JP2012530722A - Organometallic framework and method for producing the same - Google Patents

Abstract

The present disclosure provides an organic framework that includes increased stability.
[Selection] Figure 6

Description

Cross-reference to related applications This application is subject to provisional patent application 61 / 218,891 filed on June 19, 2009 and 61 / 247,351 filed September 30, 2009 in accordance with section 119 of the US Patent Act. The disclosures of which are incorporated herein by reference).

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was funded by grant number DE-FG36-05GO15001 awarded by the Department of Energy and grant number HDTRA1-08-10023 awarded by the Department of Defense. The United States government has certain rights in this invention.

TECHNICAL FIELD The present disclosure provides organometallic frameworks for gas separation, storage, and use as sensors with chemical stability.

  The framework for gas separation, storage, and purification is important.

The present disclosure provides a chemically stable open skeleton comprising specified elements including, but not limited to, zirconium, titanium, aluminum, and magnesium ions. The present disclosure encompasses all open framework materials constructed from organic linkages linked by a multidentate organic or inorganic core. All classes of open skeleton materials: covalent organic skeleton (COF), zeolitic imidazolate skeleton (ZIF), and metal organic skeleton (MOF), as well as reticulated chemical structural resources ( http: //rcsr.anu. edu.au/ ) including all possible resulting network topologies. The present disclosure utilizes these materials to provide a stable framework in harsh industrial conditions. Such materials will be used in a variety of applications such as gas storage and separation, chemical and biological sensing, molecular reorganization, and catalysis.

The present disclosure provides an organometallic skeleton comprising the general structure MLM, where M is a skeletal metal and L is a linking moiety having a heterocyclic carbene or imine group attached to a modified metal. . In one embodiment, the imine group comprises a chelating group. In yet other embodiments, the linking moiety is metallized prior to reaction with the skeletal metal. In other further embodiments, the linking moiety comprises an N-heterocyclic carbene. In one embodiment, the framework comprises a covalent organic framework (COF), a zeolitic imidizole framework (ZIF), or a metal organic framework (MOF). In yet other embodiments, the imine group is post-skeleton chelated to the metal. In one embodiment, the skeletal metal is 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 ⁺ , Pd2 ⁺ , Pd ⁺ , Pt2 ⁺ , Pt ⁺ , Cu2 ⁺ , Cu ⁺ , Au ⁺ , Zn2 ⁺ , Al3 ⁺ , Ga3 ⁺ , In3 ⁺ , Si4 ⁺ , Si It is selected from the group consisting of ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Bi ⁵⁺ , Bi ³⁺ . In yet another embodiment, the modified metal is 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⁺ . In other further embodiments, the modified metal extends into the pores of the framework. In some embodiments, the skeleton includes a guest species, while in other embodiments, the skeleton remains stable without the guest species.

  The present disclosure includes reacting a link moiety comprising a heterocyclic carbene and comprising a protected link cluster with a modified metal to obtain a metalated link moiety, deprotecting the link cluster, And a method for producing an organometallic skeleton as described above, comprising reacting with a skeleton metal.

  The present disclosure also reacts an organic backbone containing an amine group with 2-pyridinecarboxaldehyde to obtain an imine functionalized link moiety and contacts the backbone with a metal that chelates the imine functionalized link moiety. And providing a method for producing an organometallic skeleton.

  The organometallic skeleton according to the present disclosure is useful for gas separation and catalysis. Accordingly, the present disclosure provides gas sorption materials and gas sorption devices and catalyst compositions and catalyst devices comprising an organometallic framework according to the present disclosure.

  The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

A, B, and C PXRD patterns are shown along with A simulated pattern (bottom). Shows Ar gas adsorption isotherms at 87K for A (upper black circle in the graph), B (upper white circle), and C (lower line) (adsorption and desorption points are represented by black and white circles, respectively). . Pd K absorption edge EXAFS Fourier transform of C and (inset) EXAFS spectrum is shown. The solid line shows experimental data and the dotted line shows the best fit using the parameters listed in Table 1. Dichloro (N- (2-pyridylmethylene) aniline-N, N ') palladium (II) (a), (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ (b ) And PdCl ₂ (CH ₃ CN) (c) show the spectrum near the absorption edge of the Pd K absorption edge. 2 shows an ESI mass spectrum of an imine ligand fragment. (AC) The structures of IRMOF-76 and -77 are shown. (a) Single crystal structure of IRMOF-76 (Zn ₄ O (C ₂₃ H ₁₅ N ₂ O ₄ ) ₃ (X) ₃ (X = BF ₄ , PF ₆ , OH)). (b) Single crystal structure of IRMOF-77 (Zn ₄ O (C ₂₈ H ₂₁ I ₂ N ₃ O ₄ Pd) ₃ ) shown to have only one pcu network. Atomic color: tetrahedron: Zn, I, Pd, O, sphere: N. The spheres represent the largest spheres that occupy voids without contacting the inner van der Waals surface of IRMOF-76 and the single skeleton of IRMOF-77 (approximately 19 mm and 15 mm, respectively). All hydrogen atoms, counter anions (X), and guest molecules were omitted for clarity. (c) IRMOF-77 space filling diagram. Two intertwined pcu nets are shown in blue and gold, respectively. The N ₂ isotherm measurement result of IRMOF-77 measured at 77K is shown. The PXRD pattern of the as-synthesized IRMOF-77 (middle), the quinoline-exchanged IRMOF-77 (bottom), and the PXRD pattern simulated from the single crystal X-ray structure (top) are shown. It is an ORTEP diagram of an asymmetric unit of IRMOF-76. All ellipsoids are displayed with a probability level of 10%, excluding hydrogen atoms. FIG. 4 is an ORTEP diagram of IRMOF-77 with half of the Zn ₄ O unit and one link. All ellipsoids are displayed at a 30% probability level, excluding hydrogen atoms. PXRD patterns of as-synthesized IRMOF-76 (black) and IRMOF-15, 16 (blue and red, respectively) simulated from single crystal X-ray structures are shown. It is a TGA trace of IRMOF-76 as synthesized. The very large weight loss up to 150 ° C. corresponds to the loss of guest solvent (DMF, H ₂ O). Significant weight loss at 300-400 ° C suggests material degradation. It is a TGA trace of IRMOF-77 as synthesized. The very large weight loss up to 150 ° C. corresponds to the loss of guest solvents (DEF, pyridine, and H ₂ O). Presumably the material loses the coordination molecule (pyridine) by 250 ° C., and a significant weight loss at 300-400 ° C. suggests decomposition of the material. It is a TGA trace of active IRMOF-77. The weight loss at about 180 ° C. is due to a partial loss of coordination pyridine (calculated as 8.6% of the total loss). It is a TGA trace of organometallic linker L1. The weight loss up to 250 ° C. (9.7%) is based on the formation of dimer S4 due to the loss of pyridine (calculated to be 9.3%). Active Zr-MOF is shown. The stability test in the presence of various chemicals is shown. It shows a useful reaction to form imines as chelating agents. Shows reversible imine formation in the skeleton. PXRD data for imine is shown. 2 shows solid state NMR data of imine. Shows SA of imine reaction. Shows SA of imine reaction. Data on reverse reaction of imine reaction is shown. Figure 3 illustrates ligands useful in the methods and compositions according to the present disclosure.

  As used in this specification and the appended claims, the singular forms “a”, “and”, and “the” include plural references unless the context clearly dictates otherwise. . Thus, for example, reference to “a framework” includes a plurality of such frameworks, and “the metal” reference refers to one or more metals and those known to those skilled in the art. The reference object of the equivalent is included, and the same applies to other cases.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and reagents similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, representative methods and materials are now described.

  Also, unless stated otherwise, the use of “or (or or or)” means “and / or (and / or and / or and / or and / or)”. Similarly, “comprise”, “comprises”, “comprising”, “include”, “includes”, and “ "Including" is synonymous and is not intended to be limiting.

  Further, it will be appreciated that when the term “comprising” is used in the description of various embodiments, in certain instances, “consisting essentially of” Those skilled in the art will appreciate that an embodiment may be described using the expression “consisting of” or “consisting of”.

  All publications cited herein are hereby incorporated by reference in their entirety for the purpose of describing and disclosing the methods described in the publications that may be used in connection with the description herein. Shall be. The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior disclosure.

  Metal organic frameworks (MOFs) have been synthesized in the art, but these prior MOFs lack chemical stability or have low porosity and limited cage / channel problems So their use in the industry is greatly limited.

  Fine control of the functionality of the metal complex is generally achieved with molecular coordination chemistry. Developing similar chemistry within an extended crystal structure remains a challenge because it tends to lose order and connectivity when subjected to chemical reactions. The metal organic framework (MOF) is an ideal candidate for conducting coordination chemistry in an extended structure because it is highly ordered and flexible allowing modification of organic links. This is illustrated by the successful application of an isonetwork scheme that can change the functionality and distance of the expanded porous structure without changing its basic topology.

  The present disclosure provides a method for forming an organometallic framework by two methods. The first method utilizes a post skeleton synthesis reaction in which a reactive side group of a link ligand functions as a metal chelating agent to chelate a metal into the skeleton. The second method utilizes a pre-skeleton synthesis method in which a linking ligand is modified to include a metal and then a metal-ligand is reacted to form a skeleton. The present disclosure also encompasses compositions resulting from these methods and devices incorporating the compositions.

  The present disclosure provides a method of forming a stable organometallic framework comprising MOF, ZIF, or COF using a series of chemical reactions. One of the advantages of the framework according to the present disclosure is that it easily incorporates the desired metal center and organic link so that the porosity, functionality, and channel environment can be easily adjusted and adapted to the target function and application. It is to go.

  In one embodiment of the present invention, the present disclosure provides a precursor organic framework comprising a linking moiety having reactive side groups useful for chelating metals. In one embodiment, the reactive side group comprises an amine group. Next, a post skeleton reaction chelation process is used to react the precursor organic skeleton with a metal to form an organometallic skeleton by reaction of the skeleton.

  The present disclosure involves subjecting a MOF material selected from the enormous number reported in the literature to a series of chemical reactions to produce a covalently bound chelate ligand, which is subsequently converted to Pd (II ) That can be used for complexation of The skeleton containing the chelated metal can then be further reacted to incorporate additional functionality (eg, space constraints, charge, etc.) within the pores of the skeleton.

