Hydroxamate-based metal-organic frameworks

Abstract

Novel compositions comprising a hydroxamate-based metal-organic framework are useful for indications such as catalysis, gas separation, sensing, pollutant removal, and water harvesting.

Description

[0001] Hydroxamate -based Metal-organic Frameworks

[0002] This invention was made with government support under HR0011-21-C-0020 awarded by the DOD Advanced Research Projects Agency. The government has certain rights in the invention.

[0003]

[0001] Introduction

[0004]

[0002] Metal-organic frameworks (MOFs) are a class of crystalline, porous materials constructed from organic linkers and metal ions or clusters into two- or three-dimensional (2D or 3D) extended structure through coordination linkage.1Over the past decade research work on MOFs has been growing exponentially and more than 90,000 new crystal structures have been identified. ' Such structural diversity comes from the combination of various metal-containing secondary building units (SBUs) and organic linker molecules with different geometries, and even the same starting materials at different synthetic conditions (i.e. concentrations, temperature, solvents, catalysts) can lead to structurally different MOFs with distinct physical and chemical properties.4’5In particular, MOFs consisting of rod-like metal-containing SBUs are known to exhibit favorable sorption properties.6"8They also have exceptional chemical stability, particularly towards the water, which is attributed to the steric shielding of the metal ions by the linkages.9’10In addition, the channels within the framework enclosed by the rod packings are highly open, allowing for the free and fast movement of guest molecules.11In comparison to MOFs constructed from other SBUs (i.e., discrete metal clusters), rod MOFs are more desirable candidates for many applications due to these features. While it is important to discover and study the novel rod MOFs for various applications, the majority of coordination linkages in rodlike SBUs are limited to carboxylates, with some less common examples including phosphonates, azolates, and mixed functionalities. As a result, the variety of rod MOFs remains to be expanded through the development of new types of linkage.

[0005]

[0003] Summary of the Invention

[0006]

[0004] The invention provides compositions comprising a hydroxamate -based metal-organic framework, systems deploying these compositions, and methods of making and using them.

[0007]

[0005] In aspects and embodiments, the invention provides:

[0008]

[0006] 1. A composition herein comprising a hydroxamate-based metal-organic framework.

[0007] 2. A composition herein comprising a hydroxamate-based metal-organic framework, configured for an indication selected from gas separation, sensing, catalysis, adsorption-driven heat exchangers, heat pumps, adsorption / desiccation units for sewage treatment, adsorption- driven refrigeration systems, air conditioning, atmospheric water harvesting, carbon dioxide capture or the removal of volatile organic compounds (VOCs).

[0009]

[0008] 3. A method of making a composition herein, using water as the solvent to avoid using a physiologically or environmentally toxic organic solvent.

[0010]

[0009] 4. A method of using a composition herein for catalysis, gas separation, sensing, pollutant removal, or water harvesting.

[0011]

[0010] 5. A composition herein comprising a hydroxamate-based metal-organic framework comprising metal cluster-based secondary building units and hydroxamate linkers that are connected by ionic or covalent bonds.

[0012]

[0011] 6. The composition of claim 5, wherein the SBUs contain one or more species of metal ions selected from the periodic table that include Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y3+, Ti4+, Zr4+, Hl4+, V5+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, Co2+, Rh2+, Rh+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, B3+, B5+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, Bi+and their combinations.

[0013]

[0012] 7. The composition of claim 6, wherein in order to be charge-balanced, the SBUs contain anion selected from: O2", N3’ and S2'.

[0014]

[0013] 8. The composition of claim 7, wherein in addition, the bridging -OH, carboxylate acid - COO such as formate, acetate and benzolate, and neutral solvent molecules such as dimethylformamide and water are also be a part of the SBU.

[0015]

[0014] 9. A composition of claim 5, comprising a hydroxamate-based yttrium MOF, named MOF-419 | Y(HCOO)(BDH) |, with rod-SBUs, wherein: MOF = metal-organic framework; BDH = benzene- 1,4-hydroxamate; SBU = secondary building units.

