.41 (s, 2H), 7.53 (d, J=6.6Hz, 4H), 8.10 (d, J=6.6Hz, 4H), 10.64 (s, 1H); 13C NMR (100MHz, CDCl 3): δ=28.17,37.56,81.79,128.44,128.88,129.59,129.77,129.88,132.87,139.20.145.38,164.91; IR (KBr, cm -1) v=621,709,773,846,1012,1118,1165,1296,1369,1456,1608,1710 (s), 2976,3435 (br); ESI-TOF-MS
Figure BDA0000136855220000322
Ultimate analysis: C 31H 35IN 2O 4Calculated value C, 59.43; H, 5.63; N, 4.47%, experimental value: C, 56.83; H, 5.70; N, 4.72%.
Figure BDA0000136855220000323
L0: (2.1g 3.35mmol) adds HBF in the solution in methylene dichloride (35mL) to 5 4OEt 2(2.26mL, 16.5mmol).Mixture at room temperature stirred 2 hours.After with the ether dilution, filtering precipitate is also with methylene dichloride and ether thorough washing.Join in the powder toluene and evaporation.This step repeats twice to remove the residual water as azeotropic mixture.After 50 ℃ of following vacuum-drying, obtain the pulverous L0 of grey (1.7g, 100% yield).
1H?NMR(400MHz，DMSO-d 6)：δ＝3.50(s，6H)，7.54(s，2H)，7.72(d，J＝9.2Hz，4H)，8.03(d，J＝9.2Hz，4H)，9.63(s，1H)，13.2(brs，2H)； 13C?NMR(100MHz，DMSO-d 6)：δ＝37.94，128.58，128.72，129.72，130.07，130.70，131.10，140.12，145.82，163.18； 19F?NMR(376.5MHz，DMSO-d 6)：δ＝-148.9
Figure BDA0000136855220000331
MALDI-MS：
Figure BDA0000136855220000332
Figure BDA0000136855220000333
S3: with 5 (1.87g, 3mmol), Pd (CH 3CN) 2Cl 2(900mg, 3.3mmol), NaI (750mg, 6mmol) and K 2CO 3(2.07g, 15mmol) solution in the 30mL pyridine is heated to and refluxes and stirred overnight.After the mixture cool to room temperature, evaporate all volatile matters.The resistates that obtains is dissolved in chloroform (200mL) and the water (100mL).Isolating organic layer is used 5%CuSO 4Na is used in the aqueous solution (30mL, twice) and salt solution (30mL) washing then 2SO 4Dry.Extract is through too short pad filtered through silica gel and with hexane/acetone (2/1) thorough washing.Evaporate the organic solution that merges, obtain the S3 (2.5g, 88% yield) of orange powder shape.
1H NMR (400MHz, CDCl 3): δ=1.64 (s, 18H), 3.79 (s, 6H), 7.09 (s, 2H), 7.25-7.34 (m, 2H), 7.51 (d, J=8.2Hz, 4H), 7.70-7.77 (m, 1H), 8.11 (d, J=8.2Hz, 4H), 8.97-9.01 (m, 2H) 13C NMR (100MHz, CDCl 3): δ=28.24,40.04,81.53,124.60,125.01,125.80,129.27,129.93,132.06,132.87,141.45,153.85 (NHC carbon), 165.29; IR (KBr, cm -1) v=675,692,769,848,1012,1116,1165,1294,1388,1446,1604,1710 (s), 2974,3445; Ultimate analysis: C 36H 39I 2N 3O 4Pd calculated value C, 46.10; H, 4.19; N, 4.48%, experimental value: C, 43.64; H, 4.02; N, 4.79%.
Figure BDA0000136855220000341
L1: (2.5g 2.64mmol) adds Me in the solution in methylene dichloride (15mL) to S3 3SiOTf (1.67mL, 9.24mmol).Mixture at room temperature stirred 2 hours.After adding entry, filter brown throw out and water and methylene dichloride thorough washing.To the CHCl that contains brown powder (S4) 3/ MeOH (1/1, add in 25mL) pyridine (1mL, 13.2mmol).Mixture at room temperature stirred 30 minutes.The evaporation volatile matter, resistates is suspended in the methylene dichloride.In suspension-s, add 5%CuSO 4The aqueous solution.Mixture stirred 10 minutes, and orange powder is filtered and use water washing.Join in the orange powder toluene and evaporation.This step repeats twice to remove the residual water as azeotropic mixture.After the vacuum-drying, obtain the L1 (1.62g, 74% yield) of orange powder shape.
