Monomers, oligomeric complexes, coordination polymers, and methods for their preparation and use

Patent metadata

Field	Value
Publication number	US-10087289-B2
Application number	US-201414149611-A
Country	US
Kind code	B2
Filing date	Jan 7, 2014
Priority date	Feb 18, 2011
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

Implementations and techniques for preparing and using monomers, oligomeric complexes, and coordination polymers are generally disclosed.

First claim

What is claimed is:

1. A monomer compound ligand, comprising:
four pyridyl groups defined as pyridyl group Py 1 , pyridyl group Py 2 , pyridyl group Py 3 , and pyridyl group Py 4 ; and
a central linker portion, wherein:
pyridyl group Py 1 is covalently bonded to the central linker portion, pyridyl group Py 2 is covalently bonded to the central linker portion, pyridyl group Py 3 is covalently bonded to the central linker portion, and pyridyl group Py 4 is covalently bonded to the central linker portion, wherein Py 1 and Py 2 each is a 2-pyridyl moiety, and Py 3 and Py 4 each is a 4-pyridyl moiety,
the central linker portion is selected from the group consisting of a phenylenediamine group, a terphenyl diamine group, a biphenyl diamine group, and a (methylbenzene) 2 diamine group, and
Py 1 and Py 2 are attached to one of the amine groups of the central linker portion at ortho position to pyridinyl nitrogen and Py 3 and Py 4 are attached to the other amine group of the central linker portion at para position to pyridinyl nitrogen.

2. The monomer compound of claim 1 , wherein the central linker portion comprises the phenylenediamine group, wherein the phenylenediamine group has a 1,4 (para) orientation of the first amine group and the second amine group.

3. The monomer compound of claim 1 , having the structure (Py 1 Py 2 )N—C 6 H 4 —N(Py 3 Py 4 ).

4. A method of preparing the monomer compound ligand of claim 1 , the method comprising:
contacting a first bipyridylamine having pyridyl groups Py 1 and Py 2 and a second bipyridylamine having pyridyl groups Py 3 and Py 4 with a central linker portion having two reactive groups under conditions suitable to form the monomer compound ligand.

5. The method of claim 4 , wherein the contacting comprises contacting with the central linker portion comprising a phenyl group.

6. The method of claim 4 , wherein the contacting comprises simultaneously contacting the first bipyridylamine, the second bipyridylamine, and the central linker portion having two reactive groups.

7. The method of claim 4 , wherein the contacting is performed stepwise by first contacting the first bipyridylamine and the central linker portion having two reactive groups, followed by a second contacting with the second bipyridylamine.

8. The method of claim 4 , wherein the contacting comprises contacting the first bipyridylamine comprising 4,4-dipyridylamine, the second bipyridylamine comprising 2,2′-dipyridylamine, and the central linker portion having two reactive groups comprising 1,4-dibromobenzene.

9. The method of claim 4 , wherein the contacting results in the monomer compound ligand comprising N,N-di(2-pyridyl)-N′,N′-di(4-pyridyl)-1,4-phenylenediamine.

10. The method of claim 4 , wherein the contacting is performed in the presence of at least one solvent.

11. The method of claim 4 , wherein the contacting is performed in the presence of one or more of potassium carbonate, cupric sulfate, and 18-crown-6.

12. An oligomeric complex or a coordination polymer, comprising:
at least two ligands, wherein at least one of the at least two ligands comprises N,N-di(2-pyridyl)-N′N′-di(4-pyridyl)-1,4-phenylenediamine; and
at least one metal atom structurally incorporated with the at least two ligands.

13. The oligomeric complex or the coordination polymer of claim 12 , wherein at least one other of the at least two ligands comprises:
a central linker portion comprising at least one of a phenylenediamine group, a terphenyl diamine group, a biphenyl diamine group, poly-aromatic hydrocarbon (PAH) diamine group, or a (methylbenzene) 2 diamine group; and
four pyridyl groups defined as pyridyl group Py 1 , pyridyl group Py 2 , pyridyl group Py 3 , and pyridyl group Py 4 , wherein pyridyl group Py 1 is covalently bonded to the central linker portion, pyridyl group Py 2 is covalently bonded to the central linker portion, pyridyl group Py 3 is covalently bonded to the central linker portion, and pyridyl group Py 4 is covalently bonded to the central linker portion, wherein Py 1 and Py 2 each is a 2-pyridyl moiety, and Py 3 and Py 4 each is a 4-pyridyl moiety, and
wherein Py 1 and Py 2 are attached to one of the amine groups of the central linker portion at ortho position to pyridinyl nitrogen, and Py 3 and Py 4 are attached to the other amine group of the central linker portion at para position to pyridinyl nitrogen.

