Compositions and methods comprising porous metal organic frameworks and related uses

Patent metadata

Field	Value
Publication number	US-9758532-B2
Application number	US-201414270385-A
Country	US
Kind code	B2
Filing date	May 6, 2014
Priority date	May 6, 2013
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

Compositions and methods comprising metal organic frameworks (MOFs) and related uses are generally provided. In some embodiments, an MOF comprises a plurality of metal ions, each coordinated with at least one ligand comprising at least two unsaturated N-heterocyclic aromatic groups arranged about an organic core. In some embodiments, an MOF may be used in applications related to water adsorption.

First claim

What is claimed is:

1. A metal organic framework (MOF) comprising:
a plurality of metal ions, each coordinated with at least one ligand, wherein each ligand has the structure [Q-(Ar) m ] m− , wherein:
each Ar is the same or different and is an unsaturated N-heterocyclic aromatic group selected from the group consisting of pyrazolate, imidazolate, and tetrazolate;
m is 2; and
Q comprises the structure:

wherein each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 , wherein each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

2. The MOF of claim 1 , wherein a portion of the metal ions are associated with two, three, or four ligands, and each of those ligands is individually associated with two metal ions.

3. The MOF of claim 1 , wherein a portion of the metal ions are associated with four ligands, and each of those ligand is individually associated with two metal ions.

4. The MOF of claim 1 , wherein each unsaturated N-heterocyclic group is a pyrazolate group.

5. The MOF of claim 1 , wherein each metal ion is a monovalent, divalent, or trivalent metal ion.

6. The MOF of claim 1 , wherein each metal ion is selected from the group consisting of Ag + , Cu + , and Au + .

7. The MOF of claim 1 , wherein each metal ion is selected from the group consisting of Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Pd 2+ , Pt 2+ , Ru 2+ , Cd 2+ , Zn 2+ , Pb 2+ , Hg 2+ , V 2+ , Cr 2+ , and Ni +2 .

8. The MOF of claim 1 , wherein each metal ion is Zn 2+ .

9. The MOF of claim 1 , wherein each metal ion is selected from the group consisting of Fe 3+ , V 3+ , Ti 3+ , Sc 3+ , Al 3+ , In 3+ , Ga 3+ , Mn 3+ , Co 3+ , and Cr 3+ .

10. The MOF of claim 1 , wherein the ligand comprises the structure:

wherein:
each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 ;
each L is the same or different and is absent or selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, and optionally substituted heteroarylene; and
each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

11. The MOF of claim 10 , wherein the ligand comprises the structure:

wherein:
each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 ; and
each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

12. The MOF of claim 10 , wherein each R 1 is hydrogen, halide, NHR′, or SR′, wherein each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

13. The MOF of claim 10 , wherein each R 1 is hydrogen, Br, NHEt, or SEt.

14. The MOF of claim 1 , wherein the MOF is porous.

15. A method, comprising:
using an MOF for water adsorption, wherein the MOF comprising a plurality of metal ions, each coordinated with at least one ligand,
wherein each ligand has the structure [Q-(Ar) m ] m− ,
wherein each Ar is the same or different and is an unsaturated N-heterocyclic aromatic selected from the group consisting of pyrazolate, triazolate, and tetrazolate, m is 2, 3, or 4, and Q comprises the structure:

wherein each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —CF 3 —NR′ 2 , —NHR′, and —NH 2 , wherein each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

16. The method of claim 15 , wherein m is 2.

17. The method of claim 15 , wherein a portion of the metal ions are associated with four ligands, and each of those ligand is individually associated with two metal ions.

18. The method of claim 15 , wherein each ligand comprises two pyrazolates.

19. The method of claim 15 , wherein each metal ion is selected from the group consisting of Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Pd 2+ , Pt 2+ , Ru 2+ , Cd 2+ , Zn 2+ , Pb 2+ , Hg 2+ , V 2+ , Cr 2+ , and Ni +2 .

20. The method of claim 15 , wherein each metal ion is Zn 2+ .

21. The method of claim 15 , wherein the ligand comprises the structure:

wherein:
each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 ;
each L is the same or different and is absent or selected from the group consisting of optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, and optionally substituted heteroarylene; and
each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

22. The method of claim 15 , wherein the ligand comprises the structure:

wherein:
each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 ; and
each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

23. The method of claim 15 , wherein the water uptake of the MOF at a relative humidity of approximately 40% is between about 0.2 and about 2 g of water per gram of MOF.

24. A metal organic framework (MOF) comprising:
a plurality of metal ions, each coordinated with at least one ligand, wherein each ligand has the structure [Q-(Ar) m ] m− , wherein:
each Ar is the same or different and is an unsaturated N-heterocyclic aromatic group selected from the group consisting of pyrazolate, triazolate, imidazolate, and tetrazolate;
m is 2; and
Q comprises the structure:

wherein each R 1 is the same or different and is selected from the group consisting of hydrogen, —NO 2 , —R′, —F, —Cl, —Br, —I, —CN, —NC, —SO 3 R′, —SO 3 H, —OR′, —OH, —SR′, —SH, —PO 3 R′, —PO 3 H, —CF 3 , —NR′ 2 , —NHR′, and —NH 2 , wherein each R′ is the same or different and is optionally substituted alkyl or optionally substituted aryl.

25. The MOF of claim 2 , wherein each Ar is triazolate.

Assignees

• Massachusetts Inst Technology
• Massacusetts Inst Of Tech

Inventors

• Dinca Mircea
• Wade Casey R

Classifications

• C07F3/06 Primary

  Zinc compounds · CPC title