1H NMR (400MHz, DMSO-d 6): δ=3.68 (s, 6H), 7.21 (s, 2H), 7.48-7.52 (m, 2H), 7.63 (d, J=7.6Hz, 4H), 7.87-7.93 (m, 1H), 8.03 (d, J=7.6Hz, 4H), 8.83-8.86 (m, 2H), 13.1 (brs, 2H); 13C NMR (150MHz, 80 ℃, DMSO-d 6): δ=125.54,125.72,126.05,130.00,130.61,132.67,138.50,141.55,153.13 (NHC carbon), 166.57, on nitrogen through substituted methyl carbon peak (～40ppm) with the remaining peak overlapping of DMSO; 13C CP/MAS solid state NMR (75M Hz): δ=42.15,125.00,129.27,142.18,153.28 (NHC carbon), 172.74; IR (KBr, cm -1) v=549,594,673,692,769,825,862,920,1012,1078,1109,1176,1290,1386,1444,1606,1685 (s), 2546,2663,3448; ESI-TOF-MS (negatively charged ion pattern)
Figure BDA0000136855220000342
And the isotropic substance collection of illustrative plates matees with the simulation collection of illustrative plates well; Ultimate analysis: C 28H 23I 2N 3O 4Pd calculated value C, 40.73; H, 2.81; N, 5.09%, experimental value: C, 40.22; H, 2.91; N, 5.20%.
Figure BDA0000136855220000351
L2: to L1 (～80mg) add quinoline (0.2mL) in the suspension-s in the 5mL chloroform.Mixture at room temperature stirred 1 hour.The evaporation volatile matter, resistates is suspended in the chloroform and leaches, and collects the L2 of orange powder shape, and it is as the reference compound of digestion research.
Figure BDA0000136855220000352
IRMOF-76: in bottle with cover with L0 (47mg, 0.1mmol), Zn (BF 4) 2Hydrate (72mg, 0.3mmol), KPF 6(186mg, solid mixture 1mmol) is dissolved in N, dinethylformamide (DMF, 15mL) in.Reaction is heated to 100 ℃ and kept 24-48 hour, on the bottle wall, obtains bulk crystals.Bottle shifts out and naturally cools to room temperature then from baking oven.After opening bottle and from mixture, removing mother liquor, collect clear crystal also with DMF (3 * 4mL) flushings.Measure the powder and the monocrystalline X-ray diffraction of this material immediately.Sample after with chloroform exchange solvent and vacuum-drying, is used for CP/MAS NMR and IR measures.
The analytical data of IRMOF-76: DCl/DMSO-d 6(1/20) the quilt digestion IRMOF-76's in 19F NMR.Confirmed BF 4(149.2ppm, s) with (71.1ppm, d, J PF=707Hz) existence.
IR(KBr，cm -1 )v＝557，715，783，843，1012，1406，1544，1608(s)，3421
13 C CP/MAS solid state NMR (75MHz)(36.10 methyl), 129.06 *, 138.69 *, 143.60 (C2 of benzoglyoxaline), 174.11 (CO 2Zn). *Widen overlapping peaks in the aromatic series zone.
Icp analysis. the element ratio of measurement: C 69H 54.5B 0.53P 1.89F 10.9N 6.1Zn 4.3The molecular formula of estimating: Zn 4O (C 23H 17N 2O 5) 3(BF 4) 0.5(PF 6) 1.6(OH) 0.9=C 69H 51.9B 0.5P 1.6F 11.6N 6O 17.9Zn 4
Do not detect the potassium (K) or the iodine (I) that are higher than trace.
Below inspection is also unsuccessful from IRMOF-76 generation NHC in synthetic back:
-use bronsted alkali
Figure BDA0000136855220000361
(potassium tert.-butoxide/sodium/lithium, DBU, Et 3N) handle
-use Ag 2O or Ag 2CO 3Handle
-formation
Figure BDA0000136855220000362
alkoxide adducts is used for calorifics α-elimination
Figure BDA0000136855220000363
IRMOF-77: in bottle with cover with L1 (16.6mg, 0.02mmol) and Zn (NO 3) 26H 2O (18mg, solid mixture 0.06mmol) is dissolved in N, and (DEF is 1.5mL) and in the pyridine (0.02mL) for the N-DEF.Reaction is heated to 100 ℃ and kept 24-36 hour, at the bottom of bottle, obtains bulk crystals.Bottle shifts out and naturally cools to room temperature then from baking oven.After opening bottle and from mixture, removing mother liquor, collect greenish orange look crystal also with DEF (3 * 4mL) flushings.Measure the powder and the monocrystalline X-ray diffraction of this material immediately.
