Crystalline metal-organic microporous materials

• US 5,648,508 A
• Filed: 11/22/1995
• Issued: 07/15/1997
• Est. Priority Date: 11/22/1995
• Status: Expired due to Term

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Nalco Chemical Company (Ecolab, Inc.)
• Inventors: Yaghi, Omar M.
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US08/560,224
• Time in Patent Office: 601 Days
• Field of Search: 556/132, 556/9, 556/10, 556/13, 556/19, 556/28, 556/30, 556/44, 556/49, 556/55, 556/61, 556/78, 556/106, 556/115, 556/136, 556/147, 534/16
• US Class Current: 556/9
• 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 2531/16 Copper
• CPC Class Codes: B01J 2531/17 Silver
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 2531/27 Cadmium
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/847 Nickel
• 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 15/065 without a metal-carbon linkage
• CPC Class Codes: C07F 3/003 without C-Metal linkages

Abstract

Novel metal-organic microporous materials are prepared in solution using mild reaction conditions from a metal or metalloid ion with a ligand containing multidentate functional groups in the presence of a templating agent. The resultant microporous materials are useful in the purification of liquids and gases.

Claims

1. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, C²⁺, Rh²⁺, Rh⁺, Ir²⁺, Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, and Bi⁵⁺, Bi³⁺, Bi⁺ ;

along with the corresponding metal salt counteranion, with one or more ligands having at least one of;

an alkyl group substructure, having from 1 to 10 carbon atoms;

an aryl group substructure, having from 1 to 5 phenyl rings;

or, an alkyl or aryl amine substructure, consisting of alkyl groups having from 1 to 10 carbon atoms or aryl groups having from 1 to 5 phenyl rings, said ligand substructure having bound thereto multidentate functional groups, X, which are covalently bound to the substructure of the ligand, wherein X is a functional group selected from the groups consisting of;

CO₂ H, CS₂ H, NO₂, SO₃ H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃ H, AsO₃ H, AsO₄ H, P(SH)₃, As(SH)₃ ;

CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, C(CN)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, in the presence of a templating agent, selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoromethylsulfonic acid.

2. The method of claim 1 wherein the templating agent is pyridine.

3. The method of claim 1 wherein the templating agent is ethanol.

4. The method of claim 1 wherein the ligand is benzene-1,3,5-tricarboxylic acid.

5. The method of claim 1 wherein the ligand is benzene-1,4-dicarboxylic acid.

6. The method of claim 1 wherein the ligand is benzene-1,2,4,5-tetracarboxylic acid.

7. The method of claim 1 wherein the ligand is adamantane-1,3,5,7-tetracarboxylic acid.

8. The method of claim 1 wherein the ligand is 1,1'"'"',1",1'"'"'"-methanetetracarboxylic acid.

9. The method of claim 1 wherein the microporous materials are prepared in the presence of a ligand containing one or more monodentate functional groups said ligand selected from the group consisting of:

a. alkyl amines containing at least one alkyl group containing 1 to 10 carbon atoms;

b. aryl amines containing from 1 to 5 phenyl rings;

c. alkyl alcohols containing at least one alkyl group having from 1 to 10 carbon atoms;

d. aryl alcohols containing from 1 to 5 phenyl rings;

e. alkyl thiols containing at least one alkyl group having from 1 to 10 carbon atoms;

f. aryl thiols containing from 1 to 5 phenyl rings;

g. alkyl cyanides containing at least one alkyl group having from 1 to 10 carbon atoms;

h. aryl cyanides containing from 1 to 5 phenyl rings; and

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, thiocyanide, and isonitrile, and the corresponding acids and salts of said inorganic anions.

