Metal-organic materials and method for preparation

Patent metadata

Field	Value
Publication number	US-9611218-B2
Application number	US-201414904708-A
Country	US
Kind code	B2
Filing date	Jul 13, 2014
Priority date	Jul 14, 2013
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

The present invention provides metal-organic materials, more specifically organometallic polymers, comprising polypyridyl organic ligands such as tetrakis(4-(pyridin-4-ylethynyl)phenyl)methane, tetrakis(4-(2-(pyridin-4-yl)vinyl)phenyl)methane,3,5,7-tetrakis(4-(pyridin-4-ylethynyl)phenyl)adamantane or 1,3,5,7-tetrakis(4-(2-(pyridine-4-yl)vinyl)phenyl)adamantine, and metal ions structurally coordinated with said ligands, and having three-dimensional crystalline micro or sub-micro structure; as well as a method for the preparation thereof. These metal-organic materials are useful as adsorbents in processes for gas adsorption or separation.

First claim

The invention claimed is:

1. A metal-organic material, having a three-dimensional (3D) crystalline micro or sub-micro structure, comprising at least two ligands, at least two metal ions structurally coordinated with said ligands, and counter anions, wherein each one of the ligands is of the general formula I:
R 1 (R 2 —R 3 —R 4 ) 4 ,  I

wherein
R 1 is C or adamantane-1,3,5,7-tetrayl;
R 2 and R 3 each independently is absent, or selected from (C 1 -C 8 )alkylene, (C 2 -C 8 )alkenylene, (C 2 -C 8 )alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl, heteroarylene-diyl, or —N═N—, wherein said alkylene, alkenylene, alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl and heteroarylene-diyl may optionally be substituted with one or more groups each independently selected from halogen, —OR 6 , —CN, —COR 6 , —COOR 6 , —CON(R 6 ) 2 , —OCOOR 6 , —OCON(R 6 ) 2 , —(C 1 -C 4 )alkyl, —O—(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkylene-COOR 6 , —N(R 6 ) 2 , —NO 2 , —SR 6 , —SO 2 R 6 , or —S(═O)R 6 , or said alkylene, alkenylene and alkynylene may optionally be interrupted by one or more identical or different heteroatoms selected from S, O or N, and/or at least one group selected from —N═N—, —NH—CO—, —CO—NH—, —N(C 1 -C 4 alkyl)-, —N(C 6 -C 10 aryl)-, or —(C 6 -C 10 )arylene-diyl-, wherein R 6 each independently is H, (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl or (C 2 -C 4 )alkynyl;
R 4 each independently is a pyridyl of the formula II, 2,2′-bipyridyl of the formula III, or 2,2′:6′,2″-terpyridyl of the formula IV, linked through a carbon atom thereof; and

R 5 each independently is H, —COOH, —CN, —OH, or —NH 2 .

2. The metal-organic material of claim 1 , wherein R 2 and R 3 each independently is absent, or selected from (C 1 -C 8 )alkylene, (C 2 -C 8 )alkenylene, (C 2 -C 8 )alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl, heteroarylene-diyl, or —N═N—, wherein said alkylene, alkenylene, alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl and heteroarylene-diyl may optionally be substituted with one or more groups each independently selected from halogen, —OH, —CN, —COH, —COOH, —CONH 2 , —OCOOH, —OCONH 2 , —(C 1 -C 4 )alkyl, —O—(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkylene-COOH, —NH 2 , —NO 2 , —SH, —SO 2 H, or —S(═O)H, or said alkylene, alkenylene and alkynylene may optionally be interrupted by one or more identical or different heteroatoms selected from S, O or N, and/or at least one group selected from —N═N—, —NH—CO—, —CO—NH—, —N(C 1 -C 4 alkyl)-, —N(C 6 -C 10 aryl)-, or —(C 6 -C 10 )arylene-diyl-.

3. The metal-organic material of claim 2 , wherein R 2 and R 3 each independently is absent, or selected from (C 1 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl, heteroarylene-diyl, or —N═N—, wherein said alkylene, alkenylene, alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl and heteroarylene-diyl may optionally be substituted with halogen, —OH, —CN, —COH, —COOH, —CONH 2 , —OCOOH, —OCONH 2 , —(C 1 -C 2 )alkyl, —O—(C 1 -C 2 )alkyl, —(C 1 -C 2 )alkylene-COOH, —NH 2 , —NO 2 , —SH, —SO 2 H, or —S(═O)H, or said alkylene, alkenylene and alkynylene may optionally be interrupted by one or more identical or different heteroatoms selected from S, O or N, and/or at least one group selected from —N═N—, —NH—CO—, —CO—NH—, —N(C 1 -C 2 alkyl)-, —N(C 6 aryl)-, or —(C 6 )arylene-diyl-.

4. The metal-organic material of claim 3 , wherein R 2 and R 3 each independently is absent, or selected from (C 1 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, arylene-diyl, or heteroarylene-diyl.