Utilize any impurity of differential liberation of crystalline density.After decant goes out mother liquor, with DMF and CHBr 3(1: 2 ratio) joins in the crystal.The orange crystal of buoyant is collected and uses.
The activation of IRMOF-77: IRMOF-77 is activated on Tousimis Samdri PVT-3D critical evaporator.Before drying, the MOF sample of solvation is immersed anhydrous propanone, replacement dipping solution 3 days, during decant go out activation solvent and fresh supplemented 3 times.The sample of acetone-exchanged is placed in the sample chamber, and goes through and used liquid CO in 2.5 hours 2Exchange acetone fully.Upgraded once liquid CO in per during this period 30 minutes 2After last exchange, the sample chamber is heated to about 40 ℃, this makes sample chamber pressure reach about 1300psi (greater than CO 2Stagnation point).The sample chamber kept 2.5 hours under super critical condition, CO 2Time through 1-2 hour slowly discharges from the sample chamber.The sample that is dried is placed in the quartzy adsorption tube and tests porosity.Same record solid-state CP/MAS NMR, IR and ultimate analysis.
The analytical data of IRMOF-77:
Ultimate analysis
Zn 4O(C 28H 21I 2N 3O 4Pd) 3(H 2O) 4
Calculated value: C, 35.77; H, 2.54; I, 26.99; N, 4.47; Pd, 11.32; Zn, 9.28
Experimental value: C, 35.04; H, 2.62; I, 26.92; N, 4.71; Pd, 9.67; Zn, 9.32.
IR(KBr，cm -1 )
v＝597，673，694，719，756，783，846，1012，1070，1176，12215，1386(s)，1446，1541，1604(s)，3396
13 C CP/MAS solid state NMR (75MHz)
IRMOF-77:40.36 (methyl), 125.97 *, 130.47 *, 140.86 (pyridines), 154.10 (NHC carbon), 175.37 (CO 2Zn).
Link L1:42.15 (methyl), 125.03 *, 129.31 *, 142.20 (pyridines), 153.29 (NHC carbon), 173.00 (CO 2H)
*Widen overlapping peaks in the aromatic series zone.
The synthetic back ligand exchange of IRMOF-77: in the 20mL bottle, the IRMOF-77 crystal is immersed in 4%v/v quinoline/DMF solution, cover lid also left standstill 1 day.Also (after this 3 * 4mL) flushing crystal measure the PXRD collection of illustrative plates to decant quinoline solution immediately with DMF.After exchanging a whole day with chloroform, at room temperature the emptying solvent spends the night.The compound that use is dried writes down solid-state CP/MAS NMR spectrum.
The IRMOF-77's of quinoline exchange 13C CP/MAS solid state NMR (75MHz):
MOF:39.63 (methyl), 128.81 *, 140.19 *, 146.19 (quinoline), 152.86 (NHC carbon), 174.38 (CO 2Zn).
Connector L2:40.14 and 43.43 (not equivalent methyl), 128.16 *, 143.14 *, 146.32 (quinoline), 153.59 (NHC carbon), 173.42 (CO 2H)
*Widen overlapping peaks in the aromatic series zone.
The collection of monocrystalline X ray diffracting data, structure elucidation and the refinement procedure of IRMOF-76 and IRMOF-77. each sample is carried out preliminary sweep, to obtain preliminary unit cell parameter and assessment crystalline mosaic property (width of spot between the frame) to select the necessary frame of data gathering wide.In each case, judge 0.5 ° frame wide be suitable, and use Bruker APEX2 4Software suite is collected full hemisphere data, and (2 θ=28,60 °) carry out overlapping down so that set in two different detector (2 θ)
Figure BDA0000136855220000381
Scan with ω.After data gathering, to reflection sampling from the All Ranges of Ewald sphere (Ewald sphere), with the unit cell parameter of confirming to be used for data integration again with use CELL_NOW check rotation twin.After at large assessing collected frame, the resolving power of judgment data collection.Use Bruker APEX2 V 2.1 software integrated datas, wherein use the average intensity mark lower limit of narrow frame algorithm and 0.400.Proofread and correct absorption data with program SADABS subsequently.The spacer of using XPREP to lack the face twin is confirmed and check.