10. The method of claim 9 wherein the ligand containing one or more monodentate functional groups is selected from the group consisting of:

pyridine, 4,4'"'"'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, trimethylamine, triethylamine, tripropylamine, 2-aminopropane, triethanolamine, ethylbutylamine, piperidine, cyclohexylamine, 2-methylpyridine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N'"'"'-dimethylpiperazine, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methyl-piperidine, 4-methylpyridine, 1,4-diaminocyclohexane, morpholine, aniline, 1,4-diaminobenzene, 1,3,5-triaminobenzene, 1,3,5-triazine, imidazole, pyrazine, methanol, dihydroxymethane, trihydroxymethane, tetrahydroxymethane, ethanol, ethylene glycol, 1,1,2,2-tetrahydroxyethane, 1 -propanol, 2-propanol, propylene glycol, 1,3-propanediol, glycerol, 1,1,3,3-tetrahydroxypropane, allyl alcohol, n-butanol, sec-butanol, iso-butanol, tert-butanol, 1,4-butanediol, 1,3-butanediol, 1,1,4,4-tetrahydroxybutane, n-pentanol, sec-pentanol, iso-pentanol, tert-pentanol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,3,5-trihydroxypentane, n-hexanol, sec-hexanol, iso-hexanol, tert-hexanol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,3,6-trihydroxyhexane, cyclohexanol, 1,4-dihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, 1,3,5-trihydroxybenzene, 1,2,4-trihydroxy-benzene, 1,2,3-trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene, thiomethane, thioethane, thiopropane, thiocyclohexane, thiobenzene, 1,3-dithiopropane, 1,4-dithiobutane, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

11. The method according to claim 1 in which the reaction mixture containing the microporous material product is heated from 30°

C. to 500°

C. to partially or completely remove the templating agent.

12. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Sc³⁺, Ti⁴⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Mo³⁺, Mn³⁺, Mn²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Ir²⁺, Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, Sb⁵⁺, Sb³⁺, Sb⁺, and Bi⁵⁺, Bi³⁺, Bi⁺ ;

along with the corresponding metal salt counteranion with,

one or more ligand substructures being at least one of;

methane, tetraphenylmethane, ethylene, tertiary amines, tertiary alkyl mines having from 1 to 3 carbon atoms, tertiary aryl amines having from 1 to 2 phenyl rings, benzene, naphthylene, adamantane, squarane, alkanes having from 2 to 4 carbon atoms, and alkenes having from 2 to 4 carbon atoms, said ligand substructure having bound thereto multidentate functional groups, X, which are covalently bound to the substructure of the ligand, wherein X is a functional group selected from the groups consisting of;

COOH, CSSH, CH(RSH)₂, CH(RNH₂)₂, CH(ROH)₂, and CH(RCN)₂, wherein R is H or an alkyl group having from 1 to 3 carbon atoms, or an aryl group consisting of one phenyl ring in the presence of a templating agent, selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl mines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoromethylsulfonic acid.

13. The method of claim 12 wherein the templating agent is pyridine.

14. The method of claim 12 wherein the templating agent is ethanol.

15. The method of claim 12 wherein the ligand is benzene-1,3,5-tricarboxylic acid.

16. The method of claim 12 wherein the ligand is benzene-1,4-dicarboxylic acid.

17. The method of claim 12 wherein the ligand is benzene-1,2, 4, 5-tetracarboxylic acid.

18. The method of claim 12 wherein the ligand is adamantane-1,3,5,7-tetracarboxylic acid.

19. The method of claim 12 wherein the ligand is 1,1'"'"',1",1'"'"'"-methanetetracarboxylic acid.

20. The method of claim 12 wherein the microporous materials are prepared in the presence of a ligand containing one or more monodentate functional groups said ligand selected from the group consisting of:

a. alkyl amines containing at least one alkyl group containing 1 to 10 carbon atoms;

b. aryl amines containing from 1 to 5 phenyl rings;

c. alkyl alcohols containing at least one alkyl group having from 1 to 10 carbon atoms;

d. aryl alcohols containing from 1 to 5 phenyl rings;

e. alkyl thioIs containing at least one alkyl group having from 1 to 10 carbon atoms;

f. aryl thiols containing from 1 to 5 phenyl rings;

g. alkyl cyanides containing at least one alkyl group having from 1 to 10 carbon atoms;

h. aryl cyanides containing from 1 to 5 phenyl rings; and

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, thiocyanide, and isonitrile, and the corresponding acids and salts of said inorganic anions.