As an example, a crystal of (Zn ₄ O) ₃ (BDC-NH ₂ ) ₃ (BTB) ₄ (A) (Scheme 1) is reacted with 2-pyridinecarboxaldehyde to form a covalently bound iminopyridine chelate derivative (Zn ₄ O) _3- (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ (B), which is reacted with PdCl ₂ (CH ₃ CN) ₂ to form a metal complexed MOF ( Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) _3- (BTB) ₄ (C) was obtained. These reactions and their respective products were achieved without compromising structural order or skeletal connectivity. This isoreticular metallization is an important first step in exploiting the inherent advantages of molecular coordination chemistry for functionalizing extended solids. The metal complexed MOF can then function as a building block for the chelated metal addition reaction to form additional functionalized skeletons.

  Two reports on covalent metallization describe materials that have not been demonstrated to be permanently porous. The strategy depicted in Scheme 1 overcomes these limitations. The iminopyridine moiety has been found to be a versatile ligand system that binds to various transition metals in a known coordination environment. In this disclosure, such moieties are incorporated via condensation of an amine functionalized backbone with 2-pyridinecarboxaldehyde (Scheme 1).

  In yet another embodiment of the invention, the present disclosure provides an alternative method for forming an organometallic framework. In this embodiment, an organometallic complex is formed that is covalently bonded within the pores of the MOF. In this method, the reactive carbene on the link ligand is metallated, followed by deprotection of the link cluster and reacting the metalated link ligand with the metal. For example, a carbene (NHC) 5 precursor is metallated (L1, Scheme 2) and then constructed in the form of the desired metalated MOF structure (eg, IRMOF-77, Scheme 2). It is also demonstrated by this disclosure that this metallized MOF can be further modified to increase the functionality (size, charge, etc.) of the framework pores.

Scheme 2: Convergent synthesis of new dicarboxylic acid links (L0, L1) and preparation of IRMOF-76, 77:

In one embodiment, a method according to the present disclosure utilizes the process shown in Scheme 3 to produce an organometallic MOF.

  The term “cluster” means an identifiable association of two or more atoms. Such aggregates are typically established by some bond (ionic bond, covalent bond, Van der Waal bond, etc.).

“Link cluster” means one or more condensable reactive species containing atoms that can form a bond between a partial structure of a link moiety and a metal group or a bond between a link moiety and another link moiety. Examples of such species are selected from the group consisting of boron atoms, oxygen atoms, carbon atoms, nitrogen atoms, and phosphorus atoms. In some embodiments, the link cluster can include one or more different reactive species capable of forming a link having a bridging oxygen atom. For example, the link cluster is CO ₂ H, CS ₂ H, NO ₂ , SO ₃ H, Si (OH) ₃ , Ge (OH) ₃ , Sn (OH) ₃ , Si (SH) ₄ , Ge (SH) ₄ , Sn (SH) ₄ , PO ₃ H, AsO ₃ H, AsO ₄ H, P (SH) ₃ , As (SH) ₃ , CH (RSH) ₂ , C (RSH) ₃ , CH (RNH ₂ ) ₂ , C (RNH ₂ ) ₃ , CH (ROH) ₂ , C (ROH) ₃ , CH (RCN) ₂ , C (RCN) ₃ , CH (SH) ₂ , C (SH) ₃ , CH (NH ₂ ) ₂ , C (NH ₂ ) ₃ , CH (OH) ₂ , C (OH) ₃ , CH (CN) ₂ , and C (CN) _{3 wherein} R is an alkyl group having 1 to 5 carbon atoms or Is an aryl group containing 1 to 2 phenyl rings), and CH (SH) 2, C (SH) 3, CH (NH2) 2, C (NH2) 3, CH (OH) 2, C (OH) 3, CH (CN) 2, and C (CN) 3. Typically, ligands for MOF contain carboxylic acid functional groups. The present disclosure includes 1 to 5 rings consisting of carbon alone or a mixture of carbon and nitrogen, oxygen, sulfur, boron, phosphorus, silicon, and aluminum atoms constituting the ring. Including cycloalkyl or aryl partial structures.

  The “link portion” means a monodentate compound or a multidentate compound that binds to one transition metal or a plurality of transition metals. Generally, the linking moiety is an alkyl or cycloalkyl group containing 1-20 carbon atoms, an aryl group containing 1-5 phenyl rings, or an alkyl group having 1-20 carbon atoms or A partial structure comprising a cycloalkyl group or an alkylamine or arylamine containing an aryl group containing 1 to 5 phenyl rings, and a linked cluster (eg, a multidentate functional group) is covalently bonded to the partial structure. The cycloalkyl partial structure or aryl partial structure contains only carbon or a mixture of carbon and a nitrogen atom, oxygen atom, sulfur atom, boron atom, phosphorus atom, silicon atom, and / or aluminum atom constituting the ring. 1 to 5 rings can be included. Typically, the linking moiety will comprise a partial structure having one or more carboxylic acid link clusters covalently linked. In some embodiments, the carboxylic acid cluster can be protected during certain reactions and then deprotected prior to reaction with the metal.

  As used herein, a line in a chemical formula that has an atom at one end and no other end is attached to the other element at the end where the formula does not have a bonded atom. Is meant to represent a chemical fragment. For emphasis, wavy lines may intersect this line.

In one aspect, the partial structure of the link portion is selected from any of the following.

In certain embodiments, the link portion has the following structure:

Other link portions include those shown below.

(In the formula, R _{1 to} R ₁₅ are H, NH ₂ , COOH, CN, NO ₂ , F, Cl, Br, I, S, O, SH, SO ₃ H, PO ₃ H ₂ , OH, CHO, CS ₂ H, SO ₃ H, Si (OH) ₃ , Ge (OH) ₃ , Sn (OH) ₃ , Si (SH) ₄ , Ge (SH) ₄ , PO ₃ H, AsO ₃ H, AsO ₄ H, P (SH) ₃ , As (SH) ₃ , CH (RSH) ₂ , C (RSH) ₃ , CH (RNH ₂ ) ₂ , C (RNH ₂ ) ₃ , CH (ROH) ₂ , C (ROH) ₃ , CH (RCN) ₂ , C (RCN) ₃ ,

{Where X = 1, 2, or 3}
Is)
The multidentate core according to the present disclosure includes a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heteroaromatic ring, a substituted or unsubstituted non-aromatic ring, a substituted or unsubstituted non-aromatic ring A heterocyclic ring, or a saturated or unsaturated substituted or unsubstituted hydrocarbon group. A saturated or unsaturated hydrocarbon group can contain one or more heteroatoms. For example, a multidentate core can include the following examples.

[Where,
R1 to R15 are each independently H, alkyl, aryl, OH, alkoxy, alkene, alkyne, phenyl, and the above substituents, that is, a sulfur-containing group (for example, thioalkoxy), a silicon-containing group, and a nitrogen-containing group. Groups (eg, amides), oxygen-containing groups (eg, ketones and aldehydes), halogens, nitro, amino, cyano, boron-containing groups, phosphorus-containing groups, carboxylic acids, or esters, A1, A2, A3, A4, A5 and A6 are each independently any atom or group that is absent or capable of forming a stable ring structure, and T is a tetrahedral atom (eg, carbon, silicon, germanium, tin, etc.) ) Or tetrahedral groups or tetrahedral clusters. ]
The linking moiety for the MOF structure that can be functionalized to include a reactive imine group for chelating metals includes:

(In the formula, R1 to R15 are H, NH2, CN, OH, = O, = S, Cl, I, F,

{Where X = 1, 2, or 3}
Selected from)
In certain embodiments, the R group is imine functionalized to facilitate chelation of the post-synthetic metal.

Linking moieties for the ZIF structure that can be functionalized to include a reactive imine group or modified to form an N-heterocyclic carbene include:

The linking moiety for the COF structure that can be functionalized to include a reactive imine group or modified to form an N-heterocyclic carbene includes:

[Wherein R1 to R15 are each independently H, alkyl, aryl, OH, alkoxy, alkene, alkyne, phenyl, and the above substituents, that is, a sulfur-containing group (for example, thioalkoxy), silicon-containing Groups, nitrogen-containing groups (eg amides), oxygen-containing groups (eg ketones and aldehydes), halogens, nitro, amino, cyano, boron-containing groups, phosphorus-containing groups, carboxylic acids or esters, A1, A2, A3, A4, A5, and A6 are each independently any atom or group that is absent or capable of forming a stable ring structure, and T is a tetrahedral atom (eg, carbon, silicon, Germanium, tin, etc.) or tetrahedral groups or tetrahedral clusters]
All of the organic links listed above with the appropriate reactive functional groups can be chemically converted by post-skeletal synthesis reagents suitable for further functionalization of the pores. By modifying post-synthesis organic links within the backbone, it is possible and easy to use functional groups with great difficulty and / or cost, even if previously unavailable or available. Post-skeletal reactants include all known organic converters and their respective reactants, 1-20 carbon rings with functional groups containing atoms such as N, S, O, and the like. In certain embodiments, a post skeleton reactant is used to form a chelating group for metal addition. The present disclosure encompasses chelation of all metals that can be chelated to a functional group or a combination of an existing functional group and a newly added functional group to add it. There are all reactions that result in the immobilization of organometallic complexes to the skeleton for use as heterogeneous catalysts and the like.

  In addition, metals and metal-containing compounds that can be chelated to add functional groups or combinations of functional groups already present and newly added functional groups are also useful. It is possible to use reactions that result in the immobilization of organometallic complexes to the skeleton for use as heterogeneous catalysts and the like. Examples of post skeleton reactants include, but are not limited to, heterocyclic compounds. In one embodiment, the post skeletal reactant can be a saturated or unsaturated heterocycle. The term `` heterocycle '' used alone or as a suffix or prefix, has one or more polyvalent heteroatoms independently selected from N, O, and S as part of a ring structure; Moreover, it means a ring-containing structure or ring-containing molecule containing at least 3 and up to about 20 atoms in the ring (s).