All structures resolve and use the refine of SHELXTL97 software suite through direct method.According to the least-squares refinement of previous model, from the iteration inspection location atom of different F collection of illustrative plates.To anisotropically refine of final mask (if the data number allows and stablizes refine and can reach), till realization is converged fully.Wasserstoffatoms is placed in the position of calculating and as crossing in atom (riding atom) is included in, wherein isotropy displacement parameter be connect the U of carbon atom Eq1.2-1.5 doubly.
IRMOF-76: (0.60 * 0.60 * 0.40mm) is placed in the borosilicate kapillary of 1.0mm diameter, and said kapillary contains a small amount of mother liquor to prevent that desolvation takes place during data gathering with the colourless bulk crystals of IRMOF-76.With the kapillary flame sealing and be placed on the SMARTAPEXII three circle diffractometers; Said diffractometer is equipped with the CCD area detector and (40kV 30mA) operates down so that when in the nitrogen gas stream of cooled with liquid nitrogen, being cooled to 258 (2) K, produce Cu K α radiation
Figure BDA0000136855220000382
and under this temperature, collect data at 1200W power.
Using Bruker APEX2 software suite to collect full hemisphere data carries out overlapping
Figure BDA0000136855220000383
down and scans with ω to set (2 θ=28,60 °) in two kinds of different detector (2 θ).Collect 96360 reflections altogether, wherein 1260 is unique, and this wherein has 913 again greater than 2 σ (I).The scope of θ is 1.78 ° to 40.06 °.There is insignificant decay in data analysis during being presented at collection.Adjustment program scale is to minimize the difference between the symmetry reflection relevant or replicate measurement.
Analytic structure in having the cubes of Z=8
Figure BDA0000136855220000391
spacer.To the anisotropically refine of all non-hydrogen atoms except that C8, C9, N1.Because realized crystal grade and stable isotropy refine, so other situation is impossible.Find that the atom (C8, C9 and N1) in methylimidazole
Figure BDA0000136855220000392
ring is unordered, and be half occupancy in every kind of component their refine.Wasserstoffatoms is placed in the position of calculating and as crossing in atom is included in, wherein isotropy displacement parameter be connect the U of C atom Eq1.2-1.5 doubly.Use PLATON 10Adsym sub-routine inspection structure to guarantee model not to be applied extra symmetry.
Because there is unordered content in the macrovoid of skeleton, so can't differentiate the object entity in this structure to the modeling of the electron density in the skeleton space.From the unordered solvent of the height in the intracrystalline void space and from be used to lay crystalline diffuse scattering capillaceous facilitating ground unrest and high angle data ' flush away '.Solvent is not by modeling in crystalline structure.Methylimidazole
Figure BDA0000136855220000393
ring is used constraint (bond distance of C7-N1, C8-N1 and C9-N1 is fixed).Consider not good data, expected structure has high reliability factors.Because the quality of diffraction data is lower, so some atoms show high U IsoNot good length and angle are because insufficient constraint and esd are also high.Reported that this structure is presented in the skeleton with the isolating IRMOF-76 of crystallized form.This structure is a primary cubes skeleton.In order to prove the exactness of atom site in the skeleton, used the SQUEEZE of A.Spek 5Routine.Yet, also presented the atomic coordinate of " non-SQUEEZE " structure.Do not absorb correction.For F 2The refine of final complete matrix method of least squares converge to R 1=0.0549 (F＞2 σ (F)) and wR 2=0.2166 (all data), wherein GOF=0.912.For the structure of wherein not using the SQUEEZE program as yet, for F 2The refine of final complete matrix method of least squares converge to R 1=0.1465 (F＞2 σ (F)) and wR 2=0.4378 (all data), wherein GOF=1.941.For this structure, in MOF crystallography, there is the R value that raises usually, reason is described at preceding text by us and other research team.
