Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07F-013/00
C07F-015/00
C07F-011/00
출원번호
US-0137043
(2002-04-30)
§371/§102 date
20040115
(20040115)
발명자
/ 주소
Yaghi, Omar M.
Eddaoudi, Mohamed
Li, Hailian
Kim, Jaheon
Rosi, Nathaniel
출원인 / 주소
The Regents of the University of Michigan
대리인 / 주소
Dierker &
인용정보
피인용 횟수 :
80인용 특허 :
2
초록▼
An isoreticular metal-organic framework (IRMOF) and method for systematically forming the same. The method comprises the steps of dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; and crystallizing the solution under predetermi
An isoreticular metal-organic framework (IRMOF) and method for systematically forming the same. The method comprises the steps of dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF. At least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound.
대표청구항▼
1. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M4O(CO2)6 cluster; and a compound linking adjacent SBUS, the linking compound comprising a linear ditopic car
1. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M4O(CO2)6 cluster; and a compound linking adjacent SBUS, the linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group and at least one functional group X attached to the at least one substituted phenyl group; wherein the IRMOF has a substantially permanent porosity and is substantially stable; wherein the functional group X is at least one of hydrogen, amines, halides, an R group selected from at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof; and M is a metal cation; and wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the linking compound. 2. The IRMOF as defined in claim 1 wherein the linking compounds are selected from the group consisting of: wherein the functional group X is at least one of hydrogen, amines, halides, an R group selected from at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 3. The IRMOF as defined in claim 2 wherein X comprises at least one of primary, secondary or tertiary amines; aromatic amines, pyridine, pyrimidine like 5 or 6 membered rings; halides including substituted ?RX; alcohols: ROH; thiols: RSH; sulfonates ?R?SO3; nitro groups ?R(NO2?); phosphates ?R?PO2?; epoxides; aldehydes (RCOH); ketones (RCOR); esters RCO2R; carboxylic acids; cycloalkenes; cycloalkynes; silyls derivatives; boranes derivatives; ferrocenes, other metallocenes, and mixtures thereof.4. The IRMOF as defined in claim 1 wherein M in the SBU is a metal cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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.5. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution, the at least one organic linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 6. The method as defined in claim 5 wherein the at least one source of metal cations is a metal salt formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of zinc, cadmium, mercury, and transition metals, and wherein the anion is selected from the group consisting of F?, Cl?, Br?, I?, ClO2?, ClO3?, ClO4?, OH?, NO3?, NO2?, SO42?, SO32?, PO43?, CO32?, CH3CO2?, HCO2?and CF3SO3?, B4O72?and PF6?.7. The method as defined in claim 6 wherein at least one functional group X is attached to the at least one substituted phenyl group.8. The method as defined in claim 5 wherein the predetermined conditions are at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature.9. A systematically formed isoreticular metal organic framework (IRMOF), consisting essentially of:a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M4O(CO2)6 cluster, wherein M is a metal cation; and a compound linking adjacent SBUs, the linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group and at least one functional group X attached to the at least one substituted phenyl group; wherein the IRMOF has a substantially permanent porosity and is substantially stable; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the linking compound; and wherein the IRMOF is adapted to store at least one gas. 10. A systematically formed isoreticular metal organic framework (IRMOF), consisting essentially of:a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M4O(CO2)6 cluster, wherein M is a metal cation; and a compound linking adjacent SBUs, the linking compound comprising a linear ditopic carboxylate having at least one phenyl group and at least one functional group X attached to the at least one phenyl group; wherein the IRMOF has a substantially permanent porosity and is substantially stable; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the linking compound; and wherein the IRMOF is adapted to store methane. 11. The IRMOF as defined in claim 1 wherein the density of the IRMOF is between about 1.0 g/cm3 and about 0.2 g/cm3.12. The IRMOF as defined in claim 11 wherein the density of the IRMOF is between about 0.41 g/cm3 and about 0.21 g/cm3.13. The IRMOF as defined in claim 10, wherein the methane storage capacity is about 155 cm3/cm3.14. The method as defined in claim 5 wherein the at least one source of metal cations is a plurality of secondary building units (SBUs).15. The method as defined in claim 14 wherein each of the SBUs is a multi-metal nuclear carboxylate cluster.16. The method as defined in claim 15 wherein the multi-metal nuclear carboxylate cluster is M4O(CO2)6.17. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; wherein the at least one source of metal cations is a metal salt formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of zinc, cadmium, mercury, and transition metals, and wherein the anion is selected from the group consisting of F?, Cl?, Br?, I?, ClO?, ClO2?, ClO3?ClO4?, OH?, NO3?, NO2?, SO42?, SO32?, PO43?, CO32?, CH3CO2?, HCO2?and CF3SO3?, B4O72?and PF6?; wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one substituted phenyl group; and wherein the linear ditopic carboxylate is selected from the group consisting of; wherein the functional group X is at least one of hydrogen, amines, halides, an R group comprising at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 18. The method as defined in claim 17 wherein X comprises at least one of primary, secondary or tertiary amines; aromatic amines, pyridine, pyrimidine like 5 or 6 membered rings; halides including substituted ?RX; alcohols: ROH; thiols: RSH; sulfonates ?R?SO3; nitro groups ?R(NO2?); phosphates ?R?PO2?; epoxides; aldehydes (RCOH); ketones (RCOR); esters RCO2R; carboxylic acids; cycloalkenes; cycloalkynes; silyls derivatives; boranes derivatives; ferrocenes, other metallocenes, and mixtures thereof.19. The method as defined in claim 5 wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution, the at least one organic linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group; crystallizing the solution under predetermined conditions to form a predetermined IRMOF; and storing at least one gas within the IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 21. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; crystallizing the solution under predetermined conditions to form a predetermined IRMOF; and storing methane within the IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 22. The method as defined in claim 21, wherein the methane storage capacity is about 155 cm3/cm3.23. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution, the at least one organic linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the density of the IRMOF is between about 1.0 g/cm3 and about 0.2 g/cm3. 24. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution: and crystallizing the solution under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the density of the IRMOF is between about 0.41 g/cm3 and about 0.21 g/cm3. 25. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution, wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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, and wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one substituted phenyl group; and crystallizing the solution under predetermined conditions to form the IRMOF, wherein the predetermined conditions are at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 26. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution, wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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, and wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one substituted phenyl group; and crystallizing the solution under predetermined conditions to form the IRMOF, wherein the predetermined conditions are at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetetmined temperature; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the linear ditopic carboxylate is selected from the group consisting of: wherein the functional group X is at least one of hydrogen, amines, halides, an R group comprising at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 27. The method as defined in claim 26 wherein the at least one source of metal cations is a plurality of secondary building units (SBUs), and wherein each of the SBUs is a multi-metal nuclear carboxylate cluster.28. The method as defined in claim 27 wherein the multi-metal nuclear carboxylate cluster is M4O(CO2)6.29. The method as defined in claim 28 wherein X comprises at least one of primary, secondary or tertiary amines; aromatic amines, pyridine, pyrimidine like 5 or 6 membered rings; halides including substituted ?RX; alcohols: ROH; thiols: RSH; sulfonates ?R?SO3; nitro groups ?R(NO2); phosphates ?R?PO2?; epoxides; aldehydes (RCOH); ketones (RCOR); esters RCO2R carboxylic acids; cycloalkenes; cycloalkynes; silyls derivatives; boranes derivatives; ferrocenes, other metallocenes, and mixtures thereof.30. The method as defined in claim 29 wherein the at least one source of metal cations is a metal salt formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of zinc, cadmium, mercury, and transition metals, and wherein the anion is selected from the group consisting of F?, Cl?, Br?, I?, ClO?, ClO2?, ClO3?, ClO4?, OH?, NO3?, NO2?, SO42?, SO32?, PO43?, CO32?, CH3CO2?, HCO2?and CF3SO3?, B4O72?and PF6?.31. The method as defined in claim 30, further comprising the step of storing at least one gas within the IRMOF.32. A method of systematically forming an isoreticular metal-organic framework (IRMOF), the method comprising the steps of:dissolving at least one source of metal cation and at least one organic linking compound in a solvent to form a solution, wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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, and wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one phenyl group; crystallizing the solution under predetermined conditions to form the IRMOF, wherein the predetermined conditions are at least one of; leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature; and storing methane within the IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; wherein the linear ditopic carboxylate is selected from the group consisting of; and wherein the functional group X is at least one of hydrogen, amines, halides, an R group comprising at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 33. The method as defined in claim 32, wherein the methane storage capacity is about 155 cm3/cm3.34. The method as defined in claim 33 wherein the density of the IRMOF is between about 1.0 g/cm3 and about 0.2 g/cm3.35. The method as defined in claim 34 wherein the density of the IRMOF is between about 0.41 g/cm3 and about 0.21 g/cm3.36. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:at least one source of metal cations; and at least one organic linking compound comprising a linear diptopic carboxylate having at least one substituted phenyl group, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 37. The IRMOF as defined in claim 36 wherein the at least one source of metal cations is a metal salt formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of zinc, cadmium, mercury, and transition metals, and wherein the anion is selected from the group consisting of F?, Cl?, Br?, I?, ClO?, ClO2?, ClO3?, ClO4?, OH?, NO3?, NO2?, SO42?, SO32?, PO43?, CO32?, CH3CO2?, HCO2?and CF3SO3?, B4O72?and PF6?.38. The IRMOF as defined in claim 36 wherein at least one functional group X is attached to the at least one substituted phenyl group.39. The IRMOF as defined in claim 36 wherein the predetermined conditions are at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature.40. The IRMOF as defined in claim 36 wherein the at least one source of metal cations is a plurality of secondary building units (SBUs).41. The IRMOF as defined in claim 40 wherein each of the SBUs is a multi-metal nuclear carboxylate cluster.42. The IRMOF as defined in claim 41 wherein the multi-metal nuclear carboxylate cluster is M4O(CO2)6.43. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:at least one source of metal cations; and at least one organic linking compound, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one substituted phenyl group, and wherein the linear ditopic carboxylate is selected from the group consisting of: wherein the functional group X is at least one of hydrogen, amines, halides, an R group comprising at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 44. The IRMOF as defined in claim 43 wherein X comprises at least one of primary, secondary or tertiary amines; aromatic amines, pyridine, pyrimidine like 5 or 6 membered rings; halides including substituted ?RX; alcohols: ROH; thiols: RSH; sulfonates ?R?SO3; nitro groups ?R(NO2?); phosphates ?R?PO2; epoxides; aldehydes (RCOH); ketones (RCOR); esters RCO2R; carboxylic acids; cycloalkenes; cycloalkynes; silyls derivatives; boranes derivatives; ferrocenes, other metallocenes, and mixtures thereof.45. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:at least one source of metal cations; and at least one organic linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound, and wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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. 46. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:at least one source of metal cations; and at least one organic linking compound comprising a linear ditopic carboxylate having at least one substituted phenyl group, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the IRMOF is adapted to store at least one gas. 47. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:least one source of metal cations; and at least one organic linking compound, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the IRMOF is adapted to store methane. 48. The IRMOF as defined in claim 47 wherein the methane storage capacity is about 155 cm3/cm3.49. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of;at least one source of metal cations; and at least one organic linking compound comprising a linear diptopic carboxylate having at least one substituted phenyl group, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound; and wherein the density of the IRMOF is between about 1.0 g/cm3 and about 0.2 g/cm3. 50. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentialiy of;at least one source of metal cations; and at least one organic linking compound, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein at least one functionality, dimension, pore size and free volume of the IRMOF is substantially deterimned by the organic linking compound; and wherein the density of the IRMOF is between about 0.41 g/cm3 and about 0.21 g/cm3. 51. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:at least one source of metal cations, wherein the metal cation is a cation of a metal chosen from at least one of beryllium, zinc, cadmium, mercury, 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; and at least one organic linking compound, wherein the at least one organic linking compound is a linear ditopic carboxylate having at least one substituted phenyl group, wherein the at least one source of metal cations and the organic linking compound are dissolved in solution and crystallized under predetermined conditions to form a predetermined IRMOF; wherein the predetermined conditions are at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature; and wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound. 52. The IRMOF as defined in claim 51 wherein the linear ditopic carboxylate is selected from the group consisting of: wherein the functional group X is at least one of hydrogen, armines, halides, an R group selected from at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof. 53. The IRMOF as defined in claim 52 wherein the at least one source of metal cations is a plurality of secondary building units (SBUs), and wherein each of the SBUs is a multi-metal nuclear carboxylate cluster.54. The IRMOF as defined in claim 53 wherein the multi-metal nuclear carboxylate cluster is M4O(CO2)6.55. The IRMOF as defined in claim 54 wherein X comprises at least one of primary, secondary or tertiary amines; aromatic amines, pyridine, pyrimidine like 5 or 6 membered rings; halides including substituted ?RX; alcohols: ROH; thiols: RSH; sulfonates ?R?SO3; nitro groups ?R(NO2?); phosphates ?R?PO2?; epoxides; aldehydes (RCOH); ketones (RCOR); esters RCO2R; carboxylic acids; cycloalkenes; cycloalkynes; silyls derivatives; boranes derivatives; ferrocenes, other metallocenes, and mixtures thereof.56. The IRMOF as defined in claim 55 wherein the at least one source of metal cations is a metal salt formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of zinc, cadmium, mercury, and transition metals, and wherein the anion is selected from the group consisting of F?, Cl?, Br?, I?, ClO?, ClO2?, ClO3?, ClO4?, OH?, NO3?, NO2?, SO42?, SO32?, PO43?, CO32?, CH3CO2?, HCO2?and CF3SO3?, B4O72?and PF6?.57. The IRMOF as defined in claim 56 wherein the IRMOF is adapted to store at least one gas.58. The IRMOF as defined in claim 57 wherein the at least one gas is methane.59. The IRMOF as defined in claim 58, wherein the methane storage capacity is about 155 cm3/cm3.60. The IRMOF as defined in claim 59 wherein the density of the IRMOF is between about 1.0 g/cm3 and about 0.2 g/cm3.61. The IRMOF as defined in claim 60 wherein the density of the IRMOF is between about 0.41 g/cm3 and about 0.21 g/cm3.62. A systematically formed isoreticular metal-organic framework (IRMOF), consisting essentially of:a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M4O(CO2)6 cluster; and a compound linking adjacent SBUs, the linking compound comprising a linear ditopic carboxylate having at least one phenyl group and at least one functional group X attached to the at least one phenyl group; wherein the IRMOF has a substantially permanent porosity and is substantially stable; wherein the functional group X is at least one of hydrogen, amines, halides, an R group selected from at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and ether O?R, wherein R is at least one of linear, substituted or cyclo alkanes, alkenes, alkynes, chains, and mixtures thereof; wherein at least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the linking compound; and wherein M in the SBU is a metal cation of a metal chosen from at least one of beryllium, cadmium, mercury, 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.
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