  Heterocycles may be saturated or may contain one or more double bonds and be unsaturated, and heterocycles may contain more than one ring. If the heterocycle contains more than one ring, the ring can be fused or non-fused. A fused ring generally means at least two rings that share two atoms between the rings. The heterocycle may have aromatic characteristics or may not have aromatic characteristics. The term “heterocyclic group”, “heterocyclic moiety”, “heterocyclic”, or “heterocyclo” used alone or as a suffix or prefix, removes one or more hydrogens from a heterocycle This means a group derived from a heterocycle. The term “heterocyclyl” used alone or as a suffix or prefix, refers to a monovalent group derived from a heterocycle by removing one hydrogen from the heterocycle. The term “heteroaryl” used alone or as a suffix or prefix, refers to a heterocyclyl having aromatic character. Examples of the heterocycle include aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, Thiophane, piperidine, 1,2,3,6-tetrahydro-pyridine, piperazine, morpholine, thiomorpholine, pyran, thiopyran, 2,3-dihydropyran, tetrahydropyran, 1,4-dihydropyridine, 1,4-dioxane, 1 , 3-dioxane, dioxane, homopiperidine, 2,3,4,7-tetrahydro-1H-azepine, homopiperazine, 1,3-dioxepane, 4,7-dihydro-1,3-dioxepin, hexamethylene oxide, etc. A monocyclic heterocycle is mentioned. In addition, heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, furazane, pyrrole, imidazole, thiazole, oxazole, pyrazole, isothiazole, isoxazole, 1,2,3-triazole, tetrazole, 1 , 2,3-thiadiazole, 1,2,3-oxadiazole, 1,2,4-triazole, 1,2,4-thiadiazole, 1,2,4-oxadiazole, 1,3,4-triazole Aromatic heterocycles (heteroaryl groups) such as 1,3,4-thiadiazole and 1,3,4-oxadiazole.

  In addition, heterocycles include indole, indoline, isoindoline, quinoline, tetrahydroquinoline, isoquinoline, tetrahydroisoquinoline, 1,4-benzodioxane, coumarin, dihydrocoumarin, benzofuran, 2,3-dihydrobenzofuran, isobenzofuran, chromene, Chroman, isochroman, xanthene, phenoxathiin, thianthrene, indolizine, isoindole, indazole, purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine, perimidine, phenanthroline, phenazine, phenothiazine, phenoxazine, 1 , 2-Benzisoxazole, benzothiophene, benzoxazole, benzothiazole, benzimidazole, benzotriazole, thio Including trichosanthin, carbazole, carboline, acridine, pyrolizidine, a polycyclic heterocyclic ring such as quinolizidine.

  In addition to the polycyclic heterocycles described above, heterocycles include two or more bonds shared by both rings and ring fusion between two or more rings shared by both rings. And polycyclic heterocycles containing super atoms. Examples of such bridged heterocycles include quinuclidine, diazabicyclo [2.2.1] heptane, and 7-oxabicyclo [2.2.1] heptane.

  Heterocyclyl includes, for example, aziridinyl, oxiranyl, thiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl, dioxolanyl, sulforanyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl, tetrahydrofuranyl , Thiophanyl, piperidinyl, 1,2,3,6-tetrahydro-pyridinyl, piperazinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, 2,3-dihydropyranyl, tetrahydropyranyl, 1,4-dihydropyridinyl, 1, 4-dioxanyl, 1,3-dioxanyl, dioxanyl, homopiperidinyl, 2,3,4,7-tetrahydro-1H-azepinyl, homopiperazinyl, 1,3-dioxepanyl, 4,7-dihydro-1,3-dioxepinyl, hexamethylene Oxidyl etc. Of monocyclic heterocyclyl.

  In addition, heterocyclyl includes pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, furazanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, isothiazolyl, isoxazolyl, 1,2,3-triazolyl, tetrazolyl, 1,2, 3-thiadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-triazolyl, 1,2,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-triazolyl, 1,3,4- Aromatic heterocyclyl or heteroaryl such as thiadiazolyl, 1,3,4 oxadiazolyl.

  In addition, heterocyclyl includes indolyl, indolinyl, isoindolinyl, quinolinyl, tetrahydroquinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, 1,4-benzodioxanyl, coumarinyl, dihydrocoumarinyl, benzofuranyl, 2,3-dihydrobenzo Furanyl, isobenzofuranyl, chromenyl, chromanyl, isochromanyl, xanthenyl, phenoxathiinyl, thiantenyl, indolizinyl, isoindolyl, indazolyl, purinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, phenanthridinyl, perimidinyl, perimidinyl Phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, 1,2-benzisoxazolyl, benzothiophenyl, benzox Encompasses Zoriru, benzothiazolyl, benzimidazolyl, benzotriazolyl, thioxanthinyl, carbazolyl, carbolinyl, acridinyl, Pirorijijiniru, the polycyclic heterocyclyls such quinolizidinyl (including both aromatic or non-aromatic).

  In addition to the polycyclic heterocyclyls described above, heterocyclyls include more than one bond in which two or more rings are shared by both rings and more than two that are shared by both rings. And polycyclic heterocyclyl containing an atom. Examples of such bridged heterocycles include quinuclidinyl, diazabicyclo [2.2.1] heptyl, and 7-oxabicyclo [2.2.1] heptyl.

Metal ions that can be used in the synthesis of the skeleton according to the present disclosure include 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⁺ , and combinations thereof (with corresponding metal salt counter anions) ).

  Metal ions in open skeletons (MOF, ZIF, and COF) via complexation with functionalized organic linkers in the backbone (eg imines or N-heterocyclic carbenes) or by simple ion exchange Can be introduced. Therefore, it is possible to introduce any metal ion in the periodic table.

  Preparation of the scaffold according to the present disclosure can be carried out in either an aqueous or non-aqueous system. The solvent can be polar or non-polar depending on the case. The solvent can comprise a templating agent or an optional ligand containing a monodentate functional group. Examples of non-aqueous solvents include n-alkanes (eg, pentane, hexane, etc.), benzene, toluene, xylene, chlorobenzene, nitrobenzene, cyanobenzene, aniline, naphthalene, naphtha, n-alcohols (eg, methanol, ethanol, n -Propanol, isopropanol, etc.), acetone, 1,3, -dichloroethane, methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, diethylformamide, thiophene, pyridine, ethanolamine , Triethylamine, ethylenediamine and the like. One skilled in the art can readily determine a suitable solvent based on the starting reactants. In addition, the selection of the solvent is considered not so important in obtaining the material according to the present disclosure.

  The templating agent can be used in the method according to the present disclosure. The templating agent utilized in the present disclosure is added to the reaction mixture for the purpose of occupying the pores in the resulting crystal backbone. In some variations of the present disclosure, the space filler, adsorbing species, and guest species increase the surface area of the metal organic framework. Suitable space fillers include, for example, (i) alkylamines containing linear, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms and their corresponding alkylammonium salts, ( ii) arylamines having 1-5 phenyl rings and their corresponding arylammonium salts, (iii) containing linear, branched, or cyclic aliphatic groups having 1-20 carbon atoms Alkyl phosphonium salts, (iv) aryl phosphonium salts having 1 to 5 phenyl rings, (v) alkyl containing linear, branched or cyclic aliphatic groups having 1 to 20 carbon atoms An organic acid and its corresponding salt, (vi) an aryl organic acid having 1-5 phenyl rings and its corresponding salt, (vii) a linear, branched, or 1-20 carbon atom, or Aliphatic al containing cyclic aliphatic groups Lumpur, or (viii) a component selected from the group consisting of aryl alcohols having from 1 to 5 phenyl rings and the like.

  For crystallization, the solution is allowed to stand at room temperature or in a constant temperature oven up to 300 ° C., crystallization is started by adding a dilute base to the solution, and crystallization is started by diffusing the dilute base in the solution. And / or by transferring the solution to a sealed bath and heating to a predetermined temperature.

  A device for sorptive uptake of chemical species is also provided. The device includes a sorbent comprising a scaffold provided herein or obtained by a method according to the present disclosure. Uptake can be reversible or irreversible. In some embodiments, the sorbent is incorporated into discrete sorbent particles. Sorptive particles can be embedded in or immobilized on a liquid permeable and / or gas permeable solid three-dimensional carrier. In some embodiments, the sorbent particles have pores for reversible uptake or storage of the liquid or gas, in which the sorbent particles reversibly adsorb the liquid or gas. It is possible to absorb.

  In some embodiments, the devices provided herein include ammonia, carbon dioxide, carbon monoxide, hydrogen, amine, methane, oxygen, argon, nitrogen, argon, organic dyes, polycyclic organic molecules, Including a storage unit for storing chemical species such as combinations thereof.

  A method for sorption uptake of chemical species is also provided. The method includes contacting a chemical species with a sorbent comprising a skeleton provided herein. Incorporation of a chemical species can include storage of the chemical species. In some embodiments, the chemical species are stored under conditions suitable for use as an energy source.

  Also provided is a method for sorption uptake of a chemical species comprising contacting the chemical species with a device described and provided herein.

Natural gas is an important fuel gas and is widely used as a basic feedstock in the petrochemical process industry and other chemical process industries. The composition of natural gas varies greatly depending on the production area. Many natural gas storage tanks have a relatively low percentage of hydrocarbons (eg, less than 40%) and a high percentage of acid gases (mainly carbon dioxide, plus hydrogen sulfide, carbonyl sulfide, carbon disulfide, and various mercaptans). ). Conditioned or sweet dry natural gas for either pipeline delivery, natural gas liquid recovery, helium recovery, conversion to liquefied natural gas (LNG), or subsequent nitrogen removal In order to provide gas, it is desirable to remove acid gases from natural gas produced in remote locations. CO ₂ is corrosive in the presence of water and can form dry ice, hydrates, and freezes in pipelines and cryogenic equipment often used for processing natural gas May cause problems. Also, since it does not contribute to the amount of heat generated, CO ₂ simply increases the cost of gas transport.

  An important aspect of any natural gas treatment process is economics. Since natural gas is typically processed in large quantities, very small differences in processing unit capital and operating costs are important factors in the choice of process technology. Some natural gas resources are currently uneconomic in production due to process costs. There is a continuing need for improved natural gas treatment processes that are highly reliable and that exhibit operational simplicity.

  In addition, the removal of carbon dioxide from the flue exhaust gas of power plants, now the main source of anthropogenic carbon dioxide, can be achieved by cooling and pressurizing the exhaust gas or by fume in a fluidized bed of aqueous amine solution. While generally achieved by passing, both are costly and inefficient. Other methods based on chemisorption of carbon dioxide on oxide surfaces or adsorption in porous silicates, carbon, and membranes have been explored as carbon dioxide uptake means. However, to make an effective adsorption medium have long-term availability for carbon dioxide removal, two characteristics are: (i) a periodic structure in which carbon dioxide uptake and release is sufficiently reversible, and (ii) It must combine chemical functionality and flexibility to allow fine tuning at the molecular level to achieve an optimized uptake capacity.