IRMOF-77: (0.30 * 0.30 * 0.20mm) is placed in the borosilicate kapillary of 0.4mm diameter, and said kapillary contains a small amount of mother liquor to prevent that desolvation takes place during data gathering with the greenish orange color lump shape crystal of IRMOF-77.With the kapillary flame sealing and be placed on the SMARTAPEXII three circle diffractometers; Said diffractometer is equipped with the CCD area detector and (40kV 30mA) operates down so that when in the nitrogen gas stream of cooled with liquid nitrogen, being cooled to 258 (2) K, produce Cu K α radiation and under this temperature, collect data at 1200W power.
Using Bruker APEX2 software suite to collect full hemisphere data carries out overlapping down and scans with ω to set (2 θ=28,60 °) in two kinds of different detector (2 θ).Collect 51319 reflections altogether, wherein 3946 is unique, and this wherein has 2238 again greater than 2 σ (I).The scope of θ is 2.06 ° to 39.74 °.There is insignificant decay in data analysis during being presented at collection.Adjustment program scale is to minimize the difference between the symmetry reflection relevant or replicate measurement.
Structure resolves and uses the refine of SHELXTL97 software suite through direct method.According to the least-squares refinement of previous model, from the iteration inspection location atom of different F collection of illustrative plates.Analytic structure in having three prismatic crystals of Z=12 spacer.Utilize the Wasserstoffatoms that produces as the spheroid of crossing over its parent atom coordinate, to all zinc atoms (Zn1, Zn2), palladium atom (Pd1), iodine atom (I1, I2) with the skeleton main chain on other non-hydrogen atom (except C6, C12, C17) anisotropically refine.Because realized crystal grade and stable isotropy refine, so other situation is impossible.Wasserstoffatoms is placed in the position of calculating and as crossing in atom is included in, wherein isotropy displacement parameter be connect the U of C atom Eq1.2-1.5 doubly.The Adsym sub-routine inspection structure of using PLATON is to guarantee model not to be applied extra symmetry.
Because there is unordered content in the macrovoid of skeleton, so can't differentiate the object entity in this structure to the modeling of the electron density in the skeleton space.High esd causes confirming the definite position of solvent molecule.Therefore, the several the earliest unacknowledged peaks that can't be assigned to any definite entity in the void space as isolating Sauerstoffatom by modeling.
Reported that this structure represents the skeleton with the isolating IRMOF-77 of crystallized form.Structure is double IPN cubes skeleton.In order to prove the exactness of atom site in the skeleton, used the SQUEEZE routine of A.Spek.Yet, also presented the atomic coordinate of " non-SQUEEZE " structure.Therefore, the structure of report does not comprise any solvent after SQUEEZE.Do not absorb correction.For F 2The refine of final complete matrix method of least squares converge to R 1=0.0560 (F＞2 σ (F)) and wR 2=0.1389 (all data), wherein GOF=0.950.For the structure of wherein not using the SQUEEZE program as yet, for F 2The refine of final complete matrix method of least squares converge to R 1=0.1039 (F＞2 σ (F)) and wR 2=0.3399 (all data), wherein GOF=1.141.Reflection is 12.0 with the final ratio of parameter.For this structure, in MOF crystallography, there is the R value that raises usually, reason is described at preceding text by us and other research team.
Crystal data and the structure refinement of table 3.IRMOF-76
Figure BDA0000136855220000421
Crystal data and the structure refinement of table 4.IRMOF-76 (SQUEEZE)
Figure BDA0000136855220000422
Figure BDA0000136855220000431
Crystal data and the structure refinement of table 5.IRMOF-77
Figure BDA0000136855220000432
Crystal data and the structure refinement of table 6.IRMOF-77 (SQUEEZE)
Figure BDA0000136855220000442
Figure BDA0000136855220000451
The impartial netted covalency conversion of the success that this paper proved and subsequent metalization provide a kind of and have incorporated metals ion in the multiple skeleton approach.Basically, it has expanded the reaction compartment that can in MOF, carry out.
The synthesis program of the amino terephthalate MOF of Zr-: with 40mg (ZrCl 4) be placed in the vial that contains 40ml DMF with the amino terephthalic acid of 100mg 2-.Being reflected at 85 ℃ heated 3 days down.Filtering powder exchanges in 3 * 40ml chloroform.