21. The method of claim 20 wherein the ligand containing one or more monodentate functional groups is selected from the group consisting of:

pyridine, 4,4'"'"'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, trimethylamine, triethylamine, tripropylamine, 2-aminopropane, triethanolamine, ethylbutylamine, piperidine, cyclohexylamine, 2-methylpyridine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N'"'"'-dimethylpiperazine, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methyl-piperidine, 4-methylpyridine, 1,4-diaminocyclohexane, morpholine, aniline, 1,4-diaminobenzene, 1,3,5-triaminobenzene, 1,3,5-triazine, imidazole, pyrazine, methanol, dihydroxymethane, trihydroxymethane, tetrahydroxymethane, ethanol, ethylene glycol, 1,1,2,2-tetrahydroxyethane, 1-propanol, 2-propanol, propylene glycol, 1,3-propanediol, glycerol, 1,1,3,3-tetrahydroxypropane, allyl alcohol, n-butanol, sec-butanol, iso-butanol, tert-butanol, 1,4-butanediol, 1,3-butanediol, 1,1,4,4-tetrahydroxybutane, n-pentanol, sec-pentanol, iso-pentanol, tert-pentanol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,3,5-trihydroxypentane, n-hexanol, sec-hexanol, iso-hexanol, tert-hexanol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,3,6-trihydroxyhexane, cyclohexanol, 1,4-dihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, 1,3,5-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4,5-tetrahydroxybenzene, thiomethane, thioethane, thiopropane, thiocyclohexane, thiobenzene, 1,3-dithiopropane, 1,4-dithiobutane, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

22. The method according to claim 12 in which the reaction mixture containing the microporous material product is heated from 30°

C. to 500°

C. to partially or completely remove the templating agent.

23. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Sc³⁺, Ti⁴⁺, V⁴⁺, V³⁺, Cr³⁺, Mo³⁺, Mn³⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co³⁺, Co²⁺, Ni²⁺, Ni⁺, Cu²⁺, Cu⁺, Ag⁺, Zn²⁺, Cd²⁺, Al³⁺, Sn⁴⁺, Sn²⁺, and Bi⁵⁺, Bi³⁺, Bi⁺ ;

along with the corresponding metal salt counteranion with, one or more ligand substructures being at least one of;

methane, tetraphenylmethane, ethylene, benzene, naphthylene, adamantane, and squarane;

said ligand substructure having bound thereto multidentate functional groups, X, which are covalently bound to the substructure of the ligand, wherein X is a functional group selected from the groups consisting of;

COOH, CSSH, CH(RSH)₂, CH(RNH₂)₂, CH(ROH)₂, and CH(RCN)₂, wherein R is H or methyl or an aryl group consisting of one phenyl ring. in the presence of a ternplating agent, selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene-chloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoro-methylsulfonic acid.

24. The method of claim 23 wherein the templating agent is pyridine.

25. The method of claim 23 wherein the templating agent is ethanol.

26. The method of claim 23 wherein the ligand is benzene-1,3,5-tricarboxylic acid.

27. The method of claim 23 wherein the ligand is benzene-1,4-dicarboxylic acid.

28. The method of claim 23 wherein the ligand is benzene-1,2, 4, 5-tetracarboxylic acid.

29. The method of claim 23 wherein the ligand is adamantane-1,3,5,7-tetracarboxylic acid.

30. The method of claim 23 wherein the ligand is 1,1'"'"',1",1'"'"'"-methanetetracarboxylic acid.

31. The method of claim 23 wherein the microporous materials are prepared in the presence of a ligand containing one or more monodentate functional groups said ligand selected from the group consisting of:

a. alkyl amines containing at least one alkyl group containing 1 to 10 carbon atoms;

b. aryl amines containing from 1 to 5 phenyl rings;

c. alkyl alcohols containing at least one alkyl group having from 1 to 10 carbon atoms;

d. aryl alcohols containing from 1 to 5 phenyl rings;

e. alkyl thiols containing at least one alkyl group having from 1 to 10 carbon atoms;

f. aryl thioIs containing from 1 to 5 phenyl rings;

g. alkyl cyanides containing at least one alkyl group having from 1 to 10 carbon atoms; and

h. aryl cyanides containing from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, thiocyanide, and isonitrile, and the corresponding acids and salts of said inorganic anions.