  Several processes for recovering or removing carbon dioxide from gas steam have been proposed and implemented on a commercial scale. The process varies widely, but generally involves some form of solvent absorption, adsorption onto a porous adsorbent, distillation, or diffusion through a semipermeable membrane.

  The following examples are intended to illustrate but not limit the present disclosure. They are typical of those that can be used, but other procedures known to those skilled in the art can also be used as alternatives.

Example 1: Post-synthetic metallation All reagents were obtained from suppliers (Alfa Aesar, Cambridge isotope laboratories, Sigma Aldrich) and used without further purification unless otherwise stated. All handling was performed in an Ar atmosphere. The reported yield was not optimized. Elemental microanalysis was performed at the University of California, Los Angeles, Department of Chemistry and Biochemistry.

Synthesis of (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ and (Zn4O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ .

Synthesis procedure of (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ . 200 mg of (Zn ₄ O) ₃ (BDC-NH ₂ ) ₃ (BTB) ₄ was placed in a 20 ml glass vial and immersed in 10 ml of anhydrous toluene. 0.3 ml of 2-pyridinecarboxaldehyde was added to the vial and left unmoved for 5 days. The obtained yellow crystals were washed with CH ₂ Cl ₂ and dried under reduced pressure to obtain (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ (0.190 g, 87%) It was.

Synthesis procedure of (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ . 100 mg of (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ was placed in a 20 ml vial and immersed in 10 ml of anhydrous CH ₂ Cl ₂ . 0.20 g of PdCl ₂ (CH ₃ CN) ₂ was added to change the yellow crystals to dark purple. The reaction mixture was left unmoved for 12 hours, after which the dark purple crystals were washed with CH ₂ Cl ₂ and dried (Zn ₄ O) ₃ (BDCC ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ (0.098 g, 85%).

Model compound: Synthesis procedure of dichloro (N- (2-pyridylmethylene) aniline-N, N ′) palladium (II). 2.0 g of (E) -N-((pyridin-2-yl) methylene) benzenamine was reacted with PdCl ₂ (CH ₃ CN) _{2 in} acetone for 2 hours. The resulting orange powder dichloro (N- (2-pyridylmethylene) aniline-N, N ′) palladium (II) (1.45 g) was filtered, dried in air and used without further purification.

  XAS data collection. XAS measurements were performed at the Stanford Synchrotron Radiation Laboratory (SSRL) using a SPEAR storage ring containing 80-100 mA at 3.0 GeV. Pd K absorption edge data were collected using XAS beamline 7-3 for structural molecular biology operating in 2T wiggler magnetic field. A Si (220) double crystal monochromator was used. Beamline 7-3 includes a rhodium-coated vertical collimating mirror upstream of the monochromator and a downstream bent cylindrical focus mirror (also with rhodium coating). Harmonic rejection is achieved by detuning the intensity of the incident line at the end of the scan by 50%. Incident and transmitted X-ray intensities were monitored using an ionization chamber filled with argon or nitrogen. X-ray absorption was measured in transmission mode. At the time of data collection, the sample was held at a temperature of about 10K using a liquid helium flow cryostat from an Oxford instrument. For each sample, three scans were accumulated and the energy was calibrated with reference to the Pd foil absorption (assuming a minimum energy inflection point of 24349.0 eV) measured simultaneously with each scan. The energy threshold of the wide-area X-ray absorption fine structure (EXAFS) vibration was assumed to be 24370 eV.

XAS data analysis. The EXAFS vibration χ (k) was quantitatively analyzed by curve fitting using the EXAFSPAK computer program suite using theoretical phase and amplitude functions from first principles calculated using program FEFF version 8.25. No smoothing, filtering, or related operations were performed on the data.

^a coordination number N, the interatomic distance R (Å), Debye-Waller factor σ2 (Å2), and threshold energy shift ΔE0 (eV). The value in parentheses is the estimated standard deviation (accuracy) obtained from the diagonal elements of the covariance matrix. The accuracy will be significantly greater than these values, as well as numbers and Debye-Waller factors. The fitting error function F is defined as follows.

(Where sum is over all data points incorporated during refinement)
XANES measurement. Fig. 4 compares the region near the absorption edge of Pd model compounds PdCl ₂ (CH ₃ CN) ₂ and (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ . This stacking plot highlights the similarity between the model complex and (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ PdCl ₂ ) ₃ (BTB) ₄ , in which case palladium is very Suggests similar chemical and electronic environments.

  Powder X-ray diffraction. Powder X using a Bruker D8-Discover θ-2θ diffractometer with a reflective Bragg-Brentano geometry using a 1600 W (40 kV, 40 mA) power Cu Kα line focused through a Ni filter and equipped with a Vantec line detector Line data was collected. The irradiation was focused using a parallel focus Gobel mirror. The system also includes an anti-scatter shield that prevents incident scattered radiation from striking the detector and preventing usually high background at 2θ <3. The sample was placed on a zero background sample holder by dropping the powder from a wide blade spatula and then leveling the sample with a razor blade. Samples were prepared by dissolving a small amount of material in methanol followed by sonication for 10 minutes. The data was then collected after filtering the precipitate.

Mass spectrometry. A sample of (Zn4O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ was dissolved in MeOH and ESI-MS was performed in negative ion mode. (See, for example, Figure 5).

Gas adsorption measurement. Low pressure Ar adsorption isotherms were measured volumetrically using an Autosorb-1 analyzer (Quantachrome Instruments). A liquid argon bath (87K) was used for the measurement. The Ar gas and He gas used were UHP grade. From the Ar adsorption isotherm, the BET surface area (available surface area) and total pore volume of each material were calculated (Table 2). The pore volume of each material was estimated from the Dubinin-Radushkevich (DR) model, assuming that the adsorbate is in a liquid state and that adsorption is involved in the pore filling process. Using nonlocal density functional theory (NLDFT) to build a hybrid kernel for Ar adsorption at 87K based on a zeolite / silica model containing cylindrical pores to estimate the pore size distribution of MOF Ar isotherms were analyzed.

For porosity measurement, as-synthesized (Zn ₄ O) ₃ (BDC-C ₆ H ₅ N ₂ ) ₃ (BTB) ₄ was immersed in acetone for 24 hours, during which time the activating solvent was applied 3 times. Replenished. Samples were rejected with supercritical CO ₂ in a Tousimis Samdri PVT-3D critical point dryer. Briefly, an acetone containing sample was placed in the chamber and the acetone was exchanged with liquid CO ₂ . The chamber containing the sample and liquid CO ₂ was then heated to about 40 ° C. and held for 1 hour under supercritical conditions (typically 1300 psi). Porous material was obtained by gradually venting CO ₂ from the chamber at about 40 ° C. (about 1 hour).

  The iminopyridine moiety has been found to be a versatile ligand system that binds to various transition metals in a known coordination environment. The present disclosure demonstrates that such a moiety is incorporated into A by condensation of an amine functionalized backbone with 2-pyridinecarboxaldehyde (Scheme 1). Isoreticular functionalized MOF B was synthesized by adding 1.5 equivalents of 2-pyridinecarboxaldehyde to A in anhydrous toluene and allowing the reaction to proceed for 5 days. During this synthesis, the needle crystals changed color from clear to yellow, yielding a product with a composition that closely matched the expected formula, suggesting quantitative conversion. Powder X-ray diffraction (PXRD) tests (Figure 1) showed that B retains crystallinity and, after covalent transformation, possesses the same basic topology as A. Mass analysis of the decomposed sample of B showed a parent ion peak of m / z 269 ([M−H] −) that can be assigned to the ligand fragment, confirming the presence of the iminopyridine unit.

Isoreticular metalation was achieved by adding 1.5 equivalents of PdCl ₂ (CH ₃ CN) ₂ to B in anhydrous CH ₂ Cl ₂ . At that time, the yellow crystalline material turned dark purple within a few minutes. After 12 hours, the material was washed 3 times with 10 mL portions of CH ₂ Cl ₂ , then the crystals were immersed in anhydrous CH ₂ Cl ₂ and the solvent was renewed every 24 hours for 3 days to give C . Again, the PXRD pattern of C (Figure 1) confirmed that it retained crystallinity and had the same skeletal topology as that of A and B. Removal of the guest species from the pores was achieved by treating the crystals under reduced pressure at 80 ° C. for 12 hours. The molecular formula C ₅₀ H ₂₈ N ₂ O ₁₃ Zn ₄ PdCl ₂ was obtained from elemental analysis performed on a C guest-free skeleton. Its Pd / Zn ratio 1: 4 is consistent with quantitative metalation of the iminopyridine moiety.

  The porosity of B and C was evaluated by creating an 87K Ar isotherm (Figure 2). Of note, both materials retained porosity after two subsequent chemical transformations. In addition, a similar profile was observed in A to C, but there was a small hysteresis in the C isotherm, suggesting the presence of possible defects resulting from a series of chemical reactions performed on the crystal. The

In order to confirm that Pd is complexed to the iminopyridine unit and to accurately determine the Pd coordination environment in the skeleton, Pd K absorption edge broad X-ray absorption fine structure (EXAFS) spectroscopy is performed. C samples were used. FIG. 3 shows the EXAFS Fourier transform of C along with the results of the curve fitting analysis. Data analysis suggested that two Pd-Cl and two Pd-N ligands were present at 2.276 (2) 2 and 1.993 (2) Å, respectively. A survey of the Cambridge Structural Database showed that both of these distances were consistent with crystallographic data for similar Pd compounds. In addition, two Pd-C interactions of 2.793 (4) ^ belonging to the ligand backbone were required for best data fitting. EXAFS data analysis provides a quantitative structural description of the Pd coordination environment within the MOF, clearly demonstrating that Pd is bound to the backbone via the iminopyridine moiety. Furthermore, analysis of the X-ray absorption near edge structure (XANES) spectrum suggests that the main chemical form of Pd in the C skeleton is consistent with the iminopyridine bond and not the starting material PdCl ₂ (CH ₃ CN) ₂ It was done.