Experiment and simulation x-ray diffractogram of powder spectrum. use Bruker D8-Discover θ-2 θ diffractometer, collect powder x-ray diffraction (PXRD) data how much with reflectivity Bragg-Brentano.Use the plane Gobel mirror of crossing over K α line to focus on Cu K α 1Radiation (
Figure BDA0000136855220000461
1600W, 40kV, 40mA).0.6mm divergent slit is used for all measurements.Use is equipped with the radiation of Vantec straight-line detection device (Bruker AXS, the 6 ° of 2 θ sampling width) detection of diffracted of Ni monochromator.Through the crystal that drips with wide leaf spatula, shakeout sample surfaces then, all samples is placed on the slide glass that is fixed in specimen holder.Obtain best counting statistics through using from 2 ° to 50 ° 0.02 ° of 2 θ step-scan and the time shutter of every stepping 0.4s.
IRMOF-76,77 thermogravimetric analysis (TGA) data. all samples is tested on TA InstrumentsQ-500 series thermogravimetric analyzer, and wherein sample is maintained in the platinum dish under the continuous nitrogen gas stream atmosphere.In the constant rate of speed heated sample of all TGA experimental sessions with 5 ℃/min.
The porosity measurement of IRMOF-77. the low-pressure gas adsorption isothermal line is by volume measured on Autosorb-1 analyser (Quantachrome Instruments).Liquid nitrogen bath (77K) is used for N 2Thermo-isopleth is measured.Used N 2With He gas be UHP level (99.999%).For the reckoner area, use Langmuir and BET method, wherein use N 2N supposes in isothermal absorption branch 2Cross sectional area does / molecule.Estimate that Langmuir and BET surface-area are respectively 1610 and 1590m 2g -1Use Dubinin-Raduskavich (DR) method to confirm volume of voids, suppose wherein that adsorbate is in a liquid state and adsorbs and relate to the hole filling process.The bulk density of supposing IRMOF-77 is 0.922g cm -3, the pore volume (0.57cm that calculates 3g -1) corresponding to 0.53cm 3Cm -3
Present embodiment is to the structure based on well-known primitive cube body MOF-5, and utilization can be held the linear ditopic carboxylicesters connector of NHC-metal complex or its precursor.The reducing-pitch thread route of synthesis of novel connector is shown in disclosure book exhibition, its utilize cross-coupling reaction as committed step with combination imidazoles
Figure BDA0000136855220000463
core and carboxylicesters module (above scheme 2).
4; Two (the 4-carboxyl phenyls)-1 of 7-; 3-dimethylbenzimidazole
Figure BDA0000136855220000464
a tetrafluoro borate (L0) synthetic is that 7-dibromo diazosulfide (1) is as initiator with known 4.Thiadiazoles under the cobalt catalysis with sodium borohydride reduction and under acid catalysis, can be converted into benzoglyoxaline subsequently with the triethyl orthoformate condensation.Then carrying out N-methylates and can produce the dibromo benzimidazole nucleus heart (2).2 to carry out with 4-(tertbutyloxycarbonyl) phenyl tetramethyl ethylene ketone borine (3) that the Suzuki-Miyaura cross-coupling can produce with the diester under Pd (0) catalysis be the linear terphenyl structure (4) of end group.
Specifically,, select to have the module of the tert-butyl ester, because the solubleness of carboxylic acid is higher and can be gone to shelter in the later stage as masked carboxylic acid for synthetic L0.Methyl iodide processing with excessive can produce 5; It has N, N '-dimethylbenzimidazole
Figure BDA0000136855220000471
part.Then through using HBF 4To two tert-butyl esters go the protection simultaneously with counter anion with I -Be substituted by BF 4 -And acquisition L0.All conversions are feasible under the scale in gram.
IRMOF-76 uses 3 normal Zn (BF 4) 2XH 2O, 10 normal KPF 6With L0 at N, the mixture in the dinethylformamide (DMF) is synthetic.Mixture heated 36 hours down at 100 ℃, so obtain IRMOF-76 (Zn 4O (C 23H 15N 2O 4) (X) 3(X=BF 4, PF 6, OH)) and clear crystal.
Single-crystal X-ray diffraction analysis discloses IRMOF-76 and MOF-5 is impartial netted.Wherein, Zn 4The O unit is connected with 6 L0 connectors that (Fig. 6 a) with the cubes skeleton that forms the pcu topological framework.The through positively charged ion MOF of IRMOF-76 right and wrong has imidazoles
Figure BDA0000136855220000472
partly (NHC precursor) on each connector.By digestion IRMOF-76 icp analysis with 19F NMR spectrum discloses, BF 4 -And PF 6 -All as imidazoles
Figure BDA0000136855220000473
The part counter anion and in being comprised in.
