Porous reactive framework

Patent metadata

Field	Value
Publication number	US-9512145-B2
Application number	US-200913140408-A
Country	US
Kind code	B2
Filing date	Dec 18, 2009
Priority date	Dec 18, 2008
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

This disclosure relates to porous frameworks for gas separation, sensing and drug/biomolecule delivery. More particularly, the disclosure relates to reactive porous frameworks for functionalization.

First claim

What is claimed is:

1. A method of generating a post-reactive framework (PRF) comprising:
generating a porous framework comprising a ZIF, a COF, a MOF or a BOF wherein a linking moiety of the porous framework comprises one or more reactive side groups selected from the group consisting of NH 2 , CN, OH, ═O, ═S, SH, P, Br, CL, I, F,

wherein X=1, 2, or 3; and
reacting the framework with a post framework reactant comprising a heterocyclic compound under conditions wherein the post framework reactant modifies the reactive side group to form a PRF.

2. The method of claim 1 , wherein the porous framework comprises a general structure M-L-M, wherein the M is a transition metal and L is a linking moiety.

3. The method of claim 2 , wherein L comprises a substructure covalently linked to an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings and a linking cluster covalently bound to the substructure.

4. The method of claim 2 , wherein the linking moiety is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 4 =NH 2 , CN, OH, ═O, ═S, SH, P, Br, CL, I, F,

wherein X=1, 2, or 3.

5. The method of claim 1 , further comprising a metal or metal containing compound that chelates to and adds functional groups to the reactive side group.

6. The method of claim 5 , wherein the post framework reactant undergoes reaction with the porous framework that results in the tethering of organometallic complexes to the framework.

7. The method of claim 1 , wherein the heterocyclic compound has one or more multivalent heteroatoms, independently selected from N, O and S, as a part of the ring structure.

8. The method of claim 7 , wherein the heterocyclic compound comprises a monocyclic heterocycle.

9. The method of claim 8 , wherein the monocyclic heterocycle is selected from the group consisting of: aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane 2,3-dihydrofuran, 2,5-dihydrofuran tetrahydrofuran, thiophane, piperidine, 1,2,3,6-tetrahydro-pyridine, piperazine, morpholine, thiomorpholine, pyran, thiopyran, 2,3-dihydropyran, tetrahydropyran, 1,4-dihydropyridine, 1,4-dioxane, 1,3-dioxane, dioxane, homopiperidine, 2,3,4,7-tetrahydro-1H-azepine homopiperazine, 1,3-dioxepane, 4,7-dihydro-1,3-dioxepin, and hexamethylene oxide.

10. The method of claim 8 , wherein the heterocycle is selected from the group consisting of:

11. The method of claim 1 , wherein the reaction is carried out with reagents that result in a modification of a reactive side group so that the modified reactive side group extends into the pore of the framework thereby modifying pore size or charge.

12. The method of claim 1 , wherein the post reactive framework comprises a modification of the linker moiety comprising an aliphatic sulfonic acid group.

13. The method of claim 1 , wherein a guest species is removed from the porous framework prior to reacting the framework with the post framework reactant.

14. A method of generating post-reactive framework (PRF) comprising:
generating a porous framework comprising a ZIF, a COF, a MOF or a BOF wherein a linking moiety of the porous framework comprises one or more reactive side groups selected from the group consisting of secondary or tertiary amine, CN, OH, ═O, ═S, SH, P, Br, CL, I, F,

wherein X=1, 2, or 3; and
reacting the framework with a post framework reactant comprising a heterocyclic compound under conditions wherein the post framework reactant modifies the reactive side group to form a PRF.

15. The method of generating post-reactive framework (PRF) of claim 14 , wherein:
the linking moiety of the porous framework comprises one or more reactive side groups selected from the group consisting of CN, OH, ═O, ═S, SH, P, Br, CL, I, F,

wherein X=1, 2, or 3.

16. The method of generating post-reactive framework (PRF) of claim 14 , wherein:
reacting the framework with a post framework reactant comprising the heterocyclic compound under conditions wherein the post framework reactant substitutes for the reactive side group to form a PRF.

17. The method of generating post-reactive framework (PRF) of claim 14 , wherein:
reacting the framework with a post framework reactant comprising the heterocyclic compound under conditions wherein the post framework reactant adds to the reactive side group to form a PRF.

18. The method of generating post-reactive framework (PRF) of claim 14 , wherein:
reacting the framework with a post framework reactant comprising the heterocyclic compound under conditions wherein the post framework reactant adds to the reactive side group and then the reactive side group is eliminated to form a PRF.

Assignees

• Yaghi Omar M
• Czaja Alexader U
• Morris William
• Hunt Joseph R
• Britt David Kyle
• Lee Chain
• Univ California
• Basf Se

Inventors

• Yaghi Omar M
• Czaja Alexader U
• Morris William
• Hunt Joseph R
• Britt David Kyle
• Lee Chain

Classifications

• C07F3/003 Primary

  without C-Metal linkages · CPC title