Controlling the morphology of metal-organic frameworks through coordination mimicry

Abstract

Methods for the synthesis of crystalline metal-organic frameworks (MOFs) are provided that have polytopic organic linkers and cations, each linker binding to two or more cations. In the disclosed methods, the linkers are represented by the formula M n X m where each M is independently cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is anionic, and n and m are integers. The reaction is carried out in the presence of a salicylate, salicylamide, 1,3-phthalate, or hydroxybenzoate based modulator.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This disclosure claims priority to U.S. Provisional Patent Application No. 63 / 228,503, filed August 2, 2021, the entire contents of which are incorporated by reference into this specification.

[0002] Field of the Disclosure This application relates to the synthesis of metal-organic framework (MOF) crystals under conditions that result in advantageous crystal morphologies and thereby improve the bulk performance of the MOFs thus crystallized. [Background technology]

[0003] background

[0003] Porous materials have a range of applications, particularly as adsorbents and catalysts in a wide range of technologies such as chemical separation, energy storage, catalysis, drug delivery, and sensing. Potential industrial applications of one particular class of porous materials, metal-organic frameworks, include methane conversion, hydrocarbon separation and catalysis, noble gas separation, and carbon dioxide capture from flue gases. For example, Li et al.,2011,“Metal-Organic Frameworks for Separations,”Chem.Rev.112,869;Sumida et al.,2012,“Carbon Dioxide Capture in Metal-Organic Frameworks,”Chem.Rev.112,724;McDonald et al.,2015,“Cooperative Insertion of CO2in Diamine-Appended Metal-Organic Frameworks,”Nature 519,303;Milner et al.,2018,“Overcoming double-step CO2adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(4,4'-dioxidobiphenyl-3,3'-dicarboxylate),”Chem.Sci.9,160;and Bachman et al.,2016,“Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals,”Nature See Mater. 15, 845.

[0004]

[0004] Processes involving such chemical separations currently account for 10-15% of the world's energy use. See Oak Ridge National Laboratory. Materials for Separation Technologies: Energy and Emission Reduction Opportunities, 2005; and Humphrey and Keller, 1997, Separation Process Technology, McGraw-Hill. Separation performance, such as in packed bed applications, can be highly dependent on the size and shape of the crystallites, which control the surface area to volume ratio and mass transfer resistance of porous materials such as metal-organic frameworks. See Rousseau, 1987, "Handbook of Separation Process Technology," John Wiley and Sons, pp. 669-671. The catalytic performance of heterogeneous catalysts such as metal-organic frameworks can result from factors such as material phase and mass transfer resistance, the latter of which can be a function of the size and shape of the crystallites. See Fogler, 2016, Elements of Chemical Reaction Engineering, Fifth Ed., Prentice Hall.

[0005]

[0005] M2(dobdc)(M=Mg, Mn, Fe, Co, Ni, Zn, Cd; dobdc 4-Adsorbents such as M2(dobpdc) (M = 2,5-dioxido-1,4-benzenedicarboxylate, Figure 20) and the related extended class of materials M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate, Figure 21) (McDonald et al., 2015, Nature 519, p. 303; Siegelman, 2017, J. Am. Chem. Soc., 139, p. 10526) are of interest as porous solid adsorbent materials for use in separations, catalytic applications, and gas storage. Such metal-organic frameworks are of interest due to their architecture featuring coordinatively unsaturated metal sites along the pores. See Rosi et al., 2005, J. Am. Chem. Soc. 127(5), 1504; Rowsell et al., 2006, Am. Chem. Soc. 128, p. 1304; Caskey et al., 2008, J. Am. Chem. Soc. 130, p. 10870; McDonald et al., 2012, J. Am. Chem. Soc. 134, p. 7056; and WO 2013059527 A1, dated April 25, 2013, to Long et al., entitled "Alkylamine functionalized metal-organic frameworks for composite gas separations."

[0006]

[0006] One drawback of these materials is that conventional synthesis schemes typically result in crystalline metal-organic frameworks that have extended anisotropic growth, resulting in rod-like crystalline products. As shown in Figure 1, the synthesis of metal-organic frameworks typically requires a source of metal ions or clusters and partially to fully deprotonated ligands. Generally, this is done in solution at high temperatures, with deprotonation occurring via decomposition of the solvent to form a base. The solvent is often a toxic and / or expensive solvent, such as N,N-dimethylformamide.

[0007]

[0007] Macro-scale crystal properties of metal-organic frameworks, such as size and shape, have a large impact on adsorption performance, and such anisotropic crystal structures resulting from conventional metal-organic framework schemes often prevent significant diffusion in the direction of the ab plane, for example in M2(dobdc) and M2(dobpdc) compounds. See, for example, Colwell et al., “Buffered Coordination Modulation as a Means of Controlling Crystal Morphology and Molecular Diffusion in an Anisotropic Metal-Organic Framework,” J. Am. Chem. Soc. 2021, 143, 13, 5044-5052; and Forse et al., “Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal-Organic Frameworks,” Chem. Mater. 2020, 32, 8, 3570-3576. In other cases, the diffusion direction depends on the respective metal-organic framework. Therefore, the final metal-organic framework scheme of each crystal has a large impact on the diffusion rate through the crystal.

[0008]

[0008] Therefore, one of the goals of MOF synthesis is to establish synthesis conditions that can obtain crystalline metal-organic frameworks without decomposing the organic linker. At the same time, the crystallization kinetics should be suitable for nucleation and growth of the desired phase. These complex relationships make it difficult to determine the MOF synthesis reaction conditions that can obtain MOF crystallites of suitable size and shape.

[0009]

[0009] Previous work on the fundamentals of MOFs has used synthesis utilizing non-coordinating buffers to independently control the reaction pH during metal-organic framework synthesis, allowing direct investigation of the role of the coordinating species on crystal growth. This work demonstrates the effectiveness of buffered reaction conditions in the synthesis of low-dispersity single crystals of the framework Co2(dobdc) in a pH 7 buffer solution using cobalt(II) carboxylate as the metal source. This work shows that the aspect ratio of the Co2(dobdc) crystals is dependent on the pK of the carboxylate modulator used during synthesis. a See International Publication No. WO 2020 / 068996, entitled “Metal-Organic Framework Phase and Crystallite Shape Control.”

[0010]

[0010] As shown in Figures 2-4, another strategy used in the literature to affect the specific size or shape of metal-organic framework crystallites is to use additives with established synthesis, called coordination modulators. See Stock and Biswas, 2012, Chem. Rev. 112, 933; Hermes et al., 2007 J. Am. Chem. Soc. 129, 5324; Cho et al., 2008, J. Am. Chem. Soc. 130, 16943; Diring et al., 2010, Chem. Mater. 22, 4531; and Pachfule et al., 2016, Nature Chem. 8, 718. Most of these additives have the same or similar functional groups as the organic linker, which are thought to bind competitively during growth. However, all of these additives are also acids or bases, and may participate in the pH equilibrium during growth in addition to the coordination equilibrium. The only example of control of M2(dobdc) uses salicylic acid as a modulator, but does not address its involvement in acid / base equilibrium. See Pachfule et al., 2016, Nature Chem. 8, 718. Other published syntheses of M2(dobdc) or M2(dobpdc) do not form monodisperse samples of microcrystals, but rather are high aspect ratio or form polycrystalline masses. See Rosi et al., 2005, J. Am. Chem. Soc. 127(5), 1504, Rowsell and Yaghi, 2006, Am. Chem. Soc. 128, 1304; and Caskey et al., 2008, J. Am. Chem. Soc. 130, 10870. One limitation of substituted carboxylate modulators is that they only modulate the crystal morphology along the c-axis of the crystal.Based on zero-length chromatography and NMR diffusion coefficient studies, pores along the c-axis of M2(dobdc) crystals diffuse gas faster than pores along the ab-plane (see Forse et al., 2020, “Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal-Organic Frameworks,” Chem. Mater. 2020, 32(8), 3570-3576), suggesting that shorter disk shapes are ideal for fast gas diffusion and longer needle shapes are ideal for slow gas diffusion. Furthermore, Figure 5 shows how the crystal morphology of MOFs is determined by the basic anion used by the prior art. Figure 6 shows the use of different basic anions coupled with pH control to synthesize MOF crystals by the prior art. Summary of the Invention [Means for solving the problem]

[0011] overview

[0011] Therefore, in light of the above background, what is needed in the art is an improved synthesis scheme for metal-organic frameworks that results in crystalline products with controlled crystallite size. For example, what is needed in the art is a new synthesis method for controlling the morphology of MOF crystals, such as M2(dobdc) crystals, across the c-axis.

[0012]

[0012] Disclosed herein is a synthetic scheme for controlling the crystal shape of metal-organic frameworks (MOFs) beyond just the c-axis by appropriate selection of modulators present during the synthesis of such metal-organic frameworks. The disclosure utilizes modulators such as salicylates, salicylamides, 1,3-phthalates, and 3-hydroxybenzoates to obtain a series of new MOF crystal morphologies. The disclosure provides synthetic conditions for synthesizing MOF crystals with needle, disk, or rice grain shapes. In particular, needle and disk shapes are of interest because they allow new ways to tune the gas diffusion rate through MOF crystals.

[0013]

[0013] One aspect of the present disclosure provides a method for synthesizing a crystalline metal-organic framework comprising a plurality of cations and a plurality of polytopic organic linkers, each of which is bonded to two or more cations of the plurality of cations. In the method, the plurality of polytopic organic linkers are represented by the formula M n X m where each M is independently a cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, Hf, X is a basic anion, n is a positive integer, and m is a positive integer. The reaction is represented by the equation: [ka] or a salt thereof (e.g., sodium, potassium, cesium), or a mixture thereof, and R1, R2, R7, R8, R9, R 10 , and R 11are each independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl; R3, R4, R5, and R6 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl; R 10 and R 11 are not hydrogen.

[0014]

[0014] These and other features and characteristics of the disclosed synthetic schemes of the present disclosure, and their advantageous applications and / or uses, will become apparent from the following detailed description. [Brief description of the drawings]

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0015] To assist those of ordinary skill in the relevant art in making and using the subject matter herein, reference is made to the accompanying drawings.