32. The method of claim 31 wherein the ligand contains monodentate functional groups selected from the group consisting of:

pyridine, 4,4'"'"'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, trimethylamine, triethylamine, tripropylamine, 2-aminopropane, triethanolamine, aniline, 1,4-diaminobenzene, 1,3,5-triaminobenzene, 1,3,5-triazine, imidazole, pyrazine, ethanol, ethylene glycol, 1-propanol, 2-propanol, propylene glycol, n-butanol, sec-butanol, iso-butanol, tert-butanol, 1,4-butanediol, phenol, benzyl alcohol, hydroquinone, 1,3,5-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,3-trihydroxybenzene, thioethane, thiopropane, thiocyclohexane, thiobenzene, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

33. The method according to claim 23 in which the reaction mixture containing the microporous material product is heated from 30°

C. to 500°

C. to partially or completely remove the templating agent.

34. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Mn³⁺, Mn²⁺, Fe³⁺, Fe²⁺, Co³⁺, Co²⁺, Ni²⁺, Ni⁺, Cu²⁺, Cu⁺, Ag⁺, Zn²⁺, Cd²⁺ ;

along with the corresponding metal salt counteranion with, one or more ligand substructures being at least one of;

methane, tetraphenylmethane, ethylene, benzene, and adamantane, said ligand substructure having bound thereto carboxylic acid functional groups;

in the presence of a templating agent selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions selected from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene-chloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoromethylsulfonic acid.

35. The method of claim 34 wherein the templating agent is pyridine.

36. The method of claim 34 wherein the templating agent is ethanols.

37. The method of claim 34 wherein the ligand is benzene-1,3,5-tricarboxylic acid.

38. The method of claim 34 wherein the ligand is benzene-1,4-dicarboxylic acid.

39. The method of claim 34 wherein the ligand is benzene-1,2,4,5-tetracarboxylic acid.

40. The method of claim 34 wherein the ligand is adamantane-1,3,5,7-tetracarboxylic acid.

41. The method of claim 34 wherein the ligand is 1,1'"'"',1",1'"'"'"-methanetetracarboxylic acid.

42. The method of claim 34 wherein the microporous materials are prepared in the presence of a ligand containing one or more monodentate functional groups said ligand selected from the group consisting of:

a. alkyl amines containing at least one alkyl group containing 1 to 10 carbon atoms;

b. aryl amines containing from 1 to 5 phenyl rings;

c. alkyl alcohols containing at least one alkyl group having from 1 to 10 carbon atoms;

d. aryl alcohols containing from 1 to 5 phenyl rings;

e. alkyl thiols containing at least one alkyl group having from 1 to 10 carbon atoms;

f. aryl thiols containing from 1 to 5 phenyl rings;

g. alkyl cyanides containing at least one alkyl group having from 1 to 10 carbon atoms;

h. aryl cyanides containing from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, thiocyanide, and isonitrile, and the corresponding acids and salts of said inorganic anions.

43. The method of claim 42 wherein the ligand contains monodentate functional groups selected from the group consisting of:

pyridine, 4,4'"'"'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, triethylamine, tripropylamine, 2-aminopropane, triethanolamine, aniline, 1,4-diaminobenzene, 1,3,5-triaminobenzene, imidazole, ethanol, ethylene glycol, 1-propanol, 2-propanol, propylene glycol, n-butanol, tert-butanol, phenol, benzyl alcohol, hydroquinone, 1,3,5-trihydroxybenzene, thioethane, thiopropane, thiobenzene, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

44. The method according to claim 34 in which the reaction mixture containing the microporous material product is heated from 30°

C. to 500°

C. to partially or completely remove the ternplating agent.

45. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Fe³⁺, Fe²⁺, Co³⁺, Co²⁺, Ni²⁺, Ni⁺, Zn²⁺, along with the corresponding metal salt counteranion with, one or more ligand substructures being at least one of;

benzene and adamantane;

said ligand substructure having bound thereto carboxylic acid functional groups;

in the presence of a templating agent, selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions selected from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoromethylsulfonic acid.

46. A method for the preparation of microporous materials which comprises the steps of:

Admixing a solution containing one or more metal ions from the group consisting of;

Co³⁺, Co²⁺, Ni²⁺, Ni⁺, Zn²⁺, along with the corresponding metal salt counteranion with the benzene ligand substructure;

said ligand substructure having bound thereto carboxylic acid functional groups;

in the presence of a templating agent, selected from the group consisting of;

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings,

e. alkyl organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containings linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions selected from the group consisting of;

sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of said inorganic anions;

j. ammonia, carbon dioxide, methane, oxygen, argon, nitrogen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine,and trifluoromethylsulfonic acid.