Example 2: Pre-synthetic metallation Synthesis and analytical data of linkers (L0-L2) and IRMOF-76,77. Unless otherwise noted, chemical substances were purchased from suppliers and used as received. Anhydrous solvents were obtained from the EMD Chemicals DrySolv® series. Thin layer chromatography (TLC) was performed using a glass plate precoated with silica gel 60 containing a fluorescent indicator (Whatman LK6F). The plate was observed with UV light (254 nm) and iodine / silica gel. Column chromatography was performed using silica gel 60F (230-400 mesh). Solution NMR spectra of ¹ H, ¹³ C, and ¹⁹ F were recorded using a Bruker ARX400 (400 MHz) spectrometer or a Bruker AV600 (600 MHz) spectrometer. Residual solvent was used as an internal standard for ¹ H NMR and ¹³ C NMR. Trifluoroacetic acid (δ = -76.5 ppm) was used as an external standard for ¹⁹ F NMR. Chemical shifts were listed on the δ scale in ppm and the binding constants were recorded in hertz (Hz). The following abbreviations were used to represent multiplicity. s, singlet; d, doublet; t, triplet; q, quadruple; b, broad peak; m, multiplet or overlap peak.

¹³ C CP / MAS solid state NMR spectra were collected on a Bruker DSX-300 spectrometer using a standard Bruker Magic Angle Rotation (MAS) probe equipped with a 4 mm (outer diameter) zirconia rotor. Acquired at 75.47 MHz ( ¹³ C) using cross polarization (CP / MAS) combined with MAS. ^{Both 1} H and ¹³ C 90 degree pulse widths were 4 μs. CP contact time was 1.5ms. High power two-pulse phase modulation (TPPM) ¹ H decoupling was applied during data acquisition. The decoupling frequency corresponds to 72kHz. The MAS sample rotation speed was 10kHz. The recycle delay between scans was varied from 10 to 30 seconds depending on the compound, as determined by no apparent decrease in signal intensity from one scan to the next. A ¹³ C chemical shift is given relative to tetramethylsilane as zero ppm calibrated using the methine carbon signal of adamantane attributed to 29.46 ppm as the secondary standard.

  FT-IR spectra were collected using a Shimazu FT-IR spectrometer. Electrospray ionization mass spectra (ESI-MS), matrix-assisted laser desorption ionization mass spectra (MALDI-MS), and chemical ionization mass spectra with gas chromatography (CI / GC-MS) are available from the Molecular Instrumentation Center (the University of California, Los Angeles).

Elemental microanalysis was performed using a Thermo Flash EA1112 combustion CHNS analyzer. Intertek QTI performed inductively coupled plasma (ICP) analysis of IRMOF-76 and 77.

S1: Starting material (1) was prepared according to reported procedure ¹ . The reduction of 1 was carried out according to the published procedure ^{1 and 2} with slight changes to the post-treatment process. To a 2000 mL flask was added 1 (20.5 g, 70 mmol), CoCl ₂ (91 mg, 0.7 mmol), THF (200 mL), and EtOH (450 mL). The mixture was refluxed. NaBH ₄ (2.65 g, 70 mmol per time) was added three times every hour (total amount 8.0 g). After confirming the consumption of 1 by TLC analysis, the mixture was cooled to room temperature. After adding water (300 mL) and stirring vigorously for 10 minutes, the gummy precipitate was filtered off using Celite. The organic solvent was evaporated and the product was extracted 3 times with dichloromethane. The combined organic layers were washed with water and saturated brine, and dried over Na ₂ SO ₄ . The extract was filtered off, evaporated and the crude mixture was purified using short pad silica gel chromatography (eluent: hexane / acetone = 5/1). The combined solution was evaporated to give the diamine as an orange solid.

The resulting diamine was used immediately in the next step. To the diamine dissolved in MeOH (350 mL) was added HC (OEt) ₃ (13.9 mL, 84 mmol) and sulfamic acid (340 mg, 3.5 mmol). The mixture was stirred overnight producing a powder precipitate. The solvent was evaporated and the residue was rinsed with ether. Drying under air gave S1 as a yellow powder (10.1 g over 2 steps, 52% yield).

¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 7.35 (s, 2H), 8.36 (s, 1 H), 13.2 (brs, 1H); ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ = 113.75, 126.21, 132.75, 144.05; IR (KBr, cm ^-1 ) ν = 630, 792, 912, 956, 1163, 1217, 1259, 1284, 1340, 1381, 1433, 1489, 1616, 2823, 3062; CI / GC-MS [M] ⁺ C ₇ H ₄ Br ₂ N ₂ ⁺ m / z = 276; Elemental analysis: C ₇ H ₄ Br ₂ N ₂ calculated C, 30.47; H, 1.46; N, 10.15%, Observed: C, 30.21; H, 1.64; N, 10.94%.

2: To a 1000 mL flask was added S1 (19.7 g, 71.4 mmol), K ₂ CO ₃ (29.6 g, 214 mmol), and EtOH (500 mL). The mixture was heated at reflux. MeI (8.8 mL, 142.8 mmol) was added dropwise to the hot mixture and the mixture was held at reflux for 1 hour. After confirming the consumption of S2 by TLC analysis, the mixture was cooled to room temperature. After adding water (200 mL) to evaporate EtOH, a powdery precipitate was collected, washed with water and hexane / Et ₂ O (1/1) and dried to give 2 as a brown powder (21.0 g, 100% yield).

¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 4.05 (s, 3H), 7.34 (s, 2H), 8.32 (s, 1H); ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ = 34.51, 102.75, 112.82, 126.14, 128.05, 132.44, 143.80, 147.96; IR (KBr, cm ^-1 ) ν = 524, 623, 719, 781, 918, 1058, 1105, 1186, 1219, 1273, 1301, 1332 , 1390, 1465, 1500, 1604, 1816, 2940, 3086; CI / GC-MS [M] ⁺ C ₈ H ₆ Br ₂ N ₂ ⁺ m / z = 290; Elemental analysis: C ₈ H ₆ Br ₂ N ₂ Calculated C, 33.14; H, 2.09; N, 9.66%, observed C, 31.92; H, 2.13; N, 9.50%.

  S2: To a 1000 mL flask was added 4-methoxyphenylboronic acid (20.5 g, 113 mmol), pinacol (14.0 g, 118 mmol), and THF (500 mL). The mixture was heated to reflux and stirred for 2 hours, then cooled to room temperature. The solution was filtered through short pad basic aluminum oxide and the solvent was evaporated to give S2 as a white powder (26.0 g, 85% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.34 (s, 12H), 3.83 (s, 3H), 7.86 (d, J = 6.7 Hz, 2H), 8.01 (d, J = 6.7 Hz, 2H) ¹³ C NMR (100 MHz, CDCl ₃ ): δ = 24.88, 52.13, 84.16, 128.59, 132.32, 134.66, 167.12; IR (KBr, cm ^-1 ) ν = 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 ₁₄ H ₁₉ BO ₄ ⁺ m / Elemental analysis: C ₁₄ H ₁₉ BO ₄ calculated C, 64.15; H, 7.31%, observed C, 64.81; H, 7.30%.

3: Transesterification was performed according to the procedure ^{3 of the} presentation. To a stirred solution of S2 (13.2 g, 50 mmol) in 500 mL anhydrous diethyl ether, t-BuOK (28.0 g, 250 mmol) was added in portions over 30 minutes under a nitrogen atmosphere. Stirring was continued for 2 hours. The suspension was poured into water (1000 mL). After separating the organic layer, the compound was extracted three times with ethyl acetate. The combined organic layers were dried over Na ₂ SO ₄ , filtered off and evaporated to give 3 as a white powder (12.2 g, 80% yield). 3 was used in the next step without further purification.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.35 (s, 12H), 1.63 (s, 9H), 7.85 (d, J = 6.7 Hz, 2H), 7.96 (d, J = 6.7 Hz, 2H) ; ¹³ C NMR (100 MHz, CDCl ₃ ): δ = 24.87, 28.19, 81.08, 84.09, 128.42, 134.25, 134.52, 165.80; IR (KBr, cm ^-1 ) ν = 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 ₁₃ H ₁₈ BO ₄ ⁺ m / z = 249. Elemental analysis: C ₁₇ H ₂₅ BO ₄ calculated C, 67.12; H, 8.28%, observed C, 67.60; H, 8.23%.

4: 2 (1.93 g, 6.67 mmol), 3 (4.67 g, 15.35 mmol), Pd (PPh ₃ ) ₄ (385 mg, 0.33 mmol), and K ₂ CO _{3 in} 50 mL 1,4-dioxane and 12 mL water A stirred solution of (2.76 g, 20 mmol) was heated to 100 ° C. under a nitrogen atmosphere. Stirring was continued overnight and then the mixture was cooled to room temperature. Water was added and the organic compound was extracted 3 times with ethyl acetate. The combined organic layers were washed with saturated brine and dried over Na ₂ SO ₄ . The extract was filtered through short pad basic aluminum oxide and evaporated. The resulting residue was rinsed with hexane / Et ₂ O (2/1) to give 4 as a brown powder (2.0 g, 62% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.62 (s, 9H), 1.64 (s, 9H), 3.42 (s, 3H), 7.23 (d, J = 7.6 Hz, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.52 (d, J = 8.1 Hz, 2H), 7.87 (s, 1H), 8.05-8.16 (m, 6H); ¹³ C NMR (100 MHz, 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 ) ν = 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 (M -CH ₂ = C (CH ₃ ) ₂ ] ⁺ C ₂₆ H ₂₅ N ₂ O ₄ ⁺ m / z = 429 .; Elemental analysis: C ₃₀ H ₃₂ N ₂ O ₄ calculated C, 74.36; H, 6.66; N , 5.78%, observed: C, 73.05; H, 6.50; N, 6.06%.

  5: A solution of 4 (570 mg, 1.17 mmol) and MeI (0.73 mL, 11.7 mmol) in 12 mL acetonitrile was heated to reflux and stirred overnight. After the mixture was cooled to room temperature, the volatiles were evaporated. The resulting residue was rinsed with hexane / ethyl acetate (2/1) to give 5 as a brown powder (689 mg, 94% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.61 (s, 18H), 3.87 (s, 6H), 7.41 (s, 2H), 7.53 (d, J = 6.6 Hz, 4H), 8.10 (d, J = 6.6 Hz, 4H), 10.64 (s, 1H); ¹³ C NMR (100 MHz, 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 ) ν = 621, 709, 773, 846, 1012, 1118, 1165, 1296, 1369, 1456, 1608, 1710 (s), 2976, 3435 (br); ESI-TOF- MS [MI] ⁺ C ₃₁ H ₃₅ N ₂ O ₄ ⁺ m / z = 499. Elemental analysis: C ₃₁ H ₃₅ IN ₂ O ₄ calculated C, 59.43; H, 5.63; N, 4.47%, observed value: C 56.83; H, 5.70; N, 4.72%.