[0016] [Figure 1]

[0016] It shows how metal organic frameworks are formed from the combination of metal cations and ligands. [Diagram 2]

[0017] 1 shows how modulators inhibit the growth of metal-organic framework crystals. [Diagram 3]

[0018] 1 shows how modulators can control the size and shape of metal-organic framework crystals. [Figure 4]

[0019] 1 illustrates the mechanism by which modulators enable control of the size and shape of metal-organic framework crystals. [Diagram 5]

[0020] FIG. 1 shows how the basic anion used controls the MOF crystal morphology according to the prior art. [Figure 6]

[0021] 1 illustrates the different roles of modulators and pH in metal-organic framework crystals. [Figure 7]

[0022] 1 illustrates tuning the synthesis to obtain larger isotropic nanocrystals of metal organic frameworks according to embodiments of the present disclosure. [Figure 8A]

[0023] 13 shows additional modulators for controlled growth of Co2(dobdc) according to embodiments of the present disclosure. [Figure 8B]

[0023] Further modulators for controlled growth of Co2(dobdc) according to embodiments of the present disclosure are provided. [Figure 8C]

[0023] Further modulators for controlled growth of Co2(dobdc) according to embodiments of the present disclosure are provided. [Figure 9]

[0024] 1 shows the synthesis conditions for Co2(dobdc) crystals according to one embodiment of the present disclosure. [Figure 10]

[0025] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 350x magnification. [Figure 11]

[0026] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 3500x magnification. [Figure 12]

[0027] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 5000x magnification. [Figure 13]

[0028] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 8000x magnification. [Figure 14]

[0029] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 10,000x magnification. [Figure 15]

[0030] Clockwise, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate according to embodiments of the present disclosure are shown at 12000x magnification. [Figure 16]

[0031] According to one embodiment of the present disclosure, Co2(dobdc) crystals grown in the presence of the modulator salicylate are shown at 1504x magnification (top), and Co2(dobdc) crystals grown in the presence of 3-hydroxybenzoate are shown at 2000x magnification (bottom). [Figure 17]

[0032] According to one embodiment of the present disclosure, 10 equivalents of 3-hydroxybenzoate show consistently smaller crystals than 1 equivalent, but the crystal size does not decrease monotonically with modulator concentration, and the same trend is observed for salicylamide, phthalate, and bromosalicylamide. [Figure 18]

[0033] One embodiment of the present disclosure shows how a higher pH results in smaller aspect ratio crystals. [Figure 19]

[0034] FIG. 1 shows how trichloroacetate regulated metal-organic framework crystallization according to one embodiment of the present disclosure results in very low modulator contamination in the metal-organic framework, 83 ppm by elemental analysis (left panel), which is not visible by energy dispersive x-ray spectroscopy. [Figure 20]

[0035] 1 shows the structure of a metal organic framework M2(dobdc) consisting of a divalent metal cation and a ligand H4dobdc according to the prior art. [Figure 21]

[0036] 1 shows the structure of a metal organic framework M2(dobpdc) consisting of a divalent metal cation and a ligand H4dobpdc according to the prior art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Detailed Description of the Invention

[0037] I. Introduction

[0038] One of the drawbacks of conventional MOF crystal synthesis schemes is that they typically result in crystalline MOFs with extended anisotropic growth, resulting in rod-like crystalline products. Since the macroscale crystal properties of MOFs, such as size and shape, have a significant impact on adsorption performance, such anisotropic crystal structures resulting from conventional metal-organic framework schemes often prevent significant diffusion in the ab-plane direction. It is therefore speculated that most of the outer surface of high aspect ratio crystallites is not available for gas diffusion. Therefore, MOF synthesis requires synthesis conditions that result in crystalline MOFs without decomposition of the organic linkers, while at the same time promoting crystallization kinetics that allow nucleation and growth of the desired phases to occur. These complex relationships make it difficult to determine the synthesis reaction conditions for MOFs that result in MOF crystallites of appropriate size and shape.

[0018]

[0039] The present disclosure provides for the synthesis of crystalline metal-organic frameworks (MOFs). These MOFs comprise polytopic organic linkers and metal cations, each polytopic organic linker binding to two or more metal cations. In the disclosed methods, the linker is represented by the formula M n X mwhere each M is independently cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is a basic anion, n is a positive integer (e.g., 1, 2, etc.), and m is a positive integer (e.g., 1, 2, etc.). In some embodiments, the reaction is carried out in the presence of a modulator such as salicylate, salicylamide, 1,3-phthalate, 3-hydroxybenzoate, or salts thereof (e.g., sodium, potassium cesium), or mixtures thereof. As shown in FIG. 7, each type of modulator affects a particular axis or face, or the overall size of the MOF crystal. Furthermore, as shown in FIGS. 8A, 8B, and 8C, each modulator thereby has a distinct effect on the MOF crystal morphology.

[0019]

[0040] Before describing the invention in more detail, it should be understood that the invention is not limited to the specific embodiments described herein, as the embodiments may vary. It should also be understood that the terms used herein are for the purpose of describing the specific embodiments only, and that the terms are not intended to be limiting. The scope of the invention is limited only by the appended claims. Unless otherwise defined, 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 invention belongs. When a range of values ​​is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit between the upper and lower limits of that range, and any other stated or intervening value within that stated range, is included within the scope of the invention, unless otherwise clearly indicated by the context. The upper and lower limits of these smaller ranges may independently be included within the smaller ranges, and are also included within the scope of the invention, subject to any specifically excluded limits in the stated range. Where a stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention. Certain ranges are described herein using numerical ranges preceded by the term "about". The term "about" is used herein to express in words the exact number it precedes, as well as a number that is close to or approximately the same as the number it precedes. In determining whether a number is close to or approximately the same as a particular recited number, the unrecited number that is close or approximately the same may be a number that is substantially equal to the particular recited number in the context in which it is indicated. All publications, patents, and patent applications cited herein are incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. Furthermore, each cited publication, patent, or patent application is incorporated by reference herein to disclose and describe the subject matter in connection with which the publication is cited. The citation of any publication is made for its disclosure prior to the filing date and should not be construed as an admission that the inventions described herein are not entitled to any benefit by virtue of prior invention antedating the publication.Further, the dates of publication provided may be different from the actual publication dates, which may need to be independently confirmed.

[0020]

[0041] It is noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as a predicate for using exclusive terms such as "solely," "only," and the like in connection with the recitation of claim elements, or for using an "eliminating" limitation. As will be apparent to one of ordinary skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has distinct components and features that may be readily separated or combined with the features of any of the other several embodiments without departing from the scope or spirit of the invention. Any method described may be carried out in the order of events described or in any other order that is logically possible. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, representative and illustrative methods and materials are now described.

[0021]

[0042] In describing the present invention, the following terms will be used and are defined as set forth below.

[0022]

[0043] II. Definition

[0044] Where substituents are specified by their conventional chemical formula written from left to right, those structures also optionally include the chemically identical substituents that would result if the structures were written from right to left, e.g., -CH2O- is also intended to be optionally written as -OCH2-.

[0023]

[0045] The term "alkyl," by itself or as part of another substituent, means, unless otherwise stated, linear, branched or cyclic hydrocarbon radicals, or combinations thereof, which may be fully saturated, mono- or polyunsaturated, and have the specified number of carbon atoms (i.e., C1-C2). 10means 1-10 carbons), divalent, trivalent, and polyvalent groups. Examples of saturated hydrocarbon groups include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, cyclohexylmethyl, cyclopropylmethyl, e.g., homologs and isomers of n-pentyl, n-hexyl, n-heptyl, n-octyl. Unsaturated alkyl groups are those having one or more double or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologs and isomers. The term "alkyl," unless otherwise noted, is also meant to optionally include derivatives of alkyl defined in more detail below, such as "heteroalkyl." Alkyl groups that are limited to hydrocarbon groups are referred to as "homoalkyl." Representative alkyl groups include monounsaturated C 9-10 Oleoyl chain, or diunsaturated C 9-10 , 12-13 An example is a linoeyl chain.

[0024]

[0046] The term "alkylene" by itself or as part of another substituent means a divalent radical derived from an alkane, including, but not limited to, -CH2CH2CH2CH2-, and further including those groups described below as "heteroalkylene." Typically, an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred in the present invention. A "lower alkyl" or "lower alkylene" is a shorter chain alkyl or alkylene group, generally having 8 or fewer carbon atoms.

[0025]

[0047] The terms "alkoxy," "alkylamino," and "alkylthio" (or thioalkoxy) are used in their conventional sense to refer to an alkyl group attached to the remainder of the molecule through an oxygen atom, an amino group, or a sulfur atom, respectively.

[0026]

[0048] The terms "aryloxy" and "heteroaryloxy" are used in their conventional sense to refer to an aryl or heteroaryl group attached to the remainder of the molecule through an oxygen atom.

[0027]

[0049] The term "heteroalkyl," by itself or in combination with another term, means, unless otherwise specified, a stable linear or branched, or cyclic hydrocarbon radical, or combination thereof, consisting of the specified number of carbon atoms and at least one heteroatom selected from the group consisting of O, N, Si, and S, wherein the nitrogen and sulfur atoms may be optionally oxidized and the nitrogen heteroatom may be optionally quaternized. The heteroatoms O, N, S, and Si may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Examples include, but are not limited to, -CH2-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -S(O)-CH3, -CH2-CH2-S(O)2-CH3, -CH=CH-O-CH3, -Si(CH3)3, -CH2-CH=N-OCH3, and -CH=CH-N(CH3)-CH3. Up to two heteroatoms can be consecutive, such as, for example, -CH2-NH-OCH3 and -CH2-O-Si(CH3)3. Similarly, the term "heteroalkylene" by itself or as part of another substituent means a divalent radical derived from heteroalkyl, including, but not limited to, -CH2-CH2-S-CH2-CH2- and -CH2-S-CH2-CH2-NH-CH2-. For heteroalkylene groups, heteroatoms can also occupy either or both chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, etc.). Additionally, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. For example, the formula -COR'- represents both -C(O)OR' and -OC(O)R'.

[0028]

[0050] The terms "cycloalkyl" and "heterocycloalkyl", by themselves or in combination with other terms, represent, unless otherwise specified, cyclic versions of "alkyl" and "heteroalkyl", respectively. Additionally, in the case of heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Further representative cycloalkyl groups include steroids, such as cholesterol and its derivatives. Examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl, 2-piperazinyl, and the like.

[0029]

[0051] The terms "halo" or "halogen," by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. Additionally, terms such as "haloalkyl" are meant to include monohaloalkyl and polyhaloalkyl. For example, the term "halo(C1-C4)alkyl" is meant to include trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like.

[0030]

[0052] The term "aryl", unless otherwise specified, refers to a polyunsaturated aromatic substituent which may be one ring or multiple rings (preferably 1-3 rings) fused or covalently linked to each other. The term "heteroaryl" refers to an aryl substituent (or ring) containing 1-4 heteroatoms selected from N, O, S, Si, and B, where the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atoms are optionally quaternized. Representative heteroaryl groups are six-membered azines such as pyridinyl, diazinyl, and triazinyl. Heteroaryl groups can be attached to the remainder of the molecule through a heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, Examples include 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl, and 6-quinolyl. Substituents for each of the above listed aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below.

[0031]

[0053] For brevity, the term "aryl" when used in combination with other terms (e.g., aryloxy, arylthioxy, arylalkyl) includes aryl, heteroaryl, and heteroarene rings as defined above. Thus, the term "arylalkyl" is meant to include groups in which an aryl group is attached to an alkyl group (e.g., benzyl, phenethyl, pyridylmethyl, etc.) that contains an alkyl group in which a carbon atom (e.g., a methylene group) has been replaced with, for example, an oxygen atom (e.g., phenoxymethyl, 2-pyridyloxymethyl, 3-(1-naphthyloxy)propyl, etc.).

[0032]

[0054] Each of the above terms (e.g., "alkyl," "heteroalkyl," "aryl and "heteroaryl") are meant to optionally include both substituted and unsubstituted forms of the indicated species. Representative substituents for these species are provided below.