[0016]

[0015] 10. The composition of claim 5, of a structure shown in Fig. 19, wherein M comprises a metal, metal ion or metal complex, L is a hydroxamate-comprising organic linker, and n is an integer greater than 10, wherein the dash lines indicate a bond between the oxygen or nitrogen atom of the hydroxamate-comprising organic linker and a metal, metal ion, or metal complex.

[0016] 11. The composition of claim 10, wherein for the hydroxamate linkers are organic aromatic or nonaromatic rings or chains that contains two or more hyxroxamate groups.

[0017]

[0017] 12-20. The composition of claim 10, of structure as shown in an of Figs. 20-28, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

[0018]

[0018] 21. A method of synthesizing the composition of claim 10, wherein the solvent used for the synthesis method is selected from water, acetic acid, acetone, acetonitrile, benzene, butanol, carbon tetrachloride, chlorobenzene, chloroform, diethyl ether, 1 ,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, diethyl formamide, ethanol, ethyl acetate, hexane, methanol, methylene chloride, nitromethane, propanol, pyridine, tetrahydrofuran, toluene, triethyl amine, xylene, and their mixtures, and the base used to fully deprotonate the linker is selected from ammonium hydroxide, lithium hydroxide, sodium hydroxide, barium hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, cesium hydroxide, zinc hydroxide, methylamine, imidazole, and benzimidazole and the mixture of two or more of the above compounds.

[0019]

[0019] The invention encompasses all combinations of the aspects and embodiments recited herein, as if each combination had been laboriously recited.

[0020]

[0020] Brief Description of the Drawings

[0021]

[0021] Fig. 1. Single crystal X-ray structure of MOF-419 constructed from the infinite rod- like secondary building units and chelating organic linker H2BDH. The polyhedra represents the trigonal dodecahedron with Y atoms in the center, coordinated with eight surrounding oxygen atoms.

[0022]

[0022] Fig. 2. Single crystal X-ray structure of MOF-419.

[0023]

[0023] Fig. 3. Single crystal X-ray structure of MOF-419.

[0024]

[0024] Fig. 4. The rod-like SBU of MOF-419, which consists of edge-sharing YOSpolyhedra, each in the form of a trigonal dodecahedron, connected by hydroxamates and carboxylates from terminal formates.

[0025]

[0025] Fig. 5. The rod-like SBU of MOF-419, which consists of edge-sharing YOSpolyhedra, each in the form of a trigonal dodecahedron, connected by hydroxamates and carboxylates from terminal formates.

[0026]

[0026] Fig. 6. The rod-like SBU of MOF-419, which consists of edge-sharing YO§ polyhedra, each in the form of a trigonal dodecahedron, connected by hydroxamates and carboxylates from terminal formates.

[0027]

[0027] Fig. 7. The coordination environment of Y centers in MOF-419.

[0028] Fig. 8. The coordination environment of Y centers in MOF-419.

[0029] Fig. 9. The connectivity between the yttrium secondary building units and organic linker H2BDH in the single crystal structure of MOF-419.

[0030] Fig. 10. Packing in the single crystal structure of MOF-419 viewed along the a-axis.

[0028]

[0031] Fig. 11. PXRD patterns of as-synthesized and fully activated MOF-419. The simulated patterns on the top were generated using single crystal structure of MOF-419.

[0029]

[0032] Fig. 12. PXRD patterns of MOF-419 after exposure to aqueous solutions of different pH for 7 days.

[0030]

[0033] Fig. 13. Representative scanning electron microscopy micrograph of MOF-419 crystallites.

[0031]

[0034] Fig. 14.Needle-like morphology of MOF-419 crystals.

[0032]

[0035] Fig. 15. H-NMR spectrum of MOF-419 after being thoroughly washed with acetone and digested in DCl / D2O / DMSO-de solvent mixture.

[0033]

[0036] Figs. 16a-c. Nitrogen sorption analysis of MOF-419. (a) N sorption isotherm at 77 K. (b) Rouquerol plot for determination of the appropriate pressure range for BET analysis, (c) BET plot (correlation coefficient = 0.99969) yielding a BET surface area of 1130 m2 / g; P: partial pressure of argon, Po = 1 atm, STP: standard temperature and pressure).

