Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage

• US 6,930,193 B2
• Filed: 04/30/2002
• Issued: 08/16/2005
• Est. Priority Date: 04/30/2001
• Status: Expired due to Term

• Current Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Original Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Yaghi, Omar M., Eddaoudi, Mohamed, Kim, Jaheon, Li, Hailian, Rosi, Nathaniel
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US10/137,043
• Publication Number:
  US 20030004364A1
• Time in Patent Office: 1,204 Days
• Field of Search: 556/43, 556/46, 556/51, 556/58, 556/72, 556/89, 556/112, 556/113, 556/136, 556/141, 534/15
• US Class Current: 556/46
• CPC Class Codes: B01J 20/226 Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28014 characterised by their form
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28078 Pore diameter
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: B01J 20/30 Processes for preparing, regenerating, or reactivating
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: C07F 3/003 without C-Metal linkages
• CPC Class Codes: F17C 11/007 for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

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.

Claims

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.

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.

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.

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.

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.

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.

13. The IRMOF as defined in claim 10, wherein the methane storage capacity is about 155 cm³/cm³.

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.

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.