47. The method of claim 46 where the templating agent is pyridine.

48. The method of claim 46 where the templating agent is ethanol.

49. The method of claim 46 wherein the ligand is benzene-1,3,5-tricarboxylic acid.

50. The method of claim 46 wherein the ligand is benzene-1,4-dicarboxylic acid.

51. The method of claim 46 where the ligand is benzene-1,2,4,5-tetracarboxylic acid.

52. The method of claim 46 where the ligand is adamantane-1,3,5,7-tetracarboxylic acid.

53. The method of claim 46 wherein the ligand is 1,1'"'"',1",1'"'"'"-methanetetracarboxylic acid.

54. The method of claim 46 wherein the ligand contains monodentate functional groups selected from the group consisting of:

pyridine, 4,4'"'"'-bipyridine, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, triethylamine, triethanolamine, aniline, 1,4-diaminobenzene, imidazole, ethylene glycol, propylene glycol, phenol, hydroquinone, 1,3,5-trihydroxybenzene, thiobenzene, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

55. The method of claim 54 wherein the ligand contains monodentate functional groups selected from the group consisting of:

pyridine, aniline, 4,4'"'"'-bipyridine, 1,4-diaminobenzene, phenol, hydroquinone, ethylenediamine, propylenediamine, 2-aminoethanol, 3-aminopropanol, thiobenzene, 1,4-dithiobenzene, and 1,3,5-trithiobenzene, 1,4-dicyanobenzene, and 1,3,5-tricyanobenzene.

56. The method of claim 54 wherein the ligand contains monodentate functional groups selected from the group consisting of:

pyridine, ethylenediamine, propylenediamine, 4,4'"'"'-bipyridine, 2-aminoethanol, 3-aminopropanol.

57. The method of claim 46 wherein the ligand has an aryl substructure, and wherein said substructure is all carbon or a mixture of carbon, with an element selected from the group consisting of nitrogen, oxygen, sulfur, boron, phosphorous, silicon and aluminum.

58. The method of claim 46 in which the metal ion is added to the reaction in the form of Zn(NO₃).6H₂ O, the templating agent is ethanol, the ligand containing multidentate functional groups is benzene-1,3,5-tricarboxylic acid, the ligand containing monodentate functional group is nitrate, and triethylamine and ethanol are cosolvents, and said reaction is carried out in a polyethylene oxide gel at room temperature to give large colorless crystals of Zn₂ (C₉ H₃ O₆).NO₃ (H₂ O)₃.5 (C₂ H₅ OH)₀.5.

59. The method of claim 46 in which the metal ion is added to the reaction in the form of Zn(NO₃).6H₂ O, the templating agent is ethanol, the ligand containing multidentate functional groups is benzene-1,3,5-tricarboxylic acid, the ligand containing monodentate functional group is nitrate, and triethylamine and ethanol are cosolvents, and said reaction is carried out at room temperature to give colorless crystals of Zn₂ (C₉ H₃ O₆).NO₃ (H₂ O)₃.5 (C₂ H₅ OH)₀.5.

60. The method of claim 46 in which the metal ion is added as Co(NO₃)₂.6H₂ O, the ligand containing multidentate functional groups is benzene-1,3,5-tricarboxylic acid, and pyridine is the ligand containing monodentate functional group and the templating agent, and wherein the reaction is carried out in an ethanol/1,2-dichloroethane solution in the presence of a polyethylene oxide gel to give CoC₆ H₃ (COOH_1/3)₃ (NC₅ H₅)₂.2/3 NC₅ H₅.

61. The method of claim 46 in which the metal ion is added as Co(NO₃)₂.6H₂ O, the ligand containing multidentate functional groups is benzene-1,3,5-tricarboxylic acid, and pyridine is the ligand containing monodentate functional group and the templating agent, and said reaction is carried out in ethanol to give CoC₆ H₃ (COOH_1/3)₃ (NC₅ H₅)₂.2/3 NC₅ H₅.