Developed the strategy that uses connector with metal-NHC complex compound.Even metal-NHC key also is stable generally under slight acidic conditions; And chemo-selective NHC coordination has been avoided in the building process of secondary structure unit (SBU), with source metal undesired reaction taking place, and said structure depends on oxygen-metal-complexing in many cases.In specific embodiment described herein; Use [4, two (the 4-carboxyl phenyls)-1 of 7-, 3-dimethylbenzimidazole-2-subunit] (pyridyl) palladium iodide (II) (L1; Scheme 2), its conduct has the potential magnetism with the homologous catalyzer of known homogeneous catalyst system.
L1 is from intermediate 5 preparations (scheme 2).When containing Pd (II) source, alkali (K 2CO 3) and the pyridine of iodide source (NaI) in when refluxing, 5 benzoglyoxaline
Figure BDA0000136855220000474
Part is converted into NHC-PdI 2(py) complex compound.The tert-butyl ester go the protection be to carry out with trifluoromethanesulfonic acid trimethyl silane ester (TMSOTf).The Pd (II) that covalency forms even-the NHC key is being used for also keeping stable under de-protected Louis's strong acidic condition surprisingly.Yet, remove the collaborative part of pyridine to form dimer complex.Adding pyridine is to produce to have monomer NHC-PdI as part 2(py) L1 of part is necessary.
IRMOF-77 uses 3 normal Zn (NO 3) 26H 2O and L1 are at N, and be synthetic in the solvent mixture of N-DEF (DEF) and pyridine (75/1).Mixture heated 30 hours down at 100 ℃, so obtain IRMOF-77 (Zn 4O (C 28H 21I 2N 3O 4Pd) 3) orange crystal.
The x-ray crystal structure analysis discloses IRMOF-77 and MOF-5 also is impartial netted.X-ray crystal structure alleged occurrence NHC-PdI 2(py) partly (Fig. 6 b).The Zn ion that is used to make up skeleton does not have to participate in combining partly with metal-NHC.There is not undesired metal exchange on the elementary composition confirmation NHC according to the desired value measurement.The Pd-C distance of observation
Figure BDA0000136855220000481
With coordination geometry and Cambridge structural database for NHC-PdX 2(py) data found of (X=halogen ion) complex compound fit like a glove.Further through solid-state 13(for N-C:-N, δ=154.1ppm) has confirmed the existence of Pd (II)-NHC key to C cross polarization evil spirit angle rotation (CP/MAS) NMR spectrum.NHC-Pd (II) part is positioned at each face of intraskeletal cubes cage.Formed and had approximately two skeletons that interweave (Fig. 6 c) of
Figure BDA0000136855220000482
offset distance; This probably can alleviate metal-NHC part interference; Wherein from the shortest distance between two methyl carbon of two skeletons is
Figure BDA0000136855220000483
therefore; Chain effect is different with IRMOF-15, and the bond distance of IRMOF-15 is identical with L1.Because the interwoven nature of structure; The aperture is stretched in the hole for about
Figure BDA0000136855220000484
all fixed Pd (II) centers, can not stop mutually each other.
For the existence that confirms void space and the structural stability of IRMOF-77, the N of the sample through no object thing 2Adsorption isothermal line proves permanent porosity.Said thermo-isopleth shows the rapid N in the area of low pressure 2Picked-up, this shows that material is microporous (Fig. 7).The Langmuir and the BET surface-area that calculate activated state IRMOF-77 are respectively 1,610 and 1,590m 2g -1Hole (P/P 0=0.9) N in 2Intake is corresponding to every formula unit 46N 2Molecule or per unit structure cell 552.
For the reactivity at fixedly Pd (II) center of checking IRMOF-77, carry out the ligand exchange experiment over one day through at room temperature the IRMOF-77 crystal of the synthetic attitude of original position being immersed to keep in 4v/v% quinoline/DMF solution.Before the exchange with the relatively announcement of powder x-ray diffraction (PXRD) collection of illustrative plates afterwards, skeleton in exchange process, be kept perfectly (Fig. 8).After ligand exchange, digested MOF's 1Do not observe signal in the H NMR spectrum from the pyridine proton.Only at expection mole stoichiometry (carboxylicesters connector: observe signal quinoline=1: 1) from quinoline. 13C CP/MAS solid state NMR spectrum (before: 154.1ppm; Afterwards: 152.9ppm) confirmed the reservation of NHC-Pd key.There is NHC-PdI in these result's indications after ligand exchange 2(quinoline) complex compound.
