초록 ▼

The subject invention pertains to metal organic frameworks (MOF) having zeolite-net-like topology, their methods of use, and their modes of synthesis. The ZMOFs are produced by combining predesigned tetrahedral building, generated in situ using heterochelation, with polyfunctional ligands that have

The subject invention pertains to metal organic frameworks (MOF) having zeolite-net-like topology, their methods of use, and their modes of synthesis. The ZMOFs are produced by combining predesigned tetrahedral building, generated in situ using heterochelation, with polyfunctional ligands that have the commensurate angle and the required donor groups for the chelation. Each molecular building block is contrasted of a single metal ion and ligands with both heterochelation functionality and bridging functionality. Advantageously, zeolite-net-like MOFs of the subject invention are porous and contain large functional cavities, which is useful for encapsulating large molecules.

대표청구항 ▼

1. A zeolite-like metal organic framework (ZMOF) comprising a plurality of molecular building blocks (MBB) having an MXnYm cluster wherein M is a metal; X is N, O, or S; Y is N, O, or S; n is 2, 3, or 4; and m is 2, 3, or 4, wherein the ZMOF consists of rigid tetrahedral secondary building units and

1. A zeolite-like metal organic framework (ZMOF) comprising a plurality of molecular building blocks (MBB) having an MXnYm cluster wherein M is a metal; X is N, O, or S; Y is N, O, or S; n is 2, 3, or 4; and m is 2, 3, or 4, wherein the ZMOF consists of rigid tetrahedral secondary building units and organic links with the commensurate geometry of an expanded porous zeolite-net-like metal-organic framework wherein the ZMOF is a rho-ZMOF, a sod-ZMOF, or a USF-ZMOF. 2. The ZMOF according to claim 1, wherein M is beryllium, zinc, cadmium, mercury, or any of the transition metals (in the periodic table scandium through copper, yttrium through silver, lanthanum through gold, and all known elements from actinium on). 3. The ZMOF according to claim 2, wherein M is zinc, copper, lanthanum, cadmium, nickel, iron, cobalt or indium. 4. The ZMOF according to claim 1, wherein the X is N; Y is O; and n is 4. 5. The ZMOF according to claim 1, wherein the MBB comprises a ligand having a chelating functionality and a bridging functionality being i) an aromatic ring structure comprising one or more nitrogen atoms and ii) one or more carboxylate groups located in the α-position relative to said nitrogen. 6. The ZMOF according to claim 1, wherein the metal of said MBB is locked into position through the formation of five-membered rings via N—, O— heterochelation to the metal. 7. The ZMOF according to claim 1, wherein guest and H2O molecules associated with synthesis of said ZMOF are removed. 8. The ZMOF according to claim 1, wherein the MXnYm cluster comprises MN4O2, MN4O4, MN2O2, or MN2O4. 9. The ZMOF according to claim 1, wherein the ZMOF comprises a tetrahedral building unit (TBU) of InN4. 10. A method for synthesizing a metal organic framework, said method comprising reacting a metal salt and a ligand having chelating and bridging functionality relative to the metal ion of said metal salt, in a suitable solvent, in the presence of a structure directing agent (SDA) and crystallizing the solution, wherein said metal organic framework comprises a plurality of molecular building blocks (MBB) having an MXnYm cluster wherein M is a metal; X is N, O, or S; Y is N, O, or S; n is 2, 3, or 4; and m is 2, 3, or 4, and wherein the ZMOF consists of rigid tetrahedral secondary building units and organic links with the commensurate geometry of an expanded porous zeolite-net-like metal-organic framework wherein the ZMOF is a rho-ZMOF, a sod-ZMOF, or a USF-ZMOF. 11. The method according to claim 10, wherein said crystallizing step comprises heating said solution from about room temperature to about 200° C. for at least about 4 to 12 hours. 12. The method according to claim 10, wherein said metal salt is M(NO3)x where x=2 or 3. 13. The method according to claim 10, wherein said SDA is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidine (HPP), imidazole, 4,4′-trimethylenedipiperidine, or 1,2-diaminocyclohexane. 14. The method according to claim 10, wherein said crystallizing step comprises heating at about 80° C. to about 90° C. for at least 10 hours followed by heating at about 95° C. to about 110° C. for at least 12 hours. 15. The method according to claim 10, wherein said SDA is HPP and said crystallizing step comprises heating at about 85° C. for about 12 hours followed by heating at about 100° C. for about 14 hours. 16. The method according to claim 10, wherein said SDA is imidazole and said crystallizing step comprises heating at about 85° C. for about 12 hours followed by heating at about 105° C. for about 23 hours. 17. The method according to claim 10, wherein said ligand is selected from the group consisting of 1H-Imidazole-2-carboxylic acid, 1H-pyrrole-2,4-dicarboxylic acid, 1H-Imidazole-4-5-dicarboxylic acid, 2,7-Diaza-antracene-1,8-dicarboxylic acid, pyrimidine-4-6-dicarboxylic acid, pyridine-2,5,dicarboxylic acid, and 2,7-diaza-anthracene-3,6-dicarboxylic acid. 18. The method according to claim 10, wherein said metal of said metal salt has a minimum coordination number of six and a maximum of eight. 19. The method according to claim 10, wherein said metal of said metal salt is beryllium, zinc, cadmium, mercury, or any of the transition metals (in the periodic table scandium through copper, yttrium through silver, lanthanum through gold, and all known elements from actinium on). 20. The method according to claim 19, wherein said metal of said metal salt is zinc, copper, lanthanum, cadmium, nickel, iron, cobalt or indium. 21. The method according to claim 10, wherein the anion of said metal salt is selected from the group consisting of F−, Cl−, Br−, I−, ClO−, ClO2−, ClO3−, ClO4−, OH−, HCO2−, NO3−, SO42−, SO32−, PO4−, CO32−, PF4− and organic counterions. 22. The method according to claim 10, wherein said solvent is selected from the group consisting of N,N-dimethyl formamide (DMF), ethanol, 4,4′-trimethylenedipiperidine, and 1,2-diaminocyclohexane. 23. The method according to claim 22, wherein said solvent further comprises acetonitrile. 24. The method according to claim 10, wherein said solvent is made acidic. 25. A ZMOF produced by the method of claim 10. 26. The method according to claim 10, wherein said metal salt is In(NO3)3. 27. A zeolite-like metal organic framework (ZMOF), wherein said ZMOF is a USF-ZMOF and comprises the formula In2.5(C5N2O4H2)5(C6N2H16)1.25(DMF)12(CH3CN)3(H2O)8. 28. A zeolite-like metal organic framework (ZMOF), wherein said ZMOF is a rho-ZMOF and comprises the formula In48(C5N2O4H2)96(C7N3H15)24(DMF)36(H2O)192. 29. A zeolite-like metal organic framework (ZMOF), wherein said ZMOF is a sod-ZMOF and comprises the formula In(C5N2O4H2)2(C3N2H5)(DMF)4(CH3CN)(H2O)4.