L0: To a solution of 5 (2.1 g, 3.35 mmol) in dichloromethane (35 mL) was added HBF ₄ .OEt ₂ (2.26 mL, 16.5 mmol). The mixture was stirred at room temperature for 2 hours. After dilution with diethyl ether, the precipitate was filtered and washed thoroughly with dichloromethane and diethyl ether. Toluene was added to the powder and evaporated. This is repeated twice to remove residual water as an azeotrope. After drying under reduced pressure at 50 ° C., L0 was obtained as a gray powder (1.7 g, yield 100%).

¹ H NMR (400 MHz, DMSO-d ₆ ): δ = 3.50 (s, 6 H), 7.54 (s, 2H), 7.72 (d, J = 9.2Hz, 4H), 8.03 (d, J = 9.2 Hz , 4H), 9.63 (s, 1H), 13.2 (brs, 2H); ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ = 37.94, 128.58, 128.72, 129.72, 130.07, 130.70, 131.10, 140.12, 145.82 ^{, 163.18; 19 F NMR (376.5} MHz, DMSO-d 6): δ = -148.9 (s, BF 4 -); MALDI- MS: [M-BF 4] + C 23 H 19 N 2 O 4 + m / z = 387.

S3: 5 (1.87 g, 3 mmol), Pd (CH ₃ CN) ₂ Cl ₂ (900 mg, 3.3 mmol), NaI (750 mg, 6 mmol), and K ₂ CO ₃ (2.07 g, 15 mmol) in 30 mL pyridine The solution was heated to reflux and stirred overnight. After the mixture was cooled to room temperature, all volatiles were evaporated. The resulting residue was dissolved in chloroform (200 mL) and water (100 mL). The separated organic layer was washed with 5% CuSO ₄ aq. (30 mL, twice) and saturated brine (30 mL), and then dried over Na ₂ SO ₄ . The extract was filtered through short pad silica gel and washed thoroughly with hexane / acetone (2/1). The combined organic solution was evaporated to give S3 as an orange powder (2.5 g, 88% yield).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.64 (s, 18 H), 3.79 (s, 6 H), 7.09 (s, 2H), 7.25-7.34 (m, 2H), 7.51 (d, J = 8.2 Hz, 4H), 7.70-7.77 (m, 1H), 8.11 (d, J = 8.2 Hz, 4H), 8.97-9.01 (m, 2H) ¹³ C NMR (100 MHz, 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 ) ν = 675, 692, 769, 848, 1012, 1116 , 1165, 1294, 1388, 1446, 1604, 1710 (s), 2974, 3445; elemental analysis: C ₃₆ H ₃₉ I ₂ N ₃ O ₄ Pd calculated C, 46.10; H, 4.19; N, 4.48%, observation Values: C, 43.64; H, 4.02; N, 4.79%.

L1: Me ₃ SiOTf (1.67 mL, 9.24 mmol) was added to a solution of S3 (2.5 g, 2.64 mmol) in dichloromethane (15 mL). The mixture was stirred at room temperature for 2 hours. After adding water, the brown precipitate was filtered and washed thoroughly with water and dichloromethane. To the brown powder (S4) in CHCl ₃ / MeOH (1/1, 25 mL) was added pyridine (1 mL, 13.2 mmol). The mixture was stirred at room temperature for 30 minutes. Volatiles were evaporated and the residue was suspended in dichloromethane. 5% CuSO ₄ aq. Was added to the suspension. The mixture was stirred for 10 minutes and the orange powder was filtered and washed with water. Toluene was added to the orange powder and evaporated. This is repeated twice to remove residual water as an azeotrope. After drying under reduced pressure, L1 was obtained as an orange powder (1.62 g, yield 74%).

¹ H NMR (400 MHz, DMSO-d ₆ ): = 3.68 (s, 6 H), 7.21 (s, 2 H), 7.48-7.52 (m, 2H), 7.63 (d, J = 7.6 Hz, 4H) , 7.87-7.93 (m, 1H), 8.03 (d, J = 7.6 Hz, 4H), 8.83-8.86 (m, 2H), 13.1 (brs, 2H); ¹³ C NMR (150 MHz, 80 ° C, 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, the peak of methyl carbon substituted on nitrogen (about 40 ppm) is the DMSO residual peak. ¹³ C CP / MAS solid-state NMR (75 MHz): δ = 42.15, 125.00, 129.27, 142.18, 153.28 (NHC carbon), 172.74; IR (KBr, cm ^-1 ) ν = 549, 594, 673, 692, 769, 825, 862, 920, 1012, 1078, 1109, 1176, 1290, 1386, 1444, 1606, 1685 (s), 2546, 2663, 3448; ESI-TOF-MS (anionic mode) [M-pyridine _{^{-H] - C 23 H 17 I}} 2 N 2 O 4 Pd - m / z = 744 the isotopic pattern agreed well to that simulated; elemental _{analysis: C 28 H 23 I 2 N} 3 O 4 Pd Calculated C, 40.73; H, 2.81; N, 5.09%, observed: C, 40.22; H, 2.91; N, 5.20%.

L2: Quinoline (0.2 mL) was added to a suspension of L1 (about 80 mg) in 5 mL of chloroform. The mixture was stirred at room temperature for 1 hour. Volatiles were evaporated and the residue was suspended in chloroform and filtered to collect L2 as an orange powder that was used as a reference compound for degradation testing.

IRMOF-76: L0 (47mg, 0.1mmol), Zn (BF 4) 2 hydrate _{(72mg, 0.3mmol), KPF 6} (186mg, 1mmol) N solid mixture in a capped vial, N- dimethylformamide (DMF, 15 mL). The reaction was heated to 100 ° C. for 24-48 hours to produce bulk crystals on the vial wall. The vial was then removed from the oven and allowed to cool to room temperature. After opening the lid and removing the mother liquor from the mixture, colorless crystals were collected and rinsed with DMF (3 × 4 mL). X-ray diffraction of the powder and single crystal of this material was measured immediately. Samples dried under reduced pressure after solvent exchange with chloroform were used for CP / MAS NMR and IR measurements.

Analytical data for IRMOF-76: ¹⁹ F NMR of IRMOF-76 resolved in DCl / DMSO-d ₆ (1/20). The presence of BF ₄ ^- ( ^- 149.2 ppm, s) and PF ₆ ^- ( ^- 71.1 ppm, d, JPF = 707 Hz) was confirmed.

IR (KBr, cm ^-1 ) ν = 557, 715, 783, 843, 1012, 1406, 1544, 1608 (s), 3421
¹³ C CP / MAS solid NMR (75 MHz) 36.10 ^{(methyl), 129.06 *, 138.69 *,} 143.60 (C2 of _{benzimidazole), 174.11 (CO 2 Zn)} . ^* Wide overlapping peaks in the aromatic region.

ICP analysis. Measurement element ratio: C ₆₉ H _54.5 B _0.53 P _1.89 F _10.9 N _6.1 Zn _4.3 . Estimation formula: Zn ₄ O (C ₂₃ H ₁₇ N ₂ O ₅ ) ₃ (BF ₄ ) _0.5 (PF ₆ ) _1.6 (OH) _0.9 = C ₆₉ H _51.9 B _0.5 P _1.6 F _11.6 N ₆ O _17.9 Zn ₄
Neither potassium (K) nor iodine (I) was detected in excess of trace amounts.

  The post-synthetic formation of NHC from IRMOF-76 was investigated as follows and was not successful.

• Treatment with Bronsted base (potassium / sodium / lithium tert-butoxide, DBU, Et ₃ N) • Treatment with Ag ₂ O or Ag ₂ CO ₃ • Formation of CN / CCl ₃ / alkoxide adducts for thermal α elimination

IRMOF-77: A solid mixture of L1 (16.6 mg, 0.02 mmol) and Zn (NO ₃ ) ₂ · 6H ₂ O (18 mg, 0.06 mmol) in a capped vial with N, N-diethylformamide (DEF, 1.5 mL) ) And pyridine (0.02 mL). The reaction system was heated to 100 ° C. for 24-36 hours to form bulk crystals on the bottom of the vial. The vial was then removed from the oven and allowed to cool to room temperature. After opening the lid and removing the mother liquor from the mixture, light orange crystals were collected and rinsed with DEF (3 × 4 mL). X-ray diffraction of the powder and single crystal of this material was measured immediately.

All impurities were separated using the difference in crystal density. After decanting the mother liquor, DMF and CHBr ₃ (1: 2 ratio) were added to the crystals. Floating orange crystals were collected and used.

Activation of IRMOF-77: IRMOF-77 was activated using a Tousimis Samdri PVT-3D critical point dryer. Before drying, the solvated MOF sample was immersed in anhydrous acetone and the immersion solution was changed for 3 days, during which time the activated solvent was decanted and replenished anew. The acetone exchanged sample was placed in the chamber and acetone was completely exchanged with liquid CO ₂ over 2.5 hours. During this time, liquid CO ₂ was renewed every 30 minutes. After the final exchange, the chamber was heated to about 40 ° C. This brought the chamber pressure to about 1300 psi (above the critical point of CO ₂ ). After maintaining the chamber under supercritical conditions for 2.5 hours, CO ₂ was gradually vented from the chamber over 1 to 2 hours. The dried sample was placed in a quartz adsorption tube and tested for porosity. Solid state CP / MAS NMR, IR, and elemental analysis were also recorded.

Analysis data of IRMOF-77:
Elemental analysis
Zn ₄ O (C ₂₈ H ₂₁ I ₂ N ₃ O ₄ Pd) ₃ (H ₂ O) ₄
Calculated values: C, 35.77; H, 2.54; I, 26.99; N, 4.47; Pd, 11.32; Zn, 9.28
Observations: C, 35.04; H, 2.62; I, 26.92; N, 4.71; Pd, 9.67; Zn, 9.32
IR (KBr, cm ^-1 )
ν = 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 (75 MHz)
IRMOF-77: 40.36 (methyl), 125.97 ^* , 130.47 ^* , 140.86 (pyridine), 154.10 (NHC carbon), 175.37 (CO ₂ Zn)
Link L1: 42.15 (methyl), 125.03 ^* , 129.31 ^* , 142.20 (pyridine), 153.29 (NHC carbon), 173.00 (CO ₂ H)
^* Wide overlapping peaks in the aromatic region.

