Metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-9744520-B2
Application number	US-201314424780-A
Country	US
Kind code	B2
Filing date	Sep 3, 2013
Priority date	Sep 3, 2012
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The present invention relates to compounds capable of forming metal-organic frameworks (MOFs), particularly f-block metal MOFs which selectively sorb one component (e.g. para-xylene) from a mixture of components (e.g. m-/p-xylene mixture). The invention also relates to methods of producing and using said compounds.

First claim

What is claimed is:

1. A method of separating a desired component from a mixture of components, the method comprising:
selectively sorbing a desired component from a mixture of components by contacting the mixture of components with a sorbent material to selectively sorb the desired component within/to the sorbent material to produce a sorption complex;
removing any non-sorbed component(s) from contact with the sorption complex; and
optionally recovering the desired component from the sorption complex;

wherein the mixture of components comprises p-xylene and m-xylene; and
wherein the sorbent material comprises a metal-organic framework (MOF), which metal-organic framework comprises a compound comprising:
an f-block metal ion (M); and
a polydentate ligand (LIG) able to co-ordinate with M to provide a metal organic framework (MOF) structure;

wherein the LIG group is defined by Formula A (or a suitable ionised form thereof):
CORE L-R] n    (Formula A)

wherein:
n is an integer between 1 and 6 such that n individual and independently defined -L_R groups (i.e. L 1 -R 1 . . . L n -R n ) are attached to CORE;
CORE comprises one or more aromatic or heteroaromatic systems;
each L group is the same or different, each being independently either absent or a linker selected from the group including (1-3C)alkylene, (2-3C)alkenylene, (2-3C)alkynylene, O, S, SO, SO 2 , N(R′ a ), CO, CH(OR′ a ), CON(R′ a ), N(R′ a )CO, N(R′ a )CON(R′ a ), SO 2 N(R′ a ), N(R′ a )SO 2 , OC(R′ a ) 2 , SC(R′ a ) 2 and N(R′ a )C(R′ b ) 2 , wherein R′ a and R′ b are each independently hydrogen or (1-8C)alkyl;
each R group is the same or different, each being independently selected from an aryl or heteroaryl group bearing a lone pair of electrons capable of coordinating with M or substituted by a group bearing a lone pair of electrons capable of coordinating with M;
wherein CORE or any R group is optionally further substituted by one or groups selected from halogeno, trifluoromethyl, trifluoromethoxy, cyano, isocyano, nitro, hydroxy, mercapto, amino, formyl, carboxy (incl. carboxylic acid), carbamoyl, ureido, sulphonyl (incl. sulphonic acid), phosphoryl (incl. phosphonic acid), (1-8C)alkyl, (2-8C)alkenyl, (2-8C)alkynyl, (1-8C)alkoxy,
(2-8C)alkenyloxy, (2-8C)alkynyloxy, (1-8C)alkylthio, (1-8C)alkylsulphinyl, (1-8C)alkylsulphonyl, (1-8C)alkylamino, di-[(1-8C)alkyl]amino, (1-8C)alkoxycarbonyl,
N-(1-8C)alkylcarbamoyl, N,N-di-[(1-8C)alkyl]carbamoyl, (2-8C)alkanoyl, (2-8C)alkanoyloxy, (2-8C)alkanoylamino, N-(1-8C)alkyl-(2-8C)alkanoylamino, (3-6C)alkenoylamino, N-(1-6C)alkyl-(3-6C)alkenoylamino, (3-6C)alkynoylamino, N-(1-6C)alkyl-(3-6C)alkynoylamino, N′-(1-6C)alkylureido, N′,N′-di-[(1-6C)alkyl]ureido,
N-(1-6C)alkylureido, N,N′-di-[(1-6C)alkyl]ureido, N,N′,N′-tri-[(1-6C)alkyl]ureido, N-(1-6C)alkylsulphamoyl, N,N-di-[(1-6C)alkyl]sulphamoyl, (1-6C)alkanesulphonylamino and N-(1-6C)alkyl-(1-6C)alkanesulphonylamino;

or an (acceptable) salt and/or solvate thereof.

2. The method as claimed in claim 1 , wherein p-xylene is the desired component.

3. The method as claimed in claim 1 , wherein the f-block metal ion (M) is a lanthanide metal ion.

4. The method as claimed in claim 3 , wherein the f-block metal ion is selected from a lanthanum, cerium, praseodymium, neodymium, samarium, or europium ion.