[0033]

[0055] Substituents for alkyl and heteroalkyl groups (including groups often referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) are commonly referred to as "alkyl group substituents" and include, but are not limited to, H, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl ... and -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R', -N--O--R' Each of R', R", R'" and R"" preferably independently represents hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, e.g., aryl substituted with 1-3 halogens, substituted or unsubstituted alkyl, alkoxy, or thioalkoxy groups, or arylalkyl groups. When a compound of the invention includes more than one R group, for example, each R group is independently selected, such as each of R', R", R'", and R"" groups, when two or more of these groups are present. When R' and R" are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 5-, 6-, or 7-membered ring. For example, -NR'R" is meant to include, but not be limited to, 1-pyrrolidinyl and 4-morpholinyl. From the above discussion of substituents, one of skill in the art will understand that the term "alkyl" is meant to include groups that contain carbon atoms bonded to groups other than hydrogen groups, such as haloalkyl (e.g., -CF and -CHCF) and acyl (e.g., -C(O)CH, -C(O)CF, -C(O)CHOCH, etc.).These terms include groups that are considered exemplary "alkyl group substituents" that are components of exemplary "substituted alkyl" and "substituted heteroalkyl" moieties.

[0034]

[0056] Similar to the substituents described for alkyl, substituents for aryl, heteroaryl, and heteroarene groups are generally referred to as "aryl group substituents." These substituents include, for example, groups attached to the heteroaryl or heteroarene nucleus via a carbon or heteroatom (e.g., P, N, O, S, Si, or B) in a number ranging from 0 to the total number of open valences on the aromatic ring system, including, but not limited to, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, OR', =O, =NR', =N-OR', -NR'R", -SR', -halogen, -SiR'R". R"', OC(O)R', -C(O)R', CO2R', -CONR'R", -OC(O)NR'R", -NR"C(O)R', NR'C(O)NR"R"', -NR"C(O)2R', NR-C(NR'R"R'")=NR"", NRC(NR'R")=NR'", -S(O)R', -S(O)2R', -S(O)2NR'R", NRS02R', -CN and -NO2, -R', -N3, -CH(Ph)2, fluoro(C1-C4)alkoxy, and fluoro(C1-C4)alkyl. Each of the above named groups is attached to a heteroarene or heteroaryl nucleus either directly or through a heteroatom (e.g., P, N, O, S, Si, or B); where R', R", R"', and R"" are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. When a compound of the invention contains more than one R group, each R group is independently selected, as are each of the R', R", R'", and R"" groups when two or more of these groups are present.

[0035]

[0057] Two substituents on adjacent atoms of an aryl, heteroarene, or heteroaryl ring are of the formula -TC(O)-(CRR') q Alternatively, two substituents on adjacent atoms of an aryl or heteroaryl ring may be optionally replaced with a substituent of the formula -U-, where T and U are independently -NR-, -O-, -CRR'-, or a single bond, and q is an integer from 0 to 3. Alternatively, two substituents on adjacent atoms of an aryl or heteroaryl ring may be optionally replaced with a substituent of the formula -A-(CH2) r A and B may optionally be replaced with a substituent of the formula -B- (A and B are independently -CRR'-, -O-, -NR-, -S-, -S(O)-, -S(O)2-, -S(O)2NR'-, or a single bond, and r is an integer from 1 to 4). One of the single bonds of the new ring thus formed may optionally be replaced with a double bond. Alternatively, two substituents on adjacent atoms of an aryl, heteroarene, or heteroaryl ring may be optionally replaced with a substituent of the formula -(CRR') s -X-(CR”R'”) d - (wherein s and d are independently integers from 0 to 3, and X is -O-, -NR'-, -S-, -S(O)-, -S(O)2-, or -S(O)2NR'-) substituents. The substituents R, R', R", and R'" are preferably independently selected from hydrogen or substituted or unsubstituted (C1-C6)alkyl. These terms include groups that are considered representative "aryl group substituents" that are components of the representative "substituted aryl", "substituted heteroarene", and "substituted heteroaryl" moieties.

[0036]

[0058] As used herein, the term "acyl" refers to a substituent containing a carbonyl residue, C(O)R. Representative species for R include H, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl.

[0037]

[0059] As used herein, the term "fused ring system" means at least two rings, each of which has at least two atoms in common with another ring. A fused ring system can include aromatic and non-aromatic rings. Examples of "fused ring systems" are naphthalene, indole, quinoline, chromene, and the like.

[0038]

[0060] As used herein, the term "heteroatom" includes oxygen (O), nitrogen (N), sulfur (S) and silicon (Si), boron (B) and phosphorus (P).

[0039]

[0061] The symbol "R" is a general shorthand notation that represents a substituent selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heterocycloalkyl groups.

[0040]

[0062] The compounds disclosed herein may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may contain isotopes of, for example, tritium ( 3 H), iodine-125( 125 I), or carbon-14 ( 14 C). All isotopic variations of the compounds of the present invention, whether radioactive or not, are intended to be encompassed within the scope of the present invention.

[0041]

[0063] The term "salt" includes salts of compounds prepared by neutralization of an acid or base, depending on the particular ligand or substituents found on the compounds described herein. When the compounds of the present invention contain relatively acidic functional groups, base addition salts can be obtained by contacting the neutral form of such compounds with a sufficient amount of the desired base, either neat or in a suitable inert solvent. Examples of base addition salts include sodium, potassium, calcium, ammonium, organic amino, or magnesium salts, or similar salts. Examples of acid addition salts include those derived from inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, carbonic acid, monohydrogencarbonic acid, phosphoric acid, monohydrogenphosphoric acid, dihydrogenphosphoric acid, sulfuric acid, monohydrogensulfuric acid, hydroiodic acid, or phosphorous acid, as well as salts derived from relatively non-toxic organic acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, maleic acid, malic acid, malonic acid, benzoic acid, succinic acid, suberic acid, fumaric acid, lactic acid, mandelic acid, phthalic acid, benzenesulfonic acid, p-tolylsulfonic acid, citric acid, tartaric acid, methanesulfonic acid, and the like. Certain compounds of the present invention contain both basic and acidic functionalities, which allow the compounds to be converted into either base or acid addition salts. Hydrates of the salts are also included.

[0042]

[0064] When this term is used, "-COOH" means -C(O)O - and -C(O)O - X + where X + is a cationic counterion. Similarly, a substituent having the formula -N(R)(R) is + H(R)(R) and -N + H(R)(R)Y - where Y - represents an anionic counterion. Representative polymers of the invention contain protonated carboxyl moieties (COOH). Representative polymers of the invention contain deprotonated carboxyl moieties (COO - The various polymers of the present invention contain both protonated and deprotonated carboxyl moieties.

[0043]

[0065] In any compound described herein having one or more chiral centers, unless the absolute stereochemistry is specified, it is understood that each center may be independently in the R or S configuration or a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure or may be enantiomeric mixtures. Furthermore, in any compound described herein having one or more double bonds resulting in geometric isomers that can be defined as E or Z, it is understood that each double bond may be independently E or Z or a mixture thereof. Similarly, it is understood that all tautomeric forms are intended to be included in any compound described.

[0044]

[0066] Below are examples of specific embodiments of the present disclosure. These examples are provided for illustrative purposes only and are not intended to limit the scope of the invention in any way.

[0045]

[0067] III. Composition

[0068] One aspect of the present disclosure provides a crystalline material. The crystalline material comprises a metal organic framework comprising a plurality of metal ions and a plurality of polytopic organic linkers. Each polytopic organic linker in the plurality of polytopic organic linkers binds to at least two cations in the plurality of cations. In some embodiments, the adsorbent material further comprises a plurality of ligands. In some such embodiments, each ligand in the plurality of ligands binds to a metal ion in the plurality of metal ions of the metal organic framework. In some embodiments, the crystalline material is in the form of individual crystals having the shape of a needle, a disk, or a grain of rice.

[0046]

[0069] In some embodiments, the polytopic organic linker is 2,5-dioxido-1,4-benzenedicarboxylate (dobdc 4- ), 4,6-dioxido-1,3-benzenedicarboxylate (m-DOBDC 4-), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxide-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ), or dioxidobiphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- , pc-dobpdc 4- (also called).

[0047]

[0070] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 12 and R 13 and each are hydrogen. In some embodiments, the polytopic organic linker is unprotonated, partially protonated, or fully protonated in solution as shown.

[0048]

[0071] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 12 and R 13 and each are hydrogen. In some embodiments, the polytopic organic linker is unprotonated, partially protonated, or fully protonated in solution as shown.

[0049]

[0072] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 and each are hydrogen. In some embodiments, the polytopic organic linker is unprotonated, partially protonated, or fully protonated in solution as shown.

[0050]

[0073] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 20 , R 21 , R 22 , R 23 , R 24 , and R 25and each are hydrogen. In some embodiments, the polytopic organic linker is unprotonated, partially protonated, or fully protonated in solution as shown.

[0051]

[0074] In some embodiments, the polytopic organic linker is 2,5-dioxido-1,4-benzenedicarboxylate (dobdc 4- ), 4,6-dioxido-1,3-benzenedicarboxylate (m-DOBDC 4- ), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxide-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ), Dioxidobiphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- , pc-dobpdc 4- 2,5-dioxidobenzene-1,4-dicarboxylate (also called DOBD) 4- ), 1,3,5-benzenetristetrazolate (BTT), 1,3,5-benzenetristriazolate (BTTri), 1,3,5-benzenetrispyrazolate (BTP), or 1,3,5-benzenetriscarboxylate (BTC).

[0052]

[0075] In some embodiments, the formula M n X mis a magnesium(II) metal salt, a manganese(II) metal salt, an iron(II) metal salt, a cobalt(II) metal salt, a nickel(II) metal salt, a zinc(II) metal salt, or a cadmium(II) metal salt. In some embodiments, the metal salt is cobalt(II) nitrate, cobalt(II) chloride, cobalt(II) acetate, cobalt(II) sulfate, cobalt(II) iodide, cobalt(II) bromide, cobalt(II) trifluorosulfonate, cobalt(II) tetrafluoroborate, cobalt(II) oxide, cobalt(II) carbonate, cobalt(II) hydroxide, cobalt(II) hydroxycarbonate, cobalt(II) mixed halides, cobalt(II) acetylacetonate, cobalt(II) formate, cobalt(II) perchlorate, or halogenated derivatives thereof. In some embodiments, the basic anion is formate or acetate. In some embodiments, the basic anion is sulfate, bromide, iodide, or trifluorosulfonate, and the reaction is carried out in the presence of a buffer that is free of metal-coordinating functional groups.

[0053]

[0076] IV. Representative synthesis scheme

[0077] In the present disclosure, a crystalline metal-organic framework is synthesized that includes a plurality of metal cations and a plurality of polytopic organic linkers, each polytopic organic linker in the plurality of polytopic organic linkers is bonded to two or more metal cations in the plurality of metal cations, and the crystalline metal-organic framework is characterized by one or more pore channels. In some such embodiments, the plurality of polytopic organic linkers is represented by the formula M n X mwhere each M is independently cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is a basic anion (e.g., formate, acetate, sulfate, bromide, iodide, or trifluorosulfonate, etc.), n is a positive integer (e.g., 1, 2, etc.), and m is a positive integer (e.g., 1, 2, etc.). The reaction is carried out in the presence of a modulator such as salicylate, salicylamide, 1,3-phthalate, 3-hydroxybenzoate, or salts thereof (e.g., sodium, potassium cesium), or mixtures thereof. In this manner, the crystal morphology (e.g., one or more crystallographic directions or their primary bonds) of the resulting metal-organic framework crystal is controlled. For example, in some embodiments, crystal growth of the metal-organic framework results in crystals having the shape of a needle, a disk, or a grain of rice. FIG. 9 shows example concentrations of metal cations, polytopic organic linkers, and modulators, as well as example buffers, pH, solvents, and reaction temperatures used in accordance with the present disclosure to generate Co2(dobdc) crystals.