  Post-synthetic ligand exchange of IRMOF-77: IRMOF-77 crystals were immersed in 4% v / v quinoline / DMF solution in a 20 mL vial (with lid) and left for 1 day. The quinoline solution was decanted and the crystals were rinsed with DMF (3 × 4 L), after which the PXRD pattern was measured immediately. After exchanging with chloroform for 1 day, the solvent was removed under reduced pressure at room temperature overnight. Solid CP / MAS NMR spectra were recorded using the dry compound.

¹³ C CP / MAS solid state NMR (75 MHz) of quinoline exchange type IRMOF-77:
MOF: 39.63 (methyl), 128.81 ^* , 140.19 ^* , 146.19 (quinoline), 152.86 (NHC carbon), 174.38 (CO ₂ Zn)
Link L2: 40.14 and 43.43 (non-equivalent methyl), 128.16 ^* , 143.14 ^* , 146.32 (quinoline), 153.59 (NHC carbon), 173.42 (CO ₂ H)
* Wide overlapping peaks in the aromatic region.

  Single crystal X-ray diffraction data collection, structural analysis, and refinement procedures for IRMOF-76 and IRMOF-77. An initial scan of each sample was performed to obtain preliminary unit cell parameters and the crystal mosaicity (spot width between frames) was evaluated to select the frame width required for data collection. In either case, a frame width of 0.5 ° was judged appropriate. In addition, data for the entire hemisphere was collected using Bruker APEX2 software suite that overlaps φ scan and ω scan with two different detector (2θ) set values (2θ = 28 °, 60 °). After data collection, reflections from all regions of the Ewald sphere were sampled to re-determine unit cell parameters for data integration and to examine rotational twinning using CELL_NOW. After thorough examination of the collected frames, the resolution of the data set was determined. Data were integrated with Bruker APEX2 V 2.1 software using a narrow frame algorithm and an average intensity split lower limit of 0.400. Subsequently, the absorption data was corrected by the program SADABS. The determination of space group and the inspection of facet twin formation were performed by XPREP.

All structures were analyzed by direct methods and refined using the SHELXTL 97 software suite. The position of the atom was determined by repeating the test of the difference F map following the least square refinement of the previous model. The final model was refined anisotropically until sufficient convergence was achieved (if the number of allowed data and stable refinement were reachable). Hydrogen atoms were placed at calculated positions and incorporated as riding atoms with an isotropic displacement parameter of 1.2 to 1.5 times the U _eq of the bonded carbon atoms.

IRMOF-76: IRMOF-76 colorless bulk crystals (0.60 × 0.60 × 0.40 mm) were placed in a 1.0 mm diameter borosilicate capillary containing a small amount of mother liquor to prevent desolvation during data collection. Cu Kα line (λ = 1.5418Å) operated with 1200W power (40kV, 30mA) with CCD surface detector while sealing capillary and cooling to 258 (2) K in liquid N ₂ cooling stream of nitrogen Was attached to a SMART APEXII triaxial diffractometer, which generated the data at this temperature.

  Whole hemisphere data was collected using the Bruker APEX2 software suite with overlapping φ and ω scans with two different detector (2θ) settings (2θ = 28 °, 60 °). A total of 96360 reflections were collected. Of these, 1260 were unique, of which 913 were over 2σ (I). The range of θ was 1.78 ° -40.06 °. Analysis of the data showed that the attenuation during collection was negligible. The program scale was set to minimize the difference between symmetry related reflections or repetitively measured reflections.

The structure was analyzed to be a cubic Fm-3m space group with Z = 8. All non-hydrogen atoms except C8, C9 and N1 are refined anisotropically. Others are not possible because of crystal quality, and stable isotropic refinement has been achieved. The atoms in the dimethylimidazolium ring (C8, C9, and N1) turn out to be disordered and they are refined as half-occupied in each element. A hydrogen atom was placed at the calculated position and incorporated as a riding atom with an isotropic displacement parameter of 1.2-1.5 times the U _eq of the bonded C atom. We investigated the structure using the PLATON ¹⁰ Adsym subroutine and found that no other symmetry was applicable to the model.

Modeling the electron density in the framework voids did not identify the guest material in this structure because the contents of the large pores in the framework were disordered. Diffuse scattering from highly disordered solvents in the void space within the crystal and from capillaries used to allow crystal attachment can cause background noise and "washout" of high angle data. The solvent was not modeled in the crystal structure. Constraints were used for the dimethylimidazolium ring (C7-N1, C8-N1, and C9-N1 bond lengths were fixed). The structure was expected to have a high reliability factor, albeit with inadequate data. Some atoms showed high U _iso due to low quality of diffraction data. Insufficient length and angle are due to inadequate constraints and esd is also high.

The structure was reported to represent the framework of IRMOF-76 as isolated in crystalline form. The structure is a simple cubic skeleton. A. Spek's SQUEEZE ⁵ routine was applied to clarify the accuracy of atomic positions in the skeleton. However, the atomic coordinates of the “non-SQUEEZE” structure are also presented. Absorption correction was not performed. Final full matrix least-squares refinement about F ^2, converged to _{R 1 = 0.0549 (F> 2σ} (F)) and wR ₂ = 0.2166 (all data) with GOF = 0.912. For structures that did not use the SQUEEZE program, the final perfect matrix least squares refinement for F ² converged to R ₁ = 0.1465 (F> 2σ (F)) and wR ₂ = 0.4378 (all data) with GOF = 1.941 . In this structure, high R-values are often found in MOF crystallography for the reasons given above by us and other research groups.

IRMOF-77: IRMOF-77 light orange block crystals (0.30 × 0.30 × 0.20 mm) were placed in a 0.4 mm diameter borosilicate capillary containing a small amount of mother liquor to prevent desolvation during data collection. Cu Kα line (λ = 1.5418Å) operated with 1200W power (40kV, 30mA) with CCD surface detector while sealing capillary and cooling to 258 (2) K in liquid N ₂ cooling stream of nitrogen Was attached to a SMART APEXII triaxial diffractometer, which generated the data at this temperature.

  Whole hemisphere data was collected using the Bruker APEX2 software suite with overlapping φ and ω scans with two different detector (2θ) settings (2θ = 28 °, 60 °). A total of 51319 reflections were collected. Of these, 3946 was unique, of which 2238 was greater than 2σ (I). The range of θ was 2.06 ° to 39.74 °. Analysis of the data showed that the attenuation during collection was negligible. The program scale was set to minimize the difference between symmetry related reflections or repetitively measured reflections.

The structure was analyzed by direct methods and refined using the SHELXTL 97 software suite. The position of the atom was determined by repeating the test of the difference F map following the least square refinement of the previous model. The structure was analyzed to be a trigonal R-3c space group with Z = 12. All zinc atoms (Zn1, Zn2), palladium atoms (Pd1), iodine atoms (I1, I2), and other non-hydrogen atoms (except C6, C12, C17) on the backbone of the skeleton are their parents It is refined anisotropically with hydrogen atoms generated as spheres that ride on the coordinates of the atoms. Others are not possible because of crystal quality, and stable isotropic refinement has been achieved. A hydrogen atom was placed at the calculated position and incorporated as a riding atom with an isotropic displacement parameter of 1.2-1.5 times the U _eq of the bonded C atom. We investigated the structure using PLATON's Adsym subroutine and confirmed that other symmetries were not applicable to the model.

  Modeling the electron density in the framework voids did not identify the guest material in this structure because the contents of the large pores in the framework were disordered. Due to the large esd, it is impossible to determine the exact position of the solvent molecules. Therefore, we first modeled some unidentified peaks in the void space that could not be attributed to any distinct material as isolated oxygen atoms.

A structure was reported to represent the skeleton of IRMOF-77 as isolated in crystalline form. The structure is a double interpenetrating cubic skeleton. A. Spek's SQUEEZE routine was applied to clarify the correct position of atoms in the skeleton. However, the atomic coordinates of the “non-SQUEEZE” structure are also presented. Thus, the structure reported after SQUEEZE does not contain any solvent. Absorption correction was not performed. Final full matrix least-squares refinement about F ^2, converged to _{R 1 = 0.0560 (F> 2σ} (F)) and wR ₂ = 0.1389 (all data) with GOF = 0.950. For structures that did not use the SQUEEZE program, the final perfect matrix least square refinement for F ² converged to R ₁ = 0.1039 (F> 2σ (F)) and wR ₂ = 0.3399 (all data) with GOF = 1.141 . A final ratio of 12.0 between the number of reflections and the number of parameters was achieved. In this structure, high R-values are often found in MOF crystallography for the reasons given above by us and other research groups.

  The satisfactory isoreticular covalent transformations and subsequent metalation demonstrated herein provide a means for incorporating metal ions into a wide range of frameworks. Basically, this expands the reaction space that can be secured in the MOF.

Synthesis procedure for Zr-aminoterephalate MOF: 40 mg of (ZrCl ₄ ) along with 100 mg of 2-aminoterephthalic acid was placed in a glass vial containing 40 mL of DMF. The reaction was heated at 85 ° C. for 3 days. The powder was filtered and replaced with 3 × 40 mL chloroform.

  Experimental and simulation powder X-ray diffraction patterns. Powder X-ray diffraction (PXRD) data was collected using a Bruker D8-Discover θ-2θ diffractometer with reflective Bragg-Brentano geometry. Cu Kα1 line (λ = 1.5406Å, 1600W, 40kV, 40mA) was focused using a planar Gobel mirror on the Kα line. A 0.6 mm divergence slit was used for all measurements. Diffraction lines were detected using a Vantec line detector (Bruker AXS, 6 ° 2θ sampling width) equipped with a Ni monochromator. All samples were placed on a glass slide fixed on the sample holder by dropping the crystals and then leveling the sample surface with a wide blade spatula. The best count statistic was achieved by using a 0.02 ° 2θ step scan over 2-50 ° with an exposure time of 0.4 seconds per step.