5. The method as claimed in claim 1 , wherein the f-block metal ion is cerium (III)—i.e. Ce 3+ .

6. The method as claimed in claim 1 , wherein CORE is a benzene ring, optionally substituted as defined in claim 1 .

7. The method as claimed in claim 6 , wherein the LIG group is defined by Formula B (or a suitable ionised form thereof), optionally further substituted as defined in claim 1 :

where the L and R groups (i.e. L 1 , L 2 , L 3 , L 4 , and R 1 , R 2 , R 3 , R 4 ) are as defined in claim 1 .

8. The method as claimed in claim 1 , wherein the LIG group is selected from any one of (or a suitable ionised form of):

optionally further substituted as defined in claim 1 .

9. The method as claimed in claim 1 , wherein the LIG group is (or a suitable ionised form of):

optionally further substituted as defined in claim 1 .

10. A method of selectively sorbing a desired component from a mixture of components, the method comprising contacting the mixture of components with a sorbent material comprising a metal-organic framework (MOF), which metal-organic framework comprises a compound comprising:
an f-block metal ion (M); and
a polydentate ligand (LIG) able to co-ordinate with M to provide a metal organic framework (MOF) structure;

wherein the LIG group is defined by Formula A (or a suitable ionised form thereof):
CORE L-R] n    (Formula A)

wherein:
n is an integer between 1 and 6 such that n individual and independently defined -L_R groups (i.e. L 1 -R 1 . . . L n -R n ) are attached to CORE;
CORE comprises one or more aromatic or heteroaromatic systems;
each L group is the same or different, each being independently either absent or a linker selected from the group including (1-3C)alkylene, (2-3C)alkenylene, (2-3C)alkynylene, O, S, SO, SO 2 , N(R′ a ), CO, CH(OR′ a ), CON(R′ a ), N(R′ a )CO, N(R′ a )CON(R′ a ), SO 2 N(R′ a ), N(R′ a )SO 2 , OC(R′ a ) 2 , SC(R′ a ) 2 and N(R′ a )C(R′ b ) 2 , wherein R′ a and R′ b are each independently hydrogen or (1-8C)alkyl;
each R group is the same or different, each being independently selected from an aryl or heteroaryl group bearing a lone pair of electrons capable of coordinating with M or substituted by a group bearing a lone pair of electrons capable of coordinating with M;

wherein CORE or any R group is optionally further substituted by one or groups selected from halogeno, trifluoromethyl, trifluoromethoxy, cyano, isocyano, nitro, hydroxy, mercapto, amino, formyl, carboxy (incl. carboxylic acid), carbamoyl, ureido, sulphonyl (incl. sulphonic acid), phosphoryl (incl. phosphonic acid), (1-8C)alkyl, (2-8C)alkenyl, (2-8C)alkynyl, (1-8C)alkoxy,
(2-8C)alkenyloxy, (2-8C)alkynyloxy, (1-8C)alkylthio, (1-8C)alkylsulphinyl,
(1-8C)alkylsulphonyl, (1-8C)alkylamino, di-[(1-8C)alkyl]amino, (1-8C)alkoxycarbonyl,
N-(1-8C)alkylcarbamoyl, N,N-di-[(1-8C)alkyl]carbamoyl, (2-8C)alkanoyl,
(2-8C)alkanoyloxy, (2-8C)alkanoylamino, N-(1-8C)alkyl-(2-8C)alkanoylamino,
(3-6C)alkenoylamino, N-(1-6C)alkyl-(3-6C)alkenoylamino, (3-6C)alkynoylamino,
N-(1-6C)alkyl-(3-6C)alkynoylamino, N′-(1-6C)alkylureido, N′,N′-di-[(1-6C)alkyl]ureido,
N-(1-6C)alkylureido, N,N′-di-[(1-6C)alkyl]ureido, N,N′,N′-tri-[(1-6C)alkyl]ureido,
N-(1-6C)alkylsulphamoyl, N,N-di-[(1-6C)alkyl]sulphamoyl, (1-6C)alkanesulphonylamino and N-(1-6C)alkyl-(1-6C)alkanesulphonylamino;
or an (acceptable) salt and/or solvate thereof to selectively sorb the desired component within/to the sorbent material;
wherein the mixture of components comprises p-xylene and m-xylene.

Assignees

• Univ Liverpool

Inventors

• Rosseinsky Matthew J
• Perkins Catherine G
• Warren John Edward
• Jelfs Kim Elizabeth
• Boldrin Paul

Classifications

• B01J20/226 Primary

  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

• C07C63/331

  with all carboxyl groups bound to non-condensed rings · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• C07C7/12 Primary

  by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers · CPC title

• C07C51/347

  by reactions not involving formation of carboxyl groups · CPC title