Design, synthesis and characterization of metal organic frameworks

Patent metadata

Field	Value
Publication number	US-11905246-B2
Application number	US-202117171127-A
Country	US
Kind code	B2
Filing date	Feb 9, 2021
Priority date	May 26, 2014
Publication date	Feb 20, 2024
Grant date	Feb 20, 2024

Abstract

A molecular building block composition can include a metal ion component; and a ligand component including a core including at least one functional group associated with the metal ion component and the core.

First claim

What is claimed is:

1. A metal organic framework (MOF) comprising:
a plurality of polynuclear metal clusters, wherein at least one of the polynuclear metal clusters includes a rare earth metal; and
a plurality of polydentate ligands each linking two or more of the polynuclear metal clusters;
wherein the MOF has a ftw (For Twelve) or ftw-a topology, wherein the polydentate ligand is a square or quadrangular ligand.

2. The MOF of claim 1 , wherein the polydentate ligand is selected from the group consisting of 3,3″,5,5″-tetrakis(4-carboxyphenyl)-p-terphenyl, 3′,3″,5′,5″-tetrakis(4-carboxyphenyl)-1.4-diphenylnaphthalene, 3′,3″,5′,5″-tetrakis(4-carboxyphenyl)-9,10-diphenylanthracene, 3,3″,5′,5″-tetra-2-(4-carboxyphenyl)ethynyl-p-terphenyl, and 4,4′,4″,4′″-((benzene-1,2,4,5-tetrayltetrakis(methylene))tetrakis(oxy))tetrabenzoic acid.

3. The MOF of claim 1 , wherein the polynuclear cluster is a cuboctahedral 12-c molecular building block (MBB).

4. The MOF of claim 1 , wherein the rare earth metal is selected from yttrium, ytterbium, terbium, and combinations thereof.

5. The MOF of claim 1 , wherein the MOF has a (1, 12) or (4, 12) connectivity.

6. A method of making of metal organic framework (MOF) having a ftw or ftw-a topology comprising:
contacting a rare earth metal ion component and a polydentate ligand to form a mixture;
allowing the mixture to react whereby a crystalline metal organic framework with a ftw or ftw-a topology forms, wherein the polydentate ligand is a square or quadrangular ligand.

7. The method of claim 6 , wherein the mixture further comprises a reaction modulator.

8. The method of claim 7 , wherein the reaction modulator is F-Benzoic acid.

9. The method of claim 6 , wherein the polydentate ligand is selected from the group consisting of 3,3″,5,5″-tetrakis(4-carboxyphenyl)-p-terphenyl, 3′,3″,5′,5″-tetrakis(4-carboxyphenyl)-1,4-diphenylnaphthalene, 3 ‘,3 “,5’,5”-tetrakis (4-carboxyphenyl)-9, 1 0-diphenylanthracene, 3,3″,5,5″-tetra-2-(4-carboxyphenyl)ethynyl-p-terphenyl, and 4,4′,4″,4′″-((benzene-1,2,4,5-tetrayltetrakis(methylene))tetrakis(oxy))tetrabenzoic acid.

10. The method of claim 6 , wherein the mixture further comprises a solvent.

11. The method of claim 6 , wherein the rare earth metal ion component forms a 12-c molecular building block (MBB) represented by a formula M 6 (OH) 8 L 12 , where M is the rare earth metal and L is the polydentate ligand.

12. The method of claim 6 , wherein the rare earth metal is selected from yttrium, ytterbium, terbium, and combinations thereof.

13. A method of separating a compound from a mixture of gases comprising:
contacting a metal organic framework (MOF) having a ftw or ftw-a topology with a mixture of gases including at least one compound selected from the group consisting of H 2 , N 2 , O 2 , CO 2 , H 2 S, H 2 O, hydrocarbons, linear hydrocarbons, branching hydrocarbons, and aromatic hydrocarbons; and
adsorbing the at least one compound in the MOF, thereby separating the compound from the mixture;

wherein the MOF having a ftw or ftw-a topology comprises a plurality of polynuclear metal clusters, wherein at least one of the polynuclear metal clusters includes a rare earth metal; and a plurality of polydentate ligands each linking two or more of the polynuclear metal clusters wherein the plurality of polydentate ligands is a square or quadrangular ligand.

14. The method of claim 13 , wherein the polydentate ligand is selected from the group consisting of 3,3″,5,5″-tetrakis(4-carboxyphenyl)-p-terphenyl, 3′,3″,5′,5″-tetrakis(4-carboxyphenyl)-1,4-diphenylnaphthalene, 3′,3″,5′,5″-tetrakis(4-carboxyphenyl)-9,10-diphenylanthracene, 3,3″,5,5″-tetra-2-(4-carboxyphenyl)ethynyl-p-terphenyl, and 4,4′,4″,4′″-((benzene-1,2,4,5-tetrayltetrakis(methylene))tetrakis(oxy))tetrabenzoic acid.

15. The method of claim 13 , wherein the polynuclear cluster is a cuboctahedral 12-c molecular building block (MBB).

16. The method of claim 13 , wherein the rare earth metal is selected from yttrium, ytterbium, terbium, and combinations thereof.

17. The method of claim 13 , wherein the MOF has a (1,12) or (4,12) connectivity.

Assignees

• Univ King Abdullah Sci & Tech
• King Abdullah Univ Of Science & Technology

Inventors

• Eddaoudi Mohamed
• Xue Dongxu
• Luebke Ryan
• Guillerm Vincent
• Peedikakkal Abdul Malik Puthan
• Adil Karim
• Weselinski Lukasz

Classifications

• C07D209/88 Primary

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system · CPC title

• B01J20/226

  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 title

• B01J31/1691

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/06

  Washing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title