[0034]

[0037] Fig. 17. Pore size distribution plot of MOF-419 estimated from its nitrogen sorption a isotherm at 77 K (cumulative pore volume = 0.363 cm / g).

[0035]

[0038] Fig. 18. Adsorption-desorption isotherms of carbon dioxide and water vapor on MOF- 419 at a measurement temperature of 298 K.

[0036]

[0039] Fig. 19. The illustration of connetivity between the metal ions or clusters M, hydroxamate linkers L in hydroxamate MOFs, where n is an integer greater than 10. The dash line between M and L indicates the chemical bonding between the metal ions or clusters and the oxygen or nitrogen atoms from the hydroxamte groups on the linker.

[0037]

[0040] Fig. 20. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0038]

[0041] Fig. 21. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0039]

[0042] Fig. 22. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0040]

[0043] Fig. 23. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0041]

[0044] Fig. 24. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0042]

[0045] Fig. 25. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0043]

[0046] Fig. 26. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0044]

[0047] Fig. 27. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0045]

[0048] Fig. 28. General schematic for linkers that can be used for the synthesis of hydroxamate- based MOFs. The substitution functional groups are represented as R, which can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether and disulfide, the atoms on heterocycles are represented as A, which can be carbon, oxygen, nitrogen, sulfur and selenium atoms with or without hydrogen atoms, depending on the chemical bonding.

[0046]

[0049] Description of Particular Embodiments of the Invention

[0047]

[0050] Unless contraindicated or noted otherwise, in these descriptions and throughout this specification, the terms “a” and “an” mean one or more, the term “or” means and / or. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein, including citations therein, are hereby incorporated by reference in their entirety for all purposes.

[0048]

[0051] The hydroxamate groups, well known for their strong binding ability with metals, are found in siderophores and metal complex.13,14Linkers containing hydroxamate groups can be used to construct MOFs to enhance the stability and diversity of extended structures, as they are sterically unencumbered with a linking pattern similar to commonly used carboxylate linkers, but have different coordination bonding strength and geometry. Furthermore, the presence of an -NH group on the hydroxamate linker can increase the hydrophilicity of the pore environment and provide an additional adsorption site for water molecules.

[0049]

[0052] The hydroxamate MOFs prepared by our synthetic method possess permanent porosity and ultra-high stability, making them suitable for a variety of applications such as gas separation, sensing, catalysis, adsorption-driven heat exchangers, heat pumps, adsorption / desiccation units for sewage treatment, adsorption-driven refrigeration systems, air conditioning, atmospheric water harvesting, carbon dioxide capture and the removal of volatile organic compounds (VOCs).

[0050]

[0053] In comparison to MOFs constructed from other SBUs, such as discrete metal clusters, rod MOFs are more desirable candidates for applications such as catalysis, gas separation, sensing, pollutant removal, and water harvesting, due to their exceptional stability and highly- open framework channels. However, the majority of coordination linkages in rod-like SBUs are limited to carboxylates, with some less common examples including phosphonates, azolates, and mixed functionalities. Herein, we provide guidelines to prepare hydroxamate-based rod MOFs with permanent porosity, and disclose that this is also applicable to the synthesis of MOFs comprising hydroxamate linkers to improve framework stability and expand the applications. Additionally, we also disclose the green synthesis of hydroxamate MOFs, which uses water as the solvent to avoid using of toxic organic solvent, reducing production cost and environmental hazards in the industrial-scale synthesis of MOFs.

[0051]

[0054] The synthesis of the hydroxamate-based MOFs is based on the hydrothermal reaction between the metal and the hydroxamate linkers with or without additional modulators. As an example, we demonstrate a Y-hydroxamate framework, MOF-419 [Y(HCOO)(BDH)], and its structural and sorption properties. We synthesized this rod-MOF through a solvothermal reaction of Y(NO3)3• 6H3O and H3BDH in N, N-dimethylformamide (DMF) with formic acid as the modulator, resulting in the formation of light-pink needle-shaped crystals after 90 min at 100 °C. Alternatively, MOF-419 crystals can be synthesized using a green synthesis procedure with water as solvent under similar synthetic conditions.