[0054]

[0078] In some embodiments, the polytopic organic linkers are present in solution at a concentration between 1 mM and 50 mM prior to reaction and have the formula M n X m The one or more compounds of are present in solution at a concentration between 5 nM and 100 nM prior to the reaction, and the modulator is present in solution at a concentration between 15 nM and 100 nM prior to the reaction.

[0055]

[0079] In some embodiments, the plurality of polytopic organic linkers are present in the solution at a concentration of at least 0.1 mM, at least 0.5 mM, at least 1 mM, at least 5 mM, at least 10 mM, at least 15 mM, at least 20 mM, at least 25 mM, at least 30 mM, at least 35 mM, at least 40 mM, at least 45 mM, at least 50 mM, at least 60 mM, at least 70 mM, at least 80 mM, at least 90 mM, at least 100 mM, at least 150 mM, at least 200 mM, at least 300 mM, at least 400 mM, at least 500 mM, at least 600 mM, at least 700 mM, at least 800 mM, or at least 900 mM. In some embodiments, the polytopic organic linkers are present in the solution at a concentration of at least 1 M, at least 2 M, at least 3 M, at least 4 M, at least 5 M, at least 6 M, at least 7 M, at least 8 M, at least 9 M, at least 10 M, at least 15 M, at least 20 M, at least 30 M, at least 40 M, at least 50 M, at least 60 M, at least 70 M, at least 80 M, at least 90 M, at least 100 M, at least 200 M, or at least 500 M. In some embodiments, the polytopic organic linkers are present in the solution at a concentration of 800 M or less, 500 M or less, 100 M or less, 80 M or less, 50 M or less, 20 M or less, 10 M or less, 5 M or less, or 1 M or less. In some embodiments, the polytopic organic linkers are present in the solution at a concentration of 800 mM or less, 500 mM or less, 100 mM or less, 80 mM or less, 50 mM or less, 20 mM or less, 10 mM or less, 5 mM or less, or 1 mM or less. In some embodiments, the polytopic organic linkers are present in the solution at a concentration of 0.5 mM to 10 mM, 1 mM to 200 mM, 50 mM to 500 mM, 200 mM to 1 M, 1 M to 50 M, 10 M to 200 M, or 50 mM to 10 M. In some embodiments, the polytopic organic linkers are present in the solution at a concentration within another range starting from 0.1 mM or more and ending at 800 M or less.

[0056]

[0080] In some embodiments, the formula Mn X m The one or more compounds of formula M are present in the solution at a concentration of at least 0.1 nM, at least 0.5 nM, at least 1 nM, at least 5 nM, at least 10 nM, at least 15 nM, at least 20 nM, at least 25 nM, at least 30 nM, at least 35 nM, at least 40 nM, at least 45 nM, at least 50 nM, at least 60 nM, at least 70 nM, at least 80 nM, at least 90 nM, at least 100 nM, at least 150 nM, at least 200 nM, at least 300 nM, at least 400 nM, at least 500 nM, at least 600 nM, at least 700 nM, at least 800 nM, or at least 900 nM. n X m The one or more compounds of formula M are present in the solution at a concentration of at least 1 mM, at least 2 mM, at least 3 mM, at least 4 mM, at least 5 mM, at least 6 mM, at least 7 mM, at least 8 mM, at least 9 mM, at least 10 mM, at least 15 mM, at least 20 mM, at least 30 mM, at least 40 mM, at least 50 mM, at least 60 mM, at least 70 mM, at least 80 mM, at least 90 mM, at least 100 mM, at least 200 mM, or at least 500 mM. n X m The one or more compounds of formula M are present in the solution at a concentration of 1000 mM or less, 500 mM or less, 100 mM or less, 80 mM or less, 50 mM or less, 20 mM or less, 10 mM or less, 5 mM or less, or 1 mM or less. n X m The one or more compounds of formula M are present in solution at a concentration of 800 nM or less, 500 nM or less, 100 nM or less, 80 nM or less, 50 nM or less, 20 nM or less, 10 nM or less, 5 nM or less, or 1 nM or less. n X mThe one or more compounds of formula M are present in the solution at a concentration of 0.5 nM to 10 nM, 1 nM to 200 nM, 50 nM to 500 nM, 200 nM to 1 mM, 1 mM to 50 mM, 10 mM to 200 mM, or 50 nM to 10 mM. n X m One or more of the compounds of are present in the solution at concentrations within another range starting from 0.1 nM or more and ending at 1 M or less.

[0057]

[0081] In some embodiments, the modulator is present in solution at a concentration of at least 0.1 nM, at least 0.5 nM, at least 1 nM, at least 5 nM, at least 10 nM, at least 15 nM, at least 20 nM, at least 25 nM, at least 30 nM, at least 35 nM, at least 40 nM, at least 45 nM, at least 50 nM, at least 60 nM, at least 70 nM, at least 80 nM, at least 90 nM, at least 100 nM, at least 150 nM, at least 200 nM, at least 300 nM, at least 400 nM, at least 500 nM, at least 600 nM, at least 700 nM, at least 800 nM, or at least 900 nM. In some embodiments, the modulator is present in the solution at a concentration of at least 1 mM, at least 2 mM, at least 3 mM, at least 4 mM, at least 5 mM, at least 6 mM, at least 7 mM, at least 8 mM, at least 9 mM, at least 10 mM, at least 15 mM, at least 20 mM, at least 30 mM, at least 40 mM, at least 50 mM, at least 60 mM, at least 70 mM, at least 80 mM, at least 90 mM, at least 100 mM, at least 200 mM, or at least 500 mM. In some embodiments, the modulator is present in the solution at a concentration of 1000 mM or less, 500 mM or less, 100 mM or less, 80 mM or less, 50 mM or less, 20 mM or less, 10 mM or less, 5 mM or less, or 1 mM or less. In some embodiments, the modulator is present in solution at a concentration of 800 nM or less, 500 nM or less, 100 nM or less, 80 nM or less, 50 nM or less, 20 nM or less, 10 nM or less, 5 nM or less, or 1 nM or less. In some embodiments, the modulator is present in solution at a concentration of 0.5 nM to 10 nM, 1 nM to 200 nM, 50 nM to 500 nM, 200 nM to 1 mM, 1 mM to 50 mM, 10 mM to 200 mM, or 50 nM to 10 mM. In some embodiments, the modulator is present in solution at a concentration within another range starting from 0.1 nM or more and ending at 1 M or less.

[0058]

[0082] In some embodiments, n is 1 or 2 and m is 1 or 2. In some embodiments, n is 1 and m is either 1 or 2. In some embodiments, m is 2 or greater.

[0059]

[0083] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers binds to two metal cations in the plurality of metal cations.

[0060]

[0084] FIG. 17 shows consistently smaller crystals at 10 equivalents of 3-hydroxybenzoate than at 1 equivalent, according to one embodiment of the present disclosure, but the crystal size does not decrease monotonically with modulator concentration, and the same trend is observed for salicylamide, phthalate, and bromosalicylamide. Thus, in some embodiments, the number of equivalents of polytopic organic linker relative to the number of equivalents of modulator is varied to optimize the size and morphology of the MOF crystals. For example, in some embodiments, there is 1 equivalent of polytopic organic linker for between 0.5 and 20 equivalents of modulator in the solution prior to reaction. In some embodiments, there is 1 equivalent of polytopic organic linker for between 1 and 15 equivalents of modulator in the solution prior to reaction. In some embodiments, the ratio of the number of equivalents of polytopic organic linker to the number of equivalents of modulator is 1:0.001 or less, 1:0.01 or less, 1:0.1 or less, 1:0.5 or less, 1:1 or less, 1:2 or less, 1:3 or less, 1:4 or less, 1:5 or less, 1:6 or less, 1:7 or less, 1:8 or less, 1:9 or less, 1:10 or less, 1:15 or less, 1:20 or less, 1:30 or less, 1:40 or less, 1:50 or less, 1:60 or less, 1:70 or less, 1:80 or less, 1:90 or less, or 1:100 or less. In some embodiments, the ratio of the number of equivalents of the polytopic organic linker to the number of equivalents of the modulator is at least 1:200, at least 1:100, at least 1:80, at least 1:50, at least 1:40, at least 1:20, at least 1:10, at least 1:5, at least 1:2, or at least 1:1. In some embodiments, the ratio of the number of equivalents of the polytopic organic linker to the number of equivalents of the modulator is 1:5 to 1:0.1, 1:50 to 1:1, or 1:30 to 1:2. In some embodiments, the ratio of the number of equivalents of the polytopic organic linker to the number of equivalents of the modulator falls within another range beginning at or above 1:200 and ending at or below 1:0.001.

[0061]

[0085] In some embodiments, the modulator has the formula: [ka] or a salt thereof (e.g., sodium, potassium, cesium), or a mixture thereof (e.g., a mixture of any 2, 3, 4, 5, 6, 7, 8, 9, or 10 modulators, each independently having formula I, II, III, IV, or V); 10 , and R 11 are each independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl; R3, R4, R5, and R6 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl; R 10 and R 11 are not hydrogen. For example, FIG. 10 shows, in a clockwise direction, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate at 350x magnification according to embodiments of the present disclosure. FIGS. 11-15 show, in a clockwise direction, Co2(dobdc) crystals grown in the presence of modulators 3-hydroxybenzoate, acetate, salicylate, and phthalate at various magnifications. FIG. 16 shows Co2(dobdc) crystals grown in the presence of modulator salicylate at 1504x magnification (top) and Co2(dobdc) crystals grown in the presence of 3-hydroxybenzoate at 2000x magnification (bottom). FIG. 19 shows how trichloroacetate regulated metal-organic framework crystallization according to one embodiment of the present disclosure results in very low modulator incorporation into the metal-organic framework, which is 83 ppm by elemental analysis (left panel), and which is not visible by energy dispersive x-ray spectroscopy.

[0062]

[0086] In some such embodiments, R3, R4, R5, and R6 are each independently a substituted or unsubstituted linear or branched alkyl having between 1 and 10 carbon atoms.

[0063]

[0087] In some such embodiments, R3, R4, R5, and R6 are each hydrogen.

[0064]

[0088] In some embodiments, the solution includes one modulator, the one modulator having formula IV, where R1 and R2 are each hydrogen. In some such embodiments, R3, R4, R5, and R6 are each hydrogen.

[0065]

[0089] In some embodiments, the solution includes one modulator, the one modulator having Formula II, where R2, R7, and R8 are each hydrogen. In some such embodiments, R3, R4, R5, and R6 are each hydrogen.

[0066]

[0090] In some embodiments, the solution includes one modulator, the one modulator having formula III or V, where R1 and R9 are each hydrogen. In some such embodiments, R3, R4, R5, and R6 are each hydrogen.