14. The oligomeric complex or the coordination polymer of claim 12 , wherein the at least one N,N-di(2-pyridyl)-N′N′-di(4-pyridyl)-1,4-phenylenediamine ligand is designated as L 2 , and the oligomeric complex or the coordination polymer includes at least one of ZnL 2 Cl 2 , ZnL 2 Br 2 , ZnL 2 I 2 , [Cd(L 2 ) 4 Cl 8 ] n .2nDMF, [CdL 2 Br 2 ] n , [CdL 2 I 2 ] n , [HgL 2 Cl 2 ] n .0.5nDMF, [Hg 2 (L 2 ) 2 Br 4 ].H 2 O, or [Hg 2 (L 2 ) 2 I 4 ].H 2 O, wherein n is an integer of 2 or more.

15. The oligomeric complex or the coordination polymer of claim 12 , wherein the at least one metal atom comprises at least one of zinc, cadmium, silver, or mercury.

16. The oligomeric complex or the coordination polymer of claim 12 , wherein the at least one metal atom comprises at least one metal atom structurally incorporated between the at least two ligands.

17. The oligomeric complex or the coordination polymer of claim 12 , wherein the at least two ligands are N,N-di(2-pyridyl)-N′N′-di(4-pyridy 1 )-1,4-phenylenediamine ligands.

18. The oligomeric complex or the coordination polymer of claim 17 , comprising the at least one metal atom structurally incorporated between the two N,N-di(2-pyridyl)-N′N′-di(4-pyridy 1 )-1,4-phenylenediamine ligands.

19. The oligomeric complex or the coordination polymer of claim 12 , wherein each ligand of the oligomeric complex or the coordination polymer is N,N-di(2-pyridyl)-N′N′-di(4-pyridy 1 )-1,4-phenylenediamine.

20. The oligomeric complex or the coordination polymer of claim 17 , wherein each N,N-di(2-pyridyl)-N′N′-di(4-pyridyl)-1,4-phenylenediamine ligand is designated as L 2 , and the oligomeric complex or the coordination polymer includes at least one of ZnL 2 Cl 2 , ZnL 2 Br 2 , ZnL 2 I 2 , [Cd(L 2 ) 4 Cl 8 ] n .2nDMF, [CdL 2 Br 2 ] n , [CdL 2 I 2 ] n , [HgL 2 Cl 2 ] n .0.5nDMF, [Hg 2 (L 2 ) 2 Br 4 ].H 2 O, or [Hg 2 (L 2 ) 2 I 4 ].H 2 O, wherein n is an integer of 2 or more.

21. The oligomeric complex or the coordination polymer of claim 12 , wherein the coordination polymer emits visible light upon exposure to UV light.

22. The oligomeric complex or the coordination polymer of claim 12 , wherein the at least two ligands comprise at least one N,N,N′,N′-tetra(4-pyridy 1 )-1,4-phenylenediamine and at least one N,N-di(2-pyridyl)-N′,N′-di(4-pyridyl)-1,4-phenylenediamine.

23. A method of preparing an oligomeric complex or a coordination polymer, the method comprising:
providing at least two ligands, wherein at least one of the at least two ligands comprises N,N-di(2-pyridyl)-N′,N′-di(4-pyridyl)-1,4-phenylenediamine;
providing at least one metal atom; and
contacting the at least two ligands and the at least one metal atom under conditions suitable to form the oligomeric complex or the coordination polymer of the at least two ligands and the at least one metal atom.

24. The method of claim 23 , wherein providing the at least one metal atom comprises providing at least one zinc salt, at least one cadmium salt, at least one mercury salt, at least one silver salt, or mixtures thereof.

Assignees

• Univ East China Science & Tech

Inventors

• Xie Yongshu

Classifications

• C07D213/36

  Radicals substituted by singly-bound nitrogen atoms (nitro radicals C07D213/26) · CPC title

• C07D213/74 Primary

  Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals · CPC title

• C07F3/06

  Zinc compounds · CPC title

• C07F3/003

  without C-Metal linkages · CPC title

• C08G79/00 Primary

  Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon {with or without the latter elements in the main chain of the macromolecule} · CPC title