[0052]

[0055] Single crystal X-ray diffraction studies shows that MOF-419 crystals have Z4122 space group with unit cell parameters of a = 17.2055(1) A and c = 15.7079(1) A. As shown in Fig, 1 to Fig. 10, its rod-like SBU consists of edge-sharing YO§ polyhedra, each in the form of a trigonal dodecahedron, connected by hydroxamates and carboxylates from terminal formates. The Y centers are bound to four hydroxamate groups from four linkers, where two hydroxamates are bidentate and the remaining two are monodentate. The Y coordination sphere is completed with oxygen from two formates bridging two Y3+ions. The BDH2" are bonded to four polyhedrons from two chains. This leads to a 3D framework supporting square-shaped one-dimensional (ID) channels of around 9 A. In terms of topology, the underlying net of MOF-419 is described as a snp rod net in which the points of extension are defined by the carbon atoms on the hydroxamate units.

[0053]

[0056] In Fig. 11, powder X-ray diffraction (PXRD) analysis shows the high crystallinity of the synthesized hydroxamate-based MOFs. In Fig. 12, the chemical stability of MOF-419 was demonstrated by placing the crystals in a wide range of acidic and basic aqueous solutions at room temperature for 7 days. The PXRD data shows that the crystallinity did not change within the pH range of 3-13, suggesting the retention of integrity of the crystal structure under these conditions. This is likely due to the chelating nature of the hydroxamate linker and the steric shielding of metal ions under rod SBUs and we consider it as a common feature for hydroxamate MOFs. In addition, scanning electron microscopy images, as shown in Fig. 13 and Fig.14, show the homogenous morphology of MOF-419 and particle sizes with little variation.

[0054]

[0057] As shown in Fig. 15, MOF-419 was digested in a mixture of 60 pL 35 % DC1 in D2O and 600 pL of deuterated dimethyl-sulfoxide (DMSO-d,j for1H-NMR analysis. The proton signal from the hydrogen atom on formic acid and aromatic hydrogen atoms H2BDH linker showed a 1 :4 ratio, suggesting a 1 : 1 ratio between HCOO- and BDH2- in MOF-419. The proton signal at 6.37 ppm corresponds to the proton in DC1 / D2O and the signal at 2.50 was from the DMSO-dg solvent. No signal from DMF and acetone was found, suggesting the washing and activation were completed.

[0055]

[0058] The permeant porosity of the MOF-419 is confirmed by nitrogen sorption measurements at 77 K and the respective results are shown in Fig. 16 and Fig. 17. The surface area was calculated to be 1130 m2 / g from the Brunauer-Emmett-Teller (BET) model by fitting the selected adsorption points that met the consistency criteria for the BET theory. Additionally, Fig 18 shows the CO2and H2O uptake of MOF-419 measured at 298 K, and we envisioned that the hydroxamate -based MOFs are good candidates for carbon dioxide capture and water harvesting from air.

[0056]

[0059] Overall, this disclosure demonstrates that the synthesis method performs reliably in producing hydroxamate-based MOFs that have permeant porosity, in addition to high crystallinity, excellent chemical stability, and favorable sorption properties. We disclose that this synthesis method is generalizable to other hydroxamate-based MOFs.

[0057]

[0060] The hydroxamate MOFs synthesized by this method are composed of metal clusterbased secondary building units and hydroxamate linkers that are connected by ionic or covalent bonds. The SBUs can contain one or more species of metal ions from the periodic table that include Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y3+, Ti4+, Zr4+, Hl4+, V5+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, Co2+, Rh2+, Rh+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, B3+, BS+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, Bi+and their combinations. In order to be charge-balanced, the SBUs can contain anion O2’, N3’ and S2’. In addition, the bridging -OH, carboxylate acid -COO such as formate, acetate and benzolate, and neutral solvent molecules such as dimethylformamide and water can also be a part of the SBU. As shown in Fig. 19, M comprises a metal, metal ion or metal complex, L is a hydroxamate-comprising organic linker, and n is an integer greater than 10, wherein the dash lines indicate a bond between the oxygen or nitrogen atom of the hydroxamate-comprising organic linker and a metal, metal ion, or metal complex.