[0067]

[0091] In some embodiments, the formula M n X m One compound among the one or more compounds of is a magnesium(II) metal salt, a manganese(II) metal salt, an iron(II) metal salt, a cobalt(II) metal salt, a nickel(II) metal salt, a zinc(II) metal salt, or a cadmium(II) metal salt.

[0068]

[0092] In some embodiments, the one or more compounds is a single compound, and the single compound has the formula M n X m where M n X m is a magnesium(II) metal salt, a manganese(II) metal salt, an iron(II) metal salt, a cobalt(II) metal salt, a nickel(II) metal salt, a zinc(II) metal salt, or a cadmium(II) metal salt.

[0069]

[0093] In some embodiments, the reaction is carried out using a buffer that does not have a metal-coordinating functional group (non-coordinating buffer). The disclosed non-coordinating buffers were initiated by the work of Good et al., 1966, Biochem. 5(2), 467, and further developed by Kandegedara and Rorabacher, 1999, Anal. Chem. 71, 3140, each of which is incorporated herein by reference. In some embodiments, the buffer that does not have a metal-coordinating functional group is PIPES, PIPPS, PIPBS, DEPP, DESPEN, MES, TEEN, PIPES, MOBS, DESPEN, or TEMN. See Kandegedara and Rorabacher, 1999, Anal. Chem. 71, 3140. In some embodiments, the buffer that does not have a metal-coordinating functional group is an alkyl or alkyl sulfonate derivative of morpholine, piperazine, ethylenediamine, or methylenediamine.

[0070]

[0094] There are reports of surface-grown or epitaxially grown metal-organic frameworks. See Heinke et al., 2016, SURMOFs: Liquid-Phase Epitaxy of Metal-Organic Frameworks on Surfaces, in The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications (ed S. Kaskel), Wiley-VCH Verlag GmbH&Co.KGaA, Weinheim, Germany. doi:10.1002 / 9783527693078, ch17, which is incorporated herein by reference. In general, synthetic procedures for surface-grown or epitaxially grown metal-organic frameworks seek to functionalize the surface and induce nucleation directly on the surface, typically with layer-by-layer growth. This strategy is usually contrasted with solvothermal or hydrothermal synthesis, where the product is formed at high temperature in solution. Surfaces are relevant to epitaxially grown metal-organic frameworks, but little attention has been paid to their role in solvothermal and hydrothermal reactions. The process of silanization is a well-established technique for imparting functional or hydrophobic properties to glassware surfaces. See Seed, 2001, "Silanizing Glassware," Current Protocols in Cell Biology 8:3E:A.3E.1-A.3E.2, and Plueddemann, 1991, "Chemistry of Silane Coupling Agents," In: Silane Coupling Agents, Springer, Boston, MA, each of which is incorporated by reference. However, the impact of using different hydrophobic surfaces during solvothermal or hydrothermal synthesis of metal-organic frameworks has not been studied with respect to phase selection and morphology control.

[0071]

[0095] Very different synthesis methods have been found to obtain different metal-organic framework morphologies. For example, microwave heating has been found to result in different crystallites than solvothermal growth. See Stock and Biswas, 2012, Chem. Rev. 112, 933, incorporated herein by reference. However, within the scope of hydrothermal synthesis, the effect of oil bath heating versus oven heating has only been studied under limited conditions for the frameworks UiO-66 and In-MIL-68, and not at all for the synthesis of frameworks M2(dobdc) or M2(dobpdc). See Lee et al., 2017, Cryst. Eng. Comm. 19, 426, incorporated herein by reference.

[0072]

[0096] FIG. 18 shows how a higher pH results in smaller aspect ratio crystals. Thus, in some embodiments, the pH of the solution is between 6.5 and 8.5. In some embodiments, the pH of the solution is between 7.0 and 8.0. In some embodiments, the pH of the solution is at least 2, at least 3, at least 4, at least 4.5, at least 5, at least 5.5, at least 6, at least 6.5, at least 7, at least 7.5, at least 8, at least 8.5, at least 9, or at least 9.5. In some embodiments, the pH of the solution is 13 or less, 12 or less, 11 or less, 10.5 or less, 10 or less, 9.5 or less, 9 or less, 8.5 or less, 8 or less, 7.5 or less, 7 or less, or 6.5 or less. In some embodiments, the pH of the solution is 6-9, 6-10, 5-8, 7-9, or 6-8. In some embodiments, the pH of the solution is within another range starting from 1 or more and ending at 14 or less.

[0073]

[0097] One aspect of the present disclosure provides for the synthesis of metal-organic frameworks using controlled heating and / or functionalization of the reaction vessel in the presence of non-coordinating buffers or non-coordinating bases. Schemes using non-coordinating buffers, acids, or bases allow for controlled deprotonation of ligands over a wide range of pH values ​​without disturbing the coordination equilibrium desired to obtain a particular crystal morphology. Using these tools, the pH can be set independently of the solvent / ligand / counterion coordination during growth. Furthermore, controlling the pH without relying on solvent decomposition provides precise control over which coordinating agents are available in the solvent. Appropriate selection of additives or metal counterions allows preferential coordination during growth to some crystal facets and can slow growth in that direction. Although tuning is known to affect grain size and stability, preferential binding to one end of the crystal structure is not clear. Using stronger coordinating agents selectively slows growth along the direction of the pore channels. See International Publication No. WO 2020 / 068996, entitled “Metal-Organic Framework Phase and Crystallite Shape Control,” which is incorporated by reference herein.

[0074]

[0098] In some embodiments, M is cationic Fe, Co, or Zn. In some embodiments, n is 2, 3, or 4. In some embodiments, n is 2. In some embodiments, n is 5 or 6.

[0075]

[0099] In some embodiments, the basic anion has a pKa value less than 3.5. In some embodiments, the basic anion has a pKa value greater than 3.5. In some embodiments, the pKa of the anion is greater than the lowest pKa value of the polytopic organic linker.

[0076]

[0100] As an example, crystalline MOF materials can be formed by the synthetic methods of the present disclosure from various cobalt(II) salts such as cobalt(II) nitrate, cobalt(II) chloride, cobalt(II) acetate, cobalt(II) sulfate, cobalt(II) iodide, cobalt(II) bromide, cobalt(II) trifluorosulfonate, cobalt(II) tetrafluoroborate, cobalt(II) oxide, cobalt(II) carbonate, cobalt(II) hydroxide, cobalt(II) hydroxycarbonate, mixed cobalt(II) halides, cobalt(II) acetylacetonate, cobalt(II) formate, cobalt(II) perchlorate, or their halogenated derivatives.

[0077]

[0101] In some embodiments, the polytopic organic linkers are present in the solution prior to initiation of the reaction at a concentration between 1 mM and 1 M, between 3 mM and 0.5 M, or between 4 mM and 250 mM.

[0078]

[0102] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 13 and R 13 are hydrogen.

[0079]

[0103] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R12 and R 13 are hydrogen.

[0080]

[0104] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some embodiments, R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are hydrogen.

[0081]

[0105] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl. In some such embodiments, R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are hydrogen.

[0082]

[0106] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers is 2,5-dioxido-1,4-benzenedicarboxylate (DOBD). 4- ), 4,6-dioxido-1,3-benzenedicarboxylate (m-DOBDC 4- ), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxide-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ), Dioxidobiphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- , pc-dobpdc 4- 2,5-dioxidobenzene-1,4-dicarboxylate (also called DOBD) 4- ), 1,3,5-benzenetristetrazolate (BTT), 1,3,5-benzenetristriazolate (BTTri), 1,3,5-benzenetrispyrazolate (BTP), or 1,3,5-benzenetriscarboxylate (BTC).

[0083]

[0107] In some embodiments, each polytopic organic linker in the plurality of polytopic organic linkers is 2,5-dioxido-1,4-benzenedicarboxylate (DOBD). 4- ).

[0084]

[0108] In some embodiments, the reaction is carried out at a temperature above 60° C. In some embodiments, the reaction is carried out at a temperature between 70° C. and 80° C.

[0085]

[0109] In some embodiments, the salt of the modulator is a sodium salt, a potassium salt, or a cesium salt.

[0086]

[0110] In some embodiments, the reaction is carried out at a temperature below 30° C. for 2-3 days, at a temperature below 40° C. for less than 1 or 2 days, at a temperature below 45° C. for 10-25 hours, at a temperature below 50° C. for at least 11 hours, at a temperature below 60° C. for at least 8 hours, at a temperature below 70° C. for at least 2 hours, at a temperature below 80° C. for at least 30 minutes, or at a temperature below 90° C. for at least 10 minutes.

[0087]

[0111] In some embodiments, the reaction is carried out at a temperature between 30° C. and 50° C. for 2-3 days, at a temperature between 35° C. and 55° C. for 1-3 days, at a temperature between 40° C. and 60° C. for 10-25 hours, at a temperature between 45° C. and 70° C. for at least 11 hours, at a temperature between 45° C. and 70° C. for at least 8 hours, at a temperature between 60° C. and 80° C. for at least 2 hours, at a temperature between 70° C. and 90° C. for at least 30 minutes, or at a temperature between 80° C. and 100° C. for at least 10 minutes.

[0088]

[0112] In some embodiments, the reaction is carried out at a temperature above 60° C. for at least 8 hours, at a temperature above 60° C. for at least 9 hours, at a temperature above 60° C. for at least 10 hours, at a temperature above 60° C. for at least 11 hours, at a temperature above 60° C. for at least 12 hours, at a temperature above 60° C. for at least 13 hours, at a temperature above 60° C. for at least 14 hours, or at least 15 hours at a temperature above 60° C.

[0089]

[0113] In some embodiments of the reaction, the reaction is carried out at a temperature above 62°C for at least 8 hours, at least 9 hours at a temperature above 62°C, at least 10 hours at a temperature above 62°C, at least 11 hours at a temperature above 62°C, at least 12 hours at a temperature above 62°C, at least 13 hours at a temperature above 62°C, at least 14 hours at a temperature above 62°C, or at least 15 hours at a temperature above 62°C.

[0090]

[0114] In some embodiments, the reaction is carried out at a temperature above 64° C. for at least 8 hours, at least 9 hours at a temperature above 64° C., at least 10 hours at a temperature above 64° C., at least 11 hours at a temperature above 64° C., at least 12 hours at a temperature above 64° C., at least 13 hours at a temperature above 64° C., at least 14 hours at a temperature above 64° C., or at least 15 hours at a temperature above 64° C.

[0091]

[0115] In some embodiments, the reaction is carried out at a temperature above 66° C. for at least 8 hours, at least 9 hours at a temperature above 66° C., at least 10 hours at a temperature above 66° C., at least 11 hours at a temperature above 66° C., at least 12 hours at a temperature above 66° C., at least 13 hours at a temperature above 66° C., at least 14 hours at a temperature above 66° C., or at least 20 hours at a temperature above 66° C.

[0092]

[0116] In some embodiments, the reaction is carried out at a temperature above 68° C. for at least 8 hours, at least 9 hours at a temperature above 68° C., at least 10 hours at a temperature above 68° C., at least 11 hours at a temperature above 68° C., at least 12 hours at a temperature above 68° C., at least 13 hours at a temperature above 68° C., at least 14 hours at a temperature above 68° C., or at least 20 hours at a temperature above 68° C.