  Thermogravimetric analysis (TGA) data for IRMOF-76, 77. All samples were tested on a TA Instruments Q-500 series thermogravimetric analyzer with the samples held in a platinum dish in a continuous flow nitrogen atmosphere. Samples were heated at a constant rate of 5 ° C./min during all TGA experiments.

Measurement of porosity of IRMOF-77. Low pressure gas adsorption isotherms were measured volumetrically using an Autosorb-1 analyzer (Quantachrome Instruments). A liquid N ₂ bath (77K) was used for N ₂ isotherm measurements. The N ₂ gas and He gas used were UHP grade (99.999%). To calculate the surface area, the Langmuir and BET methods were applied using the N ₂ isotherm adsorption branch assuming an N ₂ cross section of 16.2 Å ² / molecule. The Langmuir surface area and BET surface area are estimated to be 1610 and 1590 m ² g ⁻¹ , respectively. The pore volume was determined using the Dubinin-Raduskavich (DR) method, assuming that the adsorbate is in a liquid state and that adsorption is involved in the pore filling process. Assuming the bulk density of IRMOF-77 (0.922 g cm ⁻³ ), the calculated pore volume (0.57 cm ³ g ⁻¹ ) corresponds to 0.53 cm ³ · cm ⁻³ .

  This example is directed to structures based on the well-known simple cubic MOF-5 and utilizing linear ditopic carboxylate links that can accommodate NHC-metal complexes or precursors thereof. This disclosure demonstrates a convergent synthetic route for a new link that utilizes a cross-coupling reaction as the primary step of combining an imidazolium core and a carboxylate module (Scheme 2, supra).

  The synthesis of 4,7-bis (4-carboxylphenyl) -1,3-dimethylbenzimidazolium tetrafluoroborate (L0) starts from the known 4,7-dibromobenzothiadiazole (1). Thiadiazole was converted to benzimidazole by cobalt-catalyzed reduction with sodium borohydride followed by acid-catalyzed condensation with triethylorthoformate. Sequential N-methylation produced the dibromobenzimidazole core (2). Diester-terminated linear terphenyl strut (4) was obtained by Pd (0) -catalyzed Suzuki-Miyaura cross-coupling between 2 and 4- (tert-butoxycarbonyl) phenylpinacol borane (3).

Specifically, in the synthesis of L0, a module having a tert-butyl ester as a masked carboxylic acid was selected because solubility was improved and unmasking of the carboxylic acid at a later stage was possible. Treatment with excess methyl iodide produced 5 with an N, N′-dimethylbenzimidazolium moiety. Next, I ^- to give the L0 by deprotecting the two tert- butyl ester using the counter anion substituted for simultaneously HBF ₄ ^- BF ₄ from. All conversions were feasible on a gram scale.

IRMOF-76 was synthesized using a mixture of 3 equivalents of Zn (BF ₄ ) ₂ .xH ₂ O, 10 equivalents of KPF ₆ , and L0 in N, N-dimethylformamide (DMF). The mixture was heated at 100 ° C. for 36 hours, after which colorless crystals of IRMOF-76 (Zn ₄ O (C ₂₃ H ₁₅ N ₂ O ₄ ) (X) ₃ (X = BF ₄ , PF ₆ , OH)) were obtained. It was.

Single crystal X-ray diffraction analysis revealed that IRMOF-76 was isoreticular, similar to MOF-5. In this case, the Zn ₄ O unit is connected to six L0 links to form a cubic skeleton with a pcu topology (FIG. 6a). IRMOF-76 is a non-interpenetrating cationic MOF with an imidazolium moiety (NHC precursor) on each link. From ICP analysis and ¹⁹ F NMR spectrum of resolved IRMOF-76, it is clear that both BF ₄ ⁻ and PF ₆ ⁻ are included as counter anions of the imidazolium moiety.

  A strategy using links with metal-NHC complexes was developed. Metal-NHC bonds are generally stable even under mildly acidic conditions, and chemoselective NHC coordination is often based on oxygen-metal coordination during the construction of secondary building units (SBUs). Avoiding undesirable reactions with metal sources. In particular examples described herein, [4,7-bis (4-carboxylphenyl) -1,3-dimethylbenzimidazol-2-ylidene] (pyridyl) palladium (II) iodide (L1, scheme) 2) was used. This is potentially attractive as a catalyst similar to known homogeneous catalyst systems.

L1 was prepared from intermediate 5 (Scheme 2). The 5 benzimidazolium moiety was converted to NHC-PdI ₂ (py) complex when refluxed in pyridine with Pd (II) source, base (K ₂ CO ₃ ), and iodide source (NaI). Deprotection of the tert-butyl ester was achieved using trimethylsilyl trifluoromethanesulfonate (TMSOTf). The covalently generated Pd (II) -NHC bond was surprisingly stable even under strong Lewis acidic conditions for deprotection. However, the pyridine co-ligand is removed to form a dimer complex. Addition of pyridine as a ligand was necessary to produce L1 with a monomeric NHC-PdI ₂ (pyridine) moiety.

IRMOF-77 was synthesized using 3 equivalents of Zn (NO ₃ ) ₂ · 6H ₂ O with respect to L1 in a solvent mixture (75/1) of N, N-diethylformamide (DEF) and pyridine. . The mixture was heated at 100 ° C. for 30 hours, after which orange crystals of IRMOF-77 (Zn ₄ O (C ₂₈ H ₂₁ I ₂ N ₃ O ₄ Pd) ₃ ) were obtained.

From X-ray single crystal structure analysis, it is clear that IRMOF-77 is also reticulated like MOF-5. The X-ray crystal structure verifies the presence of NHC-PdI ₂ (py) moiety (FIG. 6b). The Zn ions used to build the skeleton do not participate in binding with the metal-NHC moiety. The measured elemental composition is consistent with the expected value, confirming the absence of undesirable metal exchange on NHC. The observed Pd-C distance (1.925 mm) and coordination geometry are in good agreement with those found in the Cambridge Structural Database for NHC-PdX ₂ (py) (X = halide) complexes. The presence of Pd (II) -NHC bond was further confirmed by solid state ¹³ C cross-polarization magic angle rotation (CP / MAS) NMR spectrum (NC: -N σ = 154.1 ppm). NHC-Pd (II) moieties are located on all faces of the cubic cage in the skeleton. Two interwoven skeletons are formed with an offset distance of about 7 mm (Figure 6c) (possibly to mitigate mutual interference between the metal-NHC moieties), and the shortest distance between the two methyl carbons of the two skeletons is 4.06 mm Met. As a result, the catenation is different from that of IRMOF-15, whose link length is the same as L1. Due to the interwoven nature of the structure, the pore opening is about 5 mm × 10 mm. All immobilized Pd (II) centers protrude into the pores without interfering with each other.

To confirm the structural stability of the presence and IRMOF-77 of the void space, demonstrating a permanent porous by N ₂ adsorption isotherm of the guest-free sample. The isotherm shows rapid N ₂ uptake in the low pressure region, suggesting that the material is microporous (Figure 7). The Langmuir and BET surface areas of active IRMOF-77 are calculated to be 1,610 and 1,590 m ² g ⁻¹ , respectively. The amount of N ₂ incorporation into the pore (P / P ₀ = 0.9) corresponds to 46 N ₂ molecules per formula unit or 552 per unit cell.

To investigate the reactivity of the immobilized Pd (II) center of IRMOF-77, coordination was performed by immersing the as-synthesized IRMOF-77 crystal in a 4v / v% quinoline / DMF solution at room temperature for 1 day. A child exchange experiment was conducted. From a comparison of powder X-ray diffraction (PXRD) patterns before and after the exchange, it is clear that the skeleton remains intact during the exchange process (Figure 8). No signal from the pyridine proton is observed in the ¹ H NMR spectrum of MOF resolved after ligand exchange. Only the signal from the quinoline is observed at the expected molar stoichiometric ratio (carboxylate link: quinoline = 1: 1). Retention of NHC-Pd bond is confirmed by ¹³ C CP / MAS solid state NMR spectrum (front: 154.1 ppm, rear: 152.9 ppm). These results suggest the presence of NHC-PdI ₂ (quinoline) complex after ligand exchange.

  The structure of IRMOF-76 and 77 demonstrates the satisfactory application of the method according to the present disclosure for immobilizing Pd (II) -NHC organometallic complexes in MOF without losing the porosity and structural order of MOF. The

  Several embodiments of the present invention have been described. However, it will be appreciated that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims (14)

  An organometallic skeleton comprising the general structure M-L-M, wherein M is a skeletal metal and L is a linking moiety having a heterocyclic carbene or imine group bonded to a modified metal.   The organometallic skeleton of claim 1, wherein the imine group comprises a chelating group.   The organometallic skeleton of claim 1, wherein the link portion is metallized prior to reaction with the skeletal metal.   4. The organometallic skeleton of claim 3, wherein the linking moiety comprises an N-heterocyclic carbene.   The organometallic skeleton according to claim 1, wherein the skeleton includes a covalent organic skeleton (COF), a zeolite type imidizole skeleton (ZIF), or a metal organic skeleton (MOF).   The organometallic skeleton of claim 2, wherein the imine group is post skeleton chelated to a metal. The skeleton metal is 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 ^The organometallic skeleton according to claim 1, which is selected from the group consisting of ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Bi ⁵⁺ , Bi ³⁺ . The modified metal is 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 ^{2. The} organometallic skeleton of claim 1, selected from the group consisting of ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Bi ⁵⁺ , Bi ³⁺ .   The organometallic skeleton of claim 1, wherein the modified metal extends into the pores of the skeleton.   The organometallic skeleton of claim 1, wherein the skeleton lacks a guest species.   Reacting a link moiety containing a heterocyclic carbene and containing a protected link cluster with a modified metal to obtain a metalated link moiety, deprotecting the link cluster, and converting the metallized link moiety to a skeletal metal The manufacturing method of the organometallic frame | skeleton of Claim 1 including making it react with.   Reacting an organic skeleton containing an amine group with 2-pyridinecarboxaldehyde to obtain an imine functionalized link moiety; contacting the skeleton with a metal chelating the imine functionalized link moiety; The manufacturing method of the organometallic frame | skeleton of Claim 1 containing this.   A gas sorption composition comprising the organometallic skeleton of claim 1.   A catalyst composition comprising the organometallic skeleton of claim 1.

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