[0058]

[0061] For the hydroxamate linkers, they are usually organic aromatic or nonaromatic rings or chains that contains two or more hyxroxamate groups. As shown in Fig. 20 to Fig. 28, the substituting R group can be hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring can be carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-). The solvent used for the synthesis method can be water, acetic acid, acetone, acetonitrile, benzene, butanol, carbon tetrachloride, chlorobenzene, chloroform, diethyl ether, 1 ,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, diethyl formamide, ethanol, ethyl acetate, hexane, methanol, methylene chloride, nitromethane, propanol, pyridine, tetrahydrofuran, toluene, triethyl amine, xylene, and their mixtures. The base used to fully deprotonate the linker can be, but is not limited to, ammonium hydroxide, lithium hydroxide, sodium hydroxide, barium hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, cesium hydroxide, zinc hydroxide, methylamine, imidazole, and benzimidazole and the mixture of two or more of the above compounds.

[0059]

[0062] Experimental Procedures

[0060]

[0063] Synthesis of MQF-419 in DMF

[0061]

[0064] In a 20 mL scintillation vial, H2BDH (98 mg, 0.5 mmol) was dispersed in DMF (10 mL). The resulting mixture was heated for 30 min in a preheated oven at 100 °C to yield a clear solution. Yttrium (III) nitrate hexahydrate (191 mg, 0.5 mmol) was dissolved in DMF (2 mL) and added to the H2BDH solution. The combined solution was sonicated for 10 min and formic acid (4 mL, 100 mmol) was added. The vial was placed in an oven at 100 °C for 90 min. The resulting solid was collected via filtration. The single crystals were washed with DMF (10.0 mL) three times to remove the unreacted reagents in the pores. DMF solvent was removed by washing the crystals with acetone (10.0 mL) for three times. The obtained solid was collected via filtration and dried under vacuum to yield MOF-419 (148 mg, 90% based on linker).

[0062]

[0065] Synthesis of MOF-419 in water

[0063]

[0066] In a 20 mL scintillation vial, yttrium (111) nitrate hexahydrate (191 mg, 0.5 mmol) and H BDH (98 mg, 0.5 mmol) were dispersed in deionized water (12 mL). The mixture was sonicated for 10 min and formic acid (4 mL, 100 mmol) was added to the solution. The vial was placed in an oven at 100 °C overnight. The resulting solid was collected via filtration. The single crystals were washed with deionized water (10.0 mL) and acetone (10.0 mL) three times per day for two days, respectively. The obtained solid was collected via filtration and dried under vacuum to yield MOF-419 (122 mg, 72% based on linker).

[0064]

[0067] References

[0065]

[0068] 1. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).

[0066]

[0069] 2. Moghadam, P. Z. et al. Development of a Cambridge Structural Database subset. ... Chem. Mater. 29, 2618-2625 (2017).

[0067]

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[0068]

[0071] 4. Stock, N. & Biswas, S. Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites. Chem. Rev. 112, 933-969 (2012).

[0069]

[0072] 5. Barsukova, M. O. et al. Isomeric Scandium-Organic Frameworks with High Hydrolytic Stability and Selective Adsorption of Acetylene. Inorg. Chem. 60, 2996-3005 (2021).

[0070]

[0073] 6. Schoedel, A., Li, M., Li, D., O’Keeffe, M. & Yaghi, O. M. Structures of metalorganic frameworks with rod secondary building units. Chem. Rev. 116, 12466-12535 (2016).

[0071]

[0074] 7. Kalmutzki, M. J., Hanikel, N. & Yaghi, O. M. Secondary building units as the turning point in the development of the reticular chemistry of MOFs. Sci. Adv. 4, eaat9180 (2018).

[0072]

[0075] 8. Fathieh, F. et al. Practical water production from desert air. Sci. Adv. 4, eaat3198 (2018).

[0073]

[0076] 9. Hanikel, N. et al. Evolution of water structures in metal-organic frameworks for improved atmospheric water harvesting. Science 374, 454-459 (2021).