[0093]

[0117] In some embodiments, the reaction is carried out at a temperature above 70° C. for at least 8 hours, at a temperature above 70° C. for at least 9 hours, at a temperature above 70° C. for at least 10 hours, at a temperature above 70° C. for at least 11 hours, at a temperature above 70° C. for at least 12 hours, at a temperature above 70° C. for at least 13 hours, at a temperature above 70° C. for at least 14 hours, or at least 20 hours at a temperature above 70° C.

[0094]

[0118] In some embodiments, the reaction is carried out at a temperature above 72°C for at least 8 hours, at least 9 hours at a temperature above 72°C, at least 10 hours at a temperature above 72°C, at least 11 hours at a temperature above 72°C, at least 12 hours at a temperature above 72°C, at least 13 hours at a temperature above 72°C, at least 14 hours at a temperature above 72°C, or at least 20 hours at a temperature above 72°C.

[0095]

[0119] In some embodiments, the reaction is carried out at a temperature above 74° C. for at least 8 hours, at least 9 hours at a temperature above 74° C., at least 10 hours at a temperature above 74° C., at least 11 hours at a temperature above 74° C., at least 12 hours at a temperature above 74° C., at least 13 hours at a temperature above 74° C., at least 14 hours at a temperature above 74° C., or at least 20 hours at a temperature above 74° C.

[0096]

[0120] In some embodiments, the reaction is carried out at a temperature above 25° C. for at least 1 hour. In some embodiments, the reaction is carried out at a temperature above 25° C. for at least 8 hours.

[0097]

[0121] In some embodiments, the formula M n X m The compound is present in the solution prior to the reaction at a concentration between 5 mM and 1 M, between 10 mM and 0.5 M, or between 15 mM and 250 mM.

[0098]

[0122] In some embodiments, a buffer without metal-coordinating functional groups is used in the reaction. In some embodiments, the buffer is PIPES, PIPPS, PIPBS, DEPP, DESPEN, MES, TEEN, PIPES, MOBS, DESPEN, or TEMN. In some embodiments, a buffer without metal-coordinating functional groups is used, and the buffer is an alkyl or alkyl sulfonate derivative of morpholine, piperazine, ethylenediamine, or methylenediamine. See Kandegedara and Rorabacher, 1999, Anal.Chem.71,3140, which is incorporated herein by reference.

[0099]

[0123] In some embodiments, the buffering agent without a metal coordinating functional group is buffered in the solution prior to the reaction to a concentration between 0.05 M and 0.5 M, between 0.10 M and 0.4 M, between 0.15 M and 0.30 M, or between 0.18 M and 0.22 M. In some embodiments, the buffering agent without a metal coordinating functional group is used in the solution and is buffered to a pH below 5.0, between 5.0 and 6.0, between 6.0 and 7.0, between 7.0 and 8.0, or greater than 8.0.

[0100]

[0124] In some embodiments, a buffer without metal coordinating functional groups is present in solution, and the buffer does not measurably interact with or bind to the metal cation of the crystalline metal-organic framework.

[0101]

[0125] In some embodiments, the solution comprises a polar protic solvent or a mixture of polar protic solvents. In some embodiments, the solution comprises a solvent mixture of ethanol:water. In some embodiments, the solution comprises an x:y mixture of ethanol and water, where x and y are independently separate positive integers. In some embodiments, x is 1 and y is 1. In some embodiments, x is 2 and y is 1. In some embodiments, y is 2 and x is 1. In some embodiments, x is in the range between 0.5 and 5 and y is in the range between 5 and 0.5. In some embodiments, the reaction is carried out in a 1:1 ethanol:H2O solvent. In some embodiments, the reaction is carried out in t-butanol, n-propanol, ethanol, methanol, acetic acid, water, N,N-dimethylformamide, or mixtures thereof.

[0102]

[0126] Heating equipment. During hydrothermal synthesis, the method of providing heat to the same synthesis reaction affects the size, morphology, and dispersibility of the metal-organic framework sample. The dispersibility and size of the MOF crystals can be controlled by changing the heating equipment, such as an oil bath, an oven, or a metal bead bath. For otherwise identical synthesis conditions, in some embodiments, an oil bath has been found to improve the dispersibility of the crystallites for syntheses performed in non-silanized glassware. An example of a metal bead bath is the Lab Armor (Cornelius, Oregon) line of metal bead baths, such as the Lab Armor 74300-714 Waterless Bead Bath (14 L capacity). Some embodiments of the present disclosure further specify that the disclosed reactions are carried out using special configurations or heat sources as disclosed below.

[0103]

[0127] Use of an Oil Bath. In some embodiments, the disclosed reaction steps are carried out in non-silanized glassware using an oil bath.

[0104]

[0128] In one embodiment of the present disclosure, a crystalline metal-organic framework is formed according to the disclosed synthetic scheme by solubilizing a polytopic organic linker in a first polar protic solvent. n X m is dissolved in a second polar protic solvent. In some embodiments, the first polar protic solvent and the second polar protic solvent are the same. In some embodiments, the first polar protic solvent and the second polar protic solvent are different. The reaction is initiated, for example, by mixing the two solutions at 15° C. in a 250 mL three-neck round-bottom flask equipped with a Dimroth condenser. In some embodiments, the mixed solution is refluxed under stirring (e.g., 300 rpm) for a period of time (e.g., more than 10 hours) inside a round-bottom flask placed in an oil bath at elevated temperature (e.g., greater than 60° C.). After the reaction period is over, the solution is cooled to room temperature (e.g., by removing it from the oil bath or by cooling the oil bath).

[0105]

[0129] In another embodiment of the present disclosure, a crystalline metal-organic framework is formed by solubilizing a polytopic organic linker in a first polar protic solvent. n X m is dissolved in a second polar protic solvent. In some embodiments, the first polar protic solvent and the second polar protic solvent are the same. In some embodiments, the first polar protic solvent and the second polar protic solvent are different. The reaction is initiated, for example, by immediately mixing the two solutions at 15° C. in a 250 mL three-neck round-bottom flask equipped with a Dimroth condenser. In some embodiments, the mixed solution is refluxed under stirring (e.g., 300 rpm) for a period of time (e.g., more than 10 hours) inside a round-bottom flask placed in an oil bath at elevated temperature (e.g., greater than 60° C.). After the reaction period is over, the solution is cooled to room temperature (e.g., by removing it from the oil bath or by cooling the oil bath).

[0106]

[0130] In one embodiment of the present disclosure, a crystalline metal-organic framework is formed by the disclosed synthesis method by solubilizing a polytopic organic linker in a first polar protic solvent. n X m The compound of formula (I) is dissolved in a second polar protic solvent. In some embodiments, the first polar protic solvent and the second polar protic solvent are the same. In some embodiments, the first polar protic solvent and the second polar protic solvent are different. In some embodiments, the polytopic organic linker solution or M n X m The solution is buffered with a buffering agent that is free of metal coordinating functional groups. In yet another embodiment, the polytopic organic linker solution and M n X m Both solutions are buffered with a buffering agent that does not have metal-coordinating functional groups. The two solutions are mixed together at room temperature, for example, in an oven of a hermetically sealed autoclave (e.g., a Teflon cup autoclave of 200 mL size) without stirring. The reaction can be allowed to proceed in the sealed autoclave by statically placing it in a preheated one (e.g., at a temperature above 60° C.) for a period of time (e.g., more than 10 hours). After the end of the reaction period, the solution is cooled to room temperature (e.g., by removing it from the oven or by allowing the oven to cool in the air).

[0107]

[0131] In another embodiment of the present disclosure, a crystalline metal-organic framework is formed by the synthetic method of the present disclosure by solubilizing a polytopic organic linker in a first polar protic solvent. n X mThe compound of is dissolved in a second polar protic solvent. In some embodiments, the first polar protic solvent and the second polar protic solvent are the same. In some embodiments, the first polar protic solvent and the second polar protic solvent are different. The two solutions are mixed together at room temperature, for example, in a hermetically sealed autoclave without stirring (e.g., a Teflon cup autoclave of size 200 mL). The reaction can proceed in this sealed autoclave by statically placing it in a preheated (e.g., temperature above 60° C.) oven for a period of time (e.g., more than 10 hours). After the reaction period is over, the autoclave is cooled to room temperature along with the oven.

[0108]

[0132] Silanization. In some embodiments, the disclosed reactions are carried out in functionalized glassware.

[0109]

[0133] Different surface functionalities of the reaction vessels can also control the size and dispersity of the resulting crystals. Literature silanization procedures are used on borosilicate glassware to impart hydrophobicity to the surface. See Seed, 2001, "Silanizing Glassware," Current Protocols in Cell Biology. 8:3E:A.3E.1-A.3E.2, and Plueddemann, 1992, "Chemistry of Silane Coupling Agents," In: Silane Coupling Agents, Springer, Boston, MA, both of which are incorporated herein by reference. Aqueous ethanol syntheses performed in these silanized glassware yield very low crystal polydispersities. Furthermore, silanized glassware eliminates morphological differences caused by different heating regimes, indicating that it can be used to mitigate synthetic inconsistencies caused by heating variations.

[0110]

[0134] In some embodiments, reactions to form MOF crystals according to the synthetic schemes of the present disclosure are carried out in glassware that has been silanized with a silanizing agent, hi some embodiments, the silanizing agent comprises chlorotrimethylsilane, trichlorohexylsilane, N,O-bis(trimethylsilyl)acetamide, or a mixture thereof.

[0111]

[0135] In some embodiments, the silanizing agent used is (3-aminopropyl)-triethoxysilane, (3-aminopropyl)-diethoxy-methylsilane, (3-aminopropyl)-dimethyl-ethoxysilane, (3-aminopropyl)-trimethoxysilane, (3-glycidoxypropyl)-dimethyl-ethoxysilane, (3-mercaptopropyl)-trimethoxysilane, (3-mercaptopropyl)-methyl-dimethoxysilane, or mixtures thereof. In some embodiments, the silanizing agent used is one that contains a long hydrocarbon chain, such as octadecyltrichlorosilane, dodecyltrichlorosilane, or mixtures thereof. In some embodiments, the surface is functionalized to be more hydrophilic rather than hydrophobic. In some such embodiments, the silanizing agent imparts special functionality to the surface. In some embodiments, this includes functionalization of perfluoroalkanes or other alkanes, such as alcohols, carboxylic acids, amides, amines, or mixtures thereof.

[0112]

[0136] In some embodiments, the disclosed reactions are carried out in the presence of a benign surface.

[0113]

[0137] The use of benign surfaces such as plastic or steel can also result in low dispersity crystals. For example, aqueous ethanol synthesis carried out on these benign surfaces results in significantly lower crystal polydispersity than non-silanized surfaces such as the Co2(dobdc)-extended crystals formed by the second reaction scheme.

[0114]

[0138] Furthermore, the use of different surface functionalities can determine phase selection. For example, two different products can be obtained under identical reaction conditions depending on the surface functionality of the reaction vessel. Using different functionalities on glassware, for example silanized or non-silanized surfaces, can also lead to the discovery of new phases such as Zn(dobpdc) 2H2O, which is formed by a third reaction scheme.