The successful Application of the method for IRMOF-76 and 77 structure proof disclosure book in Pd (the II)-NHC organometallic complex among the fixing MOF can not lost MOF porosity and its structurally ordered property simultaneously.
Many embodiments of the present invention have been described.Yet, should be appreciated that and can under the situation of spirit that does not depart from disclosure book and scope, carry out various modifications.Therefore, other embodiment also falls in the scope of following claims.

Claims (14)

1. organometallic skeletal that comprises formula M-L-M, wherein M be the skeleton metal and wherein L have the connection portion of the modification of being connected in the heterocyclic carbene or the imine group of metal.
2. organometallic skeletal according to claim 1, wherein said imine group comprises chelation group.
3. organometallic skeletal according to claim 1, wherein said connection portion is being metallized with said skeleton metal reaction before.
4. organometallic skeletal according to claim 3, wherein said connection portion comprises the N-heterocyclic carbene.
5. organometallic skeletal according to claim 1, wherein said skeleton comprise covalency organic backbone (COF), zeolite imidazoles skeleton (ZIF) or metallic organic framework (MOF).
6. organometallic skeletal according to claim 2, wherein said imine group by skeleton after chelating in metal.
7. organometallic skeletal according to claim 1, wherein said skeleton metal is selected from by 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 group of forming.
8. organometallic skeletal according to claim 1, wherein said modification is selected from by Li with metal +, 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 group of forming.
9. organometallic skeletal according to claim 1, wherein said modification extends in the hole of said skeleton with metal.
10. organometallic skeletal according to claim 1, wherein said skeleton lacks guest species.
11. method of making organometallic skeletal according to claim 1; It comprises making and comprises heterocyclic carbene and comprise through the connection portion of the connection bunch of protection and modification with metal reaction to obtain metallized connection portion; Said connection bunch is gone protection and made said metallized connection portion and skeleton metal reaction.
12. method of making organometallic skeletal according to claim 1; It comprises make the organic backbone that comprises amido and the reaction of 2-pyridylaldehyde with obtain the functionalized connection portion of imines and make said skeleton and chelating in the metallic contact of the functionalized connection portion of said imines.
13. a gas adsorption compsn, it comprises organometallic skeletal according to claim 1.
14. a catalyst composition, it comprises organometallic skeletal according to claim 1.
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CN108152260B (en) * 2017-12-23 2019-06-07 福州大学 A kind of fluorescent optical sensor and preparation method thereof detecting uric acid
US11230562B2 (en) 2018-04-25 2022-01-25 Uti Limited Partnership Synthesis of zinc MOF materials
CN108503853A (en) * 2018-05-04 2018-09-07 武汉大学 A kind of covalent organic frame material and its preparation method and application based on secondary amine bonding
CN108503853B (en) * 2018-05-04 2020-09-08 武汉大学 Covalent organic framework material based on secondary amino bonding and preparation method and application thereof
CN109174189B (en) * 2018-09-07 2021-03-05 辽宁大学 PCN-222(Co) @ TpPa-1-based porous crystalline core-shell hybrid material and preparation method and application thereof
CN109174189A (en) * 2018-09-07 2019-01-11 辽宁大学 Porous crystalline nucleocapsid hybrid material and its preparation method and application based on PCN-222-Co@TpPa-1
CN114450327A (en) * 2019-08-29 2022-05-06 乔治亚技术研究公司 Metal organic framework material and application thereof
CN114450327B (en) * 2019-08-29 2024-04-05 乔治亚技术研究公司 Metal organic framework material and application thereof
CN111196876A (en) * 2020-02-14 2020-05-26 武汉大学 Synthetic method and application of Co-based MOF material with nucleic acid screening function and adjustable pore diameter
CN111196876B (en) * 2020-02-14 2021-08-03 武汉大学 Synthetic method and application of Co-based MOF material with nucleic acid screening function and adjustable pore diameter

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