[0074]

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[0075]

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[0076]

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[0077]

[0080] 13. Neilands, J. Siderophores: structure and function of microbial iron transport compounds. J. Biol. Chem. 270, 26723-26726 (1995).

[0078]

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Claims

CLAIMS1. A composition herein comprising a hydroxamate-based metal-organic framework.

2. A composition herein comprising a hydroxamate-based metal-organic framework, configured for an indication selected from gas separation, sensing, catalysis, adsorption-driven heat exchangers, heat pumps, adsorption / desiccation units for sewage treatment, adsorption-driven refrigeration systems, air conditioning, atmospheric water harvesting, carbon dioxide capture or the removal of volatile organic compounds (VOCs).

3. A method of making a composition herein, using water as the solvent to avoid using a physiologically or environmentally toxic organic solvent.

4. A method of using a composition herein for catalysis, gas separation, sensing, pollutant removal, or water harvesting.

5. A composition herein comprising a hydroxamate-based metal-organic framework comprising metal cluster-based secondary building units and hydroxamate linkers that are connected by ionic or covalent bonds.

6. The composition of claim 5, wherein the SBUs contain one or more species of metal ions selected from the periodic table that include Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+,Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, Bi+and their combinations.

7. The composition of claim 6, wherein in order to be charge-balanced, the SBUs contain anion selected from: O2’, N3' and S2'.

8. The composition of claim 7, wherein in addition, the bridging -OH, carboxylate acid -COO such as formate, acetate and benzolate, and neutral solvent molecules such as dimethylformamide and water are also be a part of the SBU.

9. A composition of claim 5, comprising a hydroxamate-based yttrium MOF, named MOF-419 [Y(HCOO)(BDH)], with rod-SBUs, wherein: MOF = metal-organic framework; BDH = benzene- 1,4-hydroxamate; SBU = secondary building units.

10. The composition of claim 5, of a structure shown in Fig. 19, wherein M comprises a metal, metal ion or metal complex, L is a hydroxamate-comprising organic linker, and n is an integer greater than 10, wherein the dash lines indicate a bond between the oxygen or nitrogen atom of the hydroxamate-comprising organic linker and a metal, metal ion, or metal complex.

11. The composition of claim 10, wherein for the hydroxamate linkers are organic aromatic or nonaromatic rings or chains that contains two or more hyxroxamate groups.

12. The composition of claim 10, of structure as shown in Fig. 20, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

13. The composition of claim 10, of structure as shown in Fig. 21, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

14. The composition of claim 10, of structure as shown in Fig. 22, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

15. The composition of claim 10, of structure as shown in Fig. 23, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl,alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

16. The composition of claim 10, of structure as shown in Fig. 24, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

17. The composition of claim 10, of structure as shown in Fig. 25, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

18. The composition of claim 10, of structure as shown in Fig. 26, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

19. The composition of claim 10, of structure as shown in Fig. 27, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl, alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

20. The composition of claim 10, of structure as shown in Fig. 28, wherein each substituting R group (Rl, R2, etc.) is independently selected from hydrogen, alkane, alkene, alkyne, phenyl,alcohol, ether, aldehyde, ketone, epoxide, carboxylic acid, ester acyl halide, halide, amide, acid anhydride, amine, amide, nitrile, imine, azo compounds, azide, thiol, thioether, disulfide and the atom A on the ring is selected from carbon (-CH2-), oxygen (-O-), nitrogen (-NH-), sulfur (-S-), and selenium (-Se-).

21. A method of synthesizing the composition of claim 10, wherein the solvent used for the synthesis method is selected from water, acetic acid, acetone, acetonitrile, benzene, butanol, carbon tetrachloride, chlorobenzene, chloroform, diethyl ether, 1 ,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, diethyl formamide, ethanol, ethyl acetate, hexane, methanol, methylene chloride, nitromethane, propanol, pyridine, tetrahydrofuran, toluene, triethyl amine, xylene, and their mixtures, and the base used to fully deprotonate the linker is selected from ammonium hydroxide, lithium hydroxide, sodium hydroxide, barium hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, cesium hydroxide, zinc hydroxide, methylamine, imidazole, and benzimidazole and the mixture of two or more of the above compounds.

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