[0115]

[0139] Furthermore, the crystallite size can be determined by the use of different surface functionalities, for example, two different crystallite sizes can be obtained under the same reaction conditions depending on the surface functionality of the reaction vessel.

[0116]

[0140] V. Technical applications

[0141] In one aspect of the present disclosure, numerous technical applications of the disclosed adsorbent materials are provided.

[0117]

[0142] One such application is the capture of carbon from coal flue gas or natural gas flue gas. The increasing amount of carbon dioxide (CO2) in the atmosphere, which contributes to global climate change, is the basis for new plans to reduce CO2 emissions from point sources such as power plants. In particular, coal-fired power plants are responsible for 30-40% of global CO2 emissions. See Quadrelli et al., 2007, “The energy-climate challenge: Recent trends in CO2 emissions from fuel combustion,” Energy Policy 35, pp. 5938-5952, which is incorporated herein by reference. Thus, at ambient pressure and 40°C, CO2 (15-16%), O2 (3-4%), H2O (5-7%), N2 (70-75%), and trace impurities (e.g., SO2, NO2) are xThere is a continuing need to develop new sorbents for capturing carbon from coal flue gas, a gas stream consisting of HO (saturated), O (4-12%), and N (balance). See Planas et al., 2013, “The Mechanism of Carbon Dioxide Adsorption in an Alkylamine-Functionalized Metal-organic Framework,” J. Am. Chem. Soc. 135, pp. 7402-7405, incorporated herein by reference. Similarly, the increasing use of natural gas as a fuel source has created a need for sorbents capable of capturing CO2 from the flue gas of power plants that use natural gas. Flue gas produced by the combustion of natural gas has a lower CO2 concentration of about 4-10% CO2, with the remainder of the stream consisting of H2O (saturated), O2 (4-12%), and N2 (balance). In particular, for temperature swing adsorption processes, the adsorbent should have the following properties: (a) high operating efficiency with minimal temperature swing to minimize regeneration energy costs; (b) high selectivity for CO2 over other components of coal flue gas; (c) 90% capture of CO2 under flue gas conditions; (d) effective performance under high humidity conditions; and (d) long-term stability for adsorption / desorption cycles under high humidity conditions.

[0118]

[0143] Another such application is the capture of carbon from crude biogas. Biogas, a CO2 / CH4 mixture produced by the decomposition of organic matter, is a renewable fuel source that has the potential to replace traditional fossil fuel sources. Removal of CO2 from the crude biogas mixture is one of the most challenging aspects of upgrading this promising fuel source to pipeline-quality methane. Therefore, the use of sorbents to selectively remove CO2 from CO2 / CH4 mixtures with high operational efficiency and minimal regeneration energy could significantly reduce the cost of using biogas instead of natural gas for applications in the energy sector.

[0119]

[0144] The disclosed compositions (adsorbent materials) can be used to remove a majority of the CO2 from a CO2-rich gas stream, and the CO2-rich adsorbent materials can remove the CO2 using temperature swing adsorption, pressure swing adsorption, vacuum swing adsorption, concentration swing adsorption, or combinations thereof. Examples of temperature swing adsorption and vacuum swing adsorption methods are disclosed in WO 2013 / 059527 A1, which is incorporated herein by reference.

[0120]

[0145] In some embodiments, the disclosed compositions (adsorbent materials) are used in the separation of hydrocarbon mixtures, especially ethane / ethylene, propane / propylene, and C6 alkane mixtures. In the industrial production of these hydrocarbons, mixtures of olefin / paraffin type or other isomers are produced, which do not meet the market demand and need to be separated. Some of the current technologies are very energy intensive processes such as distillation, and some are based on crystallization or adsorption. The realization of better adsorption-based materials could significantly reduce the energy costs in industrial separations.

[0121]

[0146] In some embodiments, the disclosed compositions are used as heterogeneous catalysts for the conversion of lower alkanes to value-added chemicals, such as the conversion of methane, among other processes. With the recent worldwide increase in natural gas reserves, this process becomes highly economical and environmentally impactful. Therefore, materials and routes for the conversion of methane to higher hydrocarbons are highly desirable. EXAMPLES

[0122]

[0147] VI. Working Examples

[0148] Example 1. A crystalline metal-organic framework was synthesized that includes multiple cations and multiple polytopic organic linkers, each of which is bonded to two or more cations in the multiple cations. These polytopic organic linkers have the formula: [ka] These polytopic organic linkers were reacted with a compound of formula Co(NO3)2·6H2O in a 1:1 H2O / EtOH solution buffered with 0.2 mM MOPS and adjusted to pH 7. The concentration of polytopic organic linker in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. The solution contained a compound of formula: [ka] There were modulators of

[0123]

[0149] The concentration of the modulator in the solution was 35 mM. During the reaction, the solution was maintained at a temperature of 75° C., which resulted in the formation of Co2(dobdc) crystals, as shown in the lower diagram of the upper diagram of FIG. 8A.

[0124]

[0150] Example 2. A crystalline metal-organic framework was synthesized comprising a plurality of cations and a plurality of polytopic organic linkers, each of which was bonded to two or more cations in the plurality of cations. These polytopic organic linkers have the formula: [ka] These polytopic organic linkers were reacted with a compound of formula Co(NO3)2·6H2O in a 1:1 H2O / EtOH solution buffered with 0.2 mM MOPS and adjusted to pH 7. The concentration of polytopic organic linker in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. The solution contained a compound of formula: [ka] There were modulators of

[0125]

[0151] The concentration of the modulator in the solution was 35 mM. During the reaction, the solution was maintained at a temperature of 75° C., which resulted in the Co2(dobdc) crystals shown in the lower diagram of FIG. 8A.

[0126]

[0152] Example 3. A crystalline metal-organic framework was synthesized comprising a plurality of cations and a plurality of polytopic organic linkers, each of which was bonded to two or more cations in the plurality of cations. These polytopic organic linkers have the formula: [ka] These polytopic organic linkers were reacted with a compound of formula Co(NO3)2·6H2O in a 1:1 H2O / EtOH solution buffered with 0.2 mM MOPS and adjusted to pH 7. The concentration of polytopic organic linker in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. The solution contained a compound of formula: [ka] There were modulators of

[0127]

[0153] The concentration of the modulator in the solution was 35 mM. During the reaction, the solution was maintained at a temperature of 75° C., which resulted in the Co2(dobdc) crystals shown in the lower diagram of the upper diagram of FIG. 8B.

[0128]

[0154] Example 4. A crystalline metal-organic framework was synthesized comprising a plurality of cations and a plurality of polytopic organic linkers, each of which was bonded to two or more cations in the plurality of cations. These polytopic organic linkers have the formula: [ka] These polytopic organic linkers were reacted with a compound of formula Co(NO3)2·6H2O in a 1:1 H2O / EtOH solution buffered with 0.2 mM MOPS and adjusted to pH 7. The concentration of polytopic organic linker in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. The solution contained a compound of formula: [ka] There were modulators of

[0129]

[0155] The concentration of the modulator in the solution was 35 mM. During the reaction, the solution was maintained at a temperature of 75° C., which resulted in the formation of Co2(dobdc) crystals, as shown in the lower panel of FIG. 8B.

[0130]

[0156] Example 5. A crystalline metal-organic framework was synthesized comprising a plurality of cations and a plurality of polytopic organic linkers, each of which was bonded to two or more cations in the plurality of cations. These polytopic organic linkers have the formula: [ka] These polytopic organic linkers were reacted with a compound of formula Co(NO3)2·6H2O in a 1:1 H2O / EtOH solution buffered with 0.2 mM MOPS and adjusted to pH 7. The concentration of polytopic organic linker in the solution was 5 mM and the concentration of Co(NO3)2·6H2O in the solution was 17.5 mM. The solution contained a compound of formula: [ka] There were modulators of

[0131]

[0157] The concentration of the modulator in the solution was 35 mM. During the reaction, the solution was maintained at a temperature of 75° C., which resulted in the formation of Co2(dobdc) crystals, as shown in the lower diagram of FIG. 8C.

[0132]

[0158] VII. Further Embodiments

[0159] Embodiment 1. A method for synthesizing a crystalline metal-organic framework comprising a plurality of cations and a plurality of polytopic organic linkers, wherein each polytopic organic linker in the plurality of polytopic organic linkers is bonded to two or more cations in the plurality of cations, and the method comprises: n X m wherein each M is independently a cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, Hf, X is a basic anion, n is a positive integer, and m is a positive integer, and the reaction is carried out according to the formula: [ka] or a salt thereof (e.g., sodium, potassium, cesium), or a mixture thereof, and R1, R2, R7, R8, R9, R 10 , and R 11 are each independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl; R3, R4, R5, and R6 are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl; R 10 and R 11 are not hydrogen, respectively.

[0133]

[0160] Embodiment 2. The method of embodiment 1, wherein R3, R4, R5, and R6 are each independently a substituted or unsubstituted linear or branched alkyl having between 1 and 10 carbon atoms.

[0134]

[0161] Embodiment 3. The method of embodiment 1, wherein R3, R4, R5, and R6 are each hydrogen.

[0135]

[0162] Embodiment 4. The method of embodiment 1 or 3, wherein the modulator has formula IV, and R1 and R2 are each hydrogen.

[0136]

[0163] Embodiment 5. The method of embodiment 1 or 3, wherein the modulator has Formula II, and R2, R7, and R8 are each hydrogen.

[0137]

[0164] Embodiment 6. The method of embodiment 1 or 3, wherein the modulator has formula III or V, and R1 and R9 are each hydrogen.

[0138]

[0165] Embodiment 7. The method of any one of embodiments 1-6, wherein the reaction is carried out using a buffer that is free of metal-coordinating functional groups.

[0139]

[0166] Embodiment 8. The method of embodiment 7, wherein the buffer without a metal coordinating functional group is PIPES, PIPPS, PIPBS, DEPP, DESPEN, MES, TEEN, PIPES, MOBS, DESPEN, or TEMN.

[0140]

[0167] Embodiment 9. The method of embodiment 7, wherein the buffering agent without a metal coordinating functional group is an alkyl or alkyl sulfonate derivative of morpholine, piperazine, ethylenediamine, or methylenediamine.

[0141]

[0168] Embodiment 10. Each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 The method of any one of embodiments 1-9, wherein each is independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl.

[0142]

[0169] Embodiment 11. R 12 and R 13 11. The method of embodiment 10, wherein each is hydrogen.

[0143]

[0170] Embodiment 12. Each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 12 and R 13 The method of any one of embodiments 1-9, wherein each is independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl.

[0144]

[0171] Embodiment 13. R 12 and R 13 13. The method of embodiment 12, wherein each is hydrogen.

[0145]

[0172] Embodiment 14. Each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 The method of any one of embodiments 1-9, wherein each is independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl.

[0146]

[0173] Embodiment 15. R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 The method of embodiment 14, wherein each is hydrogen.

[0147]

[0174] Embodiment 16. Each polytopic organic linker in the plurality of polytopic organic linkers has the formula: [ka] R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 The method of any one of embodiments 1-9, wherein each is independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl.

[0148]

[0175] Embodiment 17. R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 17. The method of embodiment 16, wherein each is hydrogen.