5. The metal-organic material of claim 4 , wherein (i) one of R 2 and R 3 is absent and another of R 2 and R 3 is (C 2 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, arylene-diyl, or heteroarylene-diyl; (ii) one of R 2 and R 3 is (C 2 -C 4 )alkylene, (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene, and another of R 2 and R 3 is arylene-diyl, or heteroarylene-diyl; or (iii) both R 2 and R 3 are absent.

6. The metal-organic material of claim 5 , wherein R 2 is (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene, and R 3 is (C 6 )arylene-diyl; or R 2 is (C 6 )arylene-diyl, and R 3 is (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene.

7. The metal-organic material of claim 1 , wherein R 4 each independently is a pyridyl of the formula II, wherein R 5 each independently is H, —COOH, —CN, —OH, or —NH 2 , preferably H or —COOH.

8. The metal-organic material of claim 1 ,
wherein
R 1 is C or adamantane-1,3,5,7-tetrayl;
R 2 and R 3 each independently is absent, or selected from (C 1 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl, heteroarylene-diyl, or —N═N—, wherein said alkylene, alkenylene, alkynylene, cycloalkylene, heterocycloalkylene, arylene-diyl and heteroarylene-diyl may optionally be substituted with one or more groups each independently selected from halogen, —OH, —CN, —COH, —COOH, —CONH 2 , —OCOOH, —OCONH 2 , —(C 1 -C 2 )alkyl, —O—(C 1 -C 2 )alkyl, —(C 1 -C 2 )alkylene-COOH, —NH 2 , —NO 2 , —SH, —SO 2 H, or —S(═O)H, or said alkylene, alkenylene and alkynylene may optionally be interrupted by one or more identical or different heteroatoms selected from S, O or N, and/or at least one group selected from —N═N—, —NH—CO—, —CO—NH—, —N(C 1 -C 2 alkyl)-, —N(C 6 aryl)-, or —(C 6 )arylene-diyl-;
R 4 each independently is pyridyl of the formula II; and
R 5 each independently is H, —COOH, —CN, —OH, or —NH 2 , preferably H or —COOH.

9. The metal-organic material of claim 8 , wherein R 2 and R 3 each independently is absent, or selected from (C 1 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, arylene-diyl, or heteroarylene-diyl; R 4 is a pyridyl of the formula II linked through the carbon atom para to the nitrogen atom; and R 5 is H or —COOH.

10. The metal-organic material of claim 9 , wherein (i) one of R 2 and R 3 is absent and another of R 2 and R 3 is (C 2 -C 4 )alkylene, (C 2 -C 4 )alkenylene, (C 2 -C 4 )alkynylene, arylene-diyl, or heteroarylene-diyl; (ii) one of R 2 and R 3 is (C 2 -C 4 )alkylene, (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene, and another of R 2 and R 3 is arylene-diyl, or heteroarylene-diyl; or (iii) both R 2 and R 3 are absent.

11. The metal-organic material of claim 10 , wherein R 2 is (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene, and R 3 is (C 6 )arylene-diyl; or R 2 is (C 6 )arylene-diyl, and R 3 is (C 2 -C 4 )alkenylene or (C 2 -C 4 )alkynylene.

12. The metal-organic material of claim 11 , wherein R 2 is (C 6 )arylene-diyl; and R 3 is (C 2 )alkenylene or (C 2 )alkynylene.

13. The metal-organic material of claim 12 , wherein:
(i) R 1 is C, and each one of said ligands is tetrakis(4-(pyridin-4-ylethynyl) phenyl)methane or tetrakis(4-(2-(pyridin-4-yl) vinyl)phenyl) methane, herein identified ligands L1 and L2, respectively; or
(ii) R 1 is adamantane-1,3,5,7-tetrayl, and each one of said ligands is 1,3,5,7-tetrakis(4-(pyridin-4-ylethynyl)phenyl)adamantane or 1,3,5,7-tetrakis(4-(2-(pyridin-4-yl)vinyl)phenyl)adamantane, herein identified ligands L3 and L4, respectively.

14. The metal-organic material of claim 1 , wherein said metal ions are ions of a transition metals selected from Os, Ru, Fe, Pt, Pd, Ni, Ir, Rh, Zn, Co, Cu, Re, Tc, Mn, V, Nb, Ta, Hf, Zr, Cr, Mo, W, Ti, Sc, Ag, Au, Y, or a combination thereof.

15. The metal-organic material of claim 14 , wherein said transition metal is Ni, Cu, Pd, Zn, or a c

Assignees

• Yeda Res & Dev
• Yeda Res & Dev

Inventors

• Van Der Boom Milko E
• Lahav Michal
• Balgley Renata
• Shankar Poopanal Sreejith

Classifications

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01D2253/204

  Metal organic frameworks (MOF's) · CPC title

• C07F1/08

  Copper compounds · CPC title

• C07D213/53

  Nitrogen atoms · CPC title

• C08L101/005

  Dendritic macromolecules · CPC title