[0149]

[0176] Embodiment 18. Each polytopic organic linker in the plurality of polytopic organic linkers is 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxide-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ),

[0177] Dioxidobiphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- , pc-dobpdc 4- 2,5-dioxidobenzene-1,4-dicarboxylate (also called DOBD) 4- ), 4,6-dioxido-1,3-benzenedicarboxylate (m-DOBDC 4-10. The method of any one of embodiments 1-9, wherein the benzenetris(tetrazolate) is 1,3,5-benzenetris(tetrazolate) (BTT), 1,3,5-benzenetris(triazolate) (BTTri), 1,3,5-benzenetris(pyrazolate) (BTP), or 1,3,5-benzenetris(carboxylate) (BTC).

[0150]

[0178] Embodiment 19. Each polytopic organic linker in the plurality of polytopic organic linkers is 2,5-dioxido-1,4-benzenedicarboxylate (DOBDCC). 4- 10. The method of any one of embodiments 1 to 9, wherein

[0151]

[0179] Embodiment 20. Formula M n X m 20. The method of any one of embodiments 1-19, wherein the compound among the one or more compounds of is a magnesium(II) metal salt, a manganese(II) metal salt, an iron(II) metal salt, a cobalt(II) metal salt, a nickel(II) metal salt, a zinc(II) metal salt, or a cadmium(II) metal salt.

[0152]

[0180] Embodiment 21. Formula M n X m 20. The method of any one of the preceding claims, wherein the compound among the one or more compounds of is cobalt(II) nitrate, cobalt(II) chloride, cobalt(II) acetate, cobalt(II) sulfate, cobalt(II) iodide, cobalt(II) bromide, cobalt(II) trifluorosulfonate, cobalt(II) tetrafluoroborate, cobalt(II) oxide, cobalt(II) carbonate, cobalt(II) hydroxide, cobalt(II) hydroxycarbonate, cobalt(II) mixed halides, cobalt(II) acetylacetonate, cobalt(II) formate, or halogenated derivatives thereof.

[0153]

[0181] Embodiment 22. The method of embodiment 1, wherein the pKa of the anion is greater than the lowest pKa value of the polytopic organic linker.

[0154]

[0182] Embodiment 23. The method of any one of embodiments 1 to 22, wherein the basic anion is formate, acetate, sulfate, bromide, iodide, or trifluorosulfonate.

[0155]

[0183] Embodiment 24. The method of any one of embodiments 1 to 23, wherein the reaction is carried out in non-silanized glassware using an oil bath.

[0156]

[0184] Embodiment 25. The method of any one of embodiments 1 to 23, wherein the reaction is carried out in functionalized glassware.

[0157]

[0185] Embodiment 26. The method of any one of embodiments 1 to 23, wherein the reaction is carried out in the presence of a benign surface.

[0158]

[0186] Embodiment 27. The method of any one of embodiments 1 to 23, wherein the reaction is carried out in glassware that has been silanized with a silanizing agent.

[0159]

[0187] Embodiment 28. The method of embodiment 27, wherein the silanizing agent comprises chlorotrimethylsilane, trichlorohexylsilane, N,O-bis(trimethylsilyl)acetamide, or a mixture thereof.

[0160]

[0188] Embodiment 29. The method of any one of embodiments 1-28, wherein the reaction is carried out in a 1:1 ethanol:H2O solvent.

[0161]

[0189] Embodiment 30. The method of any one of embodiments 1 to 29, wherein the reaction is carried out at a temperature above 25° C. for at least 1 hour.

[0162]

[0190] Embodiment 31. The method of any one of embodiments 1 to 29, wherein the reaction is carried out at a temperature above 25° C. for at least 8 hours.

[0163]

[0191] Embodiment 32. The method of any one of embodiments 1 to 31, wherein n is 1 and m is either 1 or 2.

[0164]

[0192] Embodiment 33. The method of any one of embodiments 1 to 31, wherein m is 2 or greater.

[0165]

[0193] Embodiment 34. The method of any one of embodiments 1-33, wherein each polytopic organic linker in the plurality of polytopic organic linkers binds to two metal cations in the plurality of metal cations.

[0166]

[0194] Embodiment 35. The method of any one of embodiments 1 to 34, wherein there is 1 equivalent of polytopic organic linker for between 0.5 and 20 equivalents of modulator in the solution prior to the reaction.

[0167]

[0195] Embodiment 36. The method of any one of embodiments 1 to 34, wherein there is 1 equivalent of polytopic organic linker for between 1 and 15 equivalents of modulator in the solution prior to the reaction.

[0168]

[0196] Embodiment 37. The method of any one of embodiments 1 to 36, wherein the pH of the solution is between 6.5 and 8.5.

[0169]

[0197] Embodiment 38. The method of any one of embodiments 1 to 36, wherein the pH of the solution is between 7.0 and 8.0.

[0170]

[0198] Embodiment 39. The method of embodiment 1, wherein the solution comprises t-butanol, n-propanol, ethanol, methanol, acetic acid, water, N,N-dimethylformamide, or a mixture thereof.

[0171]

[0199] Embodiment 40. A plurality of polytopic organic linkers are present in solution at a concentration between 1 mM and 50 mM prior to reaction, and have the formula M n X m The method of any one of embodiments 1-39, wherein one or more compounds of are present in solution at a concentration between 5 nM and 100 nM prior to the reaction, and the modulator is present in solution at a concentration between 15 nM and 100 nM prior to the reaction.

[0172]

[0200] Embodiment 41. The method of any one of embodiments 1 to 40, wherein the reaction is carried out at a temperature greater than 60° C.

[0173]

[0201] Embodiment 42. The method of any one of embodiments 1 to 40, wherein the reaction is carried out at a temperature between 70° C. and 80° C.

[0174]

[0202] Embodiment 43. The method of any one of embodiments 1-42, wherein the salt of the modulator is a sodium salt, a potassium salt, or a cesium salt.

[0175] conclusion

[0203] Numerous changes, modifications, and variations will be apparent to those of ordinary skill in the art in light of the above description without departing from the spirit and scope of the present disclosure, and where numerical lower limits and numerical upper limits are recited herein, ranges from any lower limit to any upper limit are contemplated.

[0176]

[0204] It will be understood that the examples and embodiments described herein are for illustrative purposes only, and that various modifications or changes in view thereof will be suggested by those skilled in the art and are within the spirit and scope of this application and are included within the scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.

Claims

1. A method for synthesizing a crystalline metal-organic structure comprising a plurality of cations and a plurality of polytopic organic linkers, wherein each polytopic organic linker among the plurality of polytopic organic linkers binds to two or more cations among the plurality of cations, and the method comprises: reacting the plurality of polytopic organic linkers with one or more compounds of the formula M ｎ X ｍ in solution comprising: each M is independently a cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf; X is a basic anion; n is a positive integer; m is a positive integer; the reaction is carried out in the presence of a modulator having the formula: 【Chemical Formula 1】 or a salt thereof, or a mixture thereof; R １ 、R ２ 、R ７ 、R ８ 、R ９ 、R １０ and R １１ are each independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocycloalkyl, R ３ 、 R ４ 、 R ５ 、 and R ６ is each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl, R １０ and R １１ are each not hydrogen, method.

2. R ３ , R ４ , R ５ , and R ６ is, independently of one another, a substituted or unsubstituted, linear or branched alkyl having from 1 to 10 carbon atoms, the method according to claim 1.

3. R ３ 、 R ４ 、 R ５ 、 and R ６ is hydrogen, respectively, the method according to claim 1.

4. The modulator has Formula IV, R １ and R ２ are each hydrogen, the method according to claim 1.

5. The modulator has Formula II, R ２ , R ７ , and R ８ are each hydrogen, the method of claim 1.

6. The modulator has formula III or V, and R １ and R ９ are each hydrogen, the method according to claim 1.

7. each polytopic organic linker among the plurality of polytopic organic linkers has the formula: [Chemical Formula 2] having R １２ and R １３ each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl, the method according to any one of claims 1 to 6.

8. each polytopic organic linker among the plurality of polytopic organic linkers has the formula: 【Chemical Formula 3】 having R １２ and R １３ The method according to any one of claims 1 to 6, wherein R and R are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl.

9. each polytopic organic linker among the plurality of polytopic organic linkers has the formula: 【Chemical Formula 4】 having R １４ R １５ R １６ R １７ R １８ R １９ and R are each independently selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl, the method according to any one of claims 1 to 6.

10. each polytopic organic linker among the plurality of polytopic organic linkers has the formula: 【Chemical Formula 5】 having R ２０ R ２１ R ２２ R ２３ R ２４ and R ２５ each independently is selected from H, halogen, hydroxyl, methyl, or halogen-substituted methyl, the method according to any one of claims 1 to 6.

11. Each of the plurality of polytopic organic linkers is 2,5-dioxide-1,4-benzenedicarboxylate (dobdc ４－ ), the method according to any one of claims 1 to 6.

12. Formula M ｎ X ｍ The method according to any one of claims 1 to 6, wherein the compound among the one or more compounds is a magnesium (II) metal salt, a manganese (II) metal salt, an iron (II) metal salt, a cobalt (II) metal salt, a nickel (II) metal salt, a zinc (II) metal salt, or a cadmium (II) metal salt.

13. Formula M ｎ X ｍ wherein the compound among the one or more compounds is cobalt(II) nitrate, cobalt(II) chloride, cobalt(II) acetate, cobalt(II) sulfate, cobalt(II) iodide, cobalt(II) bromide, cobalt(II) trifluoromethanesulfonate, cobalt(II) tetrafluoroborate, cobalt(II) oxide, cobalt(II) carbonate, cobalt(II) hydroxide, cobalt(II) hydroxycarbonate, mixed cobalt(II) halides, cobalt(II) acetylacetonate, cobalt(II) formate, or a halogenated derivative thereof, the method according to any one of claims 1 to 6.

14. The method according to any one of claims 1 to 6, wherein the basic anion is formate, acetate, sulfate, bromide, iodide, or trifluoromethanesulfonate.

15. The method according to any one of claims 1 to 6, wherein n is 1, m is either 1 or 2, and the pH of the solution is between 7.0 and 8.

0.

16. The method according to any one of claims 1 to 6, wherein m is 2 or more, and the pH of the solution is between 7.0 and 8.

0.

17. The method according to any one of claims 1 to 6, wherein each polytopic organic linker among the plurality of polytopic organic linkers binds to two metal cations among the plurality of metal cations.

18. The method according to any one of claims 1 to 6, wherein 1 equivalent of the polytopic organic linker is present in the solution before the reaction for every 0.5 to 20 equivalents of the modulator.

19. The method according to any one of claims 1 to 6, wherein 1 equivalent of the polytopic organic linker is present in the solution before the reaction, relative to the modulator in an amount between 1 and 15 equivalents.

20. wherein the plurality of polytopic organic linkers are present in the solution at a concentration between 1 mM and 50 mM before the reaction, Formula M ｎ X ｍ wherein said one or more compounds are present in said solution at a concentration between 5 nM and 100 nM prior to said reaction, The method according to any one of claims 1 to 6, wherein the modulator is present in the solution at a concentration between 15 nM and 100 nM before the reaction.

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