Ligand exchange thermochromic systems and high ε ligands for same

• US 8,182,718 B2
• Filed: 09/04/2007
• Issued: 05/22/2012
• Est. Priority Date: 09/01/2006
• Status: Active Grant

• Current Assignee: Pleotint LLC
• Original Assignee: Pleotint LLC
• Inventors: Byker, Harlan J., Ogburn, Paul H. Jr., Vander Griend, Douglas A., Veldkamp, Brad S., Winkle, Derick D.
• Primary Examiner(s): Joyner, Kevin
• Application Number:
  US11/849,624
• Publication Number:
  US 20080105851A1
• Time in Patent Office: 1,722 Days
• Field of Search: 252/408.1
• US Class Current: 252/408.1
• CPC Class Codes: B32B 17/10005 laminated safety glass or glazing
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10174 Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• CPC Class Codes: B32B 17/10477 thermochromic
• CPC Class Codes: B32B 17/10651 comprising colorants, e.g. dyes or pigments
• CPC Class Codes: B32B 17/10678 comprising UV absorbers or stabilizers, e.g. antioxidants
• CPC Class Codes: B32B 17/10761 containing vinyl acetal
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2369/00 Polycarbonates
• CPC Class Codes: C09K 2211/187 of the iron group metals, i.e. Fe, Co or Ni
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/0147 based on thermo-optic effects G02F1/132 takes precedence

Abstract

Ligand exchange of thermochromic, LETC, systems exhibiting a reversible change in absorbance of electromagnetic radiation as the temperature of the system is reversibly changed are described. The described LETC systems include one or more than one transition metal ion, which experiences thermally induced changes in the nature of the complexation or coordination around the transition metal ion(s) and, thereby, the system changes its ability to absorb electromagnetic radiation as the temperature changes.

In accordance with certain aspects of the present invention, a thermochromic system is disclosed comprising a transition metal ion and a ligand wherein the ligand comprises a nitrogen-containing five or six membered heterocyclic compound that coordinates through the nitrogen atom to the transition metal ion in a HεMLC formed between the transition metal ion and the ligand.

In accordance with other aspects of the present invention, thermochromic systems are disclosed comprising a transition metal ion with particularly useful ligands, such as phosphine compounds, tridentate ligands that coordinate through three nitrogen atoms, bidentate ligands, or ortho hindered pyridine monodentate ligands.

Claims

1. A thermochromic system comprising a nickel metal ion and a ligand, the ligand comprising a nitrogen-containing five- or six-membered heterocyclic compound that coordinates through the nitrogen atom to the nickel metal ion in a Hε

MLC formed between the nickel metal ion and the ligand, wherein heating the system from 25°

C. to 85°

C. causes an increase in the concentration of the Hε

MLC.

2. The thermochromic system of claim 1 wherein the ligand has the following structure:

3. The thermochromic system of claim 2 wherein the ligand is selected from the group consisting of a substituted or unsubstituted imidazole, benzimidazole, benzothiazole, pyrazole, indazole, imidazopyridine, triazole, thiazole, oxazole, thiatriazole, benzisoxazole, triazolo[1,5-a]pyrimidine, benzisoxazole, thiadiazole, benzothiadiazole, indolenine and mixtures thereof.

4. The thermochromic system of claim 1 wherein the ligand comprises a tridentate ligand that coordinates through 3 nitrogen atoms.

5. The thermochromic system of claim 4 wherein the tridentate ligand has the following structure:

6. The thermochromic system of claim 1 further comprising a halide;

and the ligand has the following structure;

7. The thermochromic system of claim 1 wherein

the ligand comprises a bidentate ligand that coordinates through a nitrogen atom and a phosphorus atom.

8. The thermochromic system of claim 1 wherein the ligand comprises an ortho hindered pyridine monodentate ligand having the following structure:

9. The thermochromic system of claim 1 wherein the ligand comprises a bidentate ligand that coordinates through two nitrogen atoms.

10. The thermochromic system of claim 9 wherein the bidentate ligand has the following structure:

11. The thermochromic system of claim 10 wherein the bidentate ligand is selected from the group consisting of 2,2′

-Butane-1,1-diylbis(1-propyl-1H-benzimidazole);

2,2′

-Methylenebis(1H-benzimidazole);

2,2′

-(1,2-Phenylene)bis(1-ethyl-1H-benzimidazole);

2,2′

-(1,2-Phenylene)bis(1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1-propyl-1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1,3-benzothiazole);

N-Pyridin-2-ylpyridin-2-amine;

2,2′

-Ethane-1,2-diyldipyridine;

2,2′

-Methylenedipyridine;

2,2′

-Propane-1,3-diyldipyridine;

2,2′

-Ethane-1,2-diylbis(1H-benzimidazole);

N-Methyl-N-pyridin-2-ylpyridin-2-amine;

N,6-Dimethyl-N-pyridin-2-ylpyridin-2-amine;

N-Octadecyl-N-pyridin-2-ylpyridin-2-amine;

N-Phenyl-N-pyridin-2-ylpyridin-2-amine;

N-Propyl-N-pyridin-2-ylpyridin-2-amine;

6-Methyl-N-(6-methylpyridin-2-yl)-N-propylpyridin-2-amine;

6-Methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine;

N-(Pyridin-2-ylmethyl)pyridin-2-amine;

N-Ethyl-N-(pyridin-2-ylmethyl)pyridin-2-amine;

N-(2-Ethylphenyl)-N-pyridin-2-ylpyridin-2-amine;

2,2′

-Propane-2,2-diylbis(1-pentyl-1H-benzimidazole);

2,2′

-Methylenebis(1-benzyl-1H-benzimidazole);

2,2′

-Ethane-1,2-diylbis(1-benzyl-1H-benzimidazole);

2,2′

-Methylenebis(1,3-benzothiazole);

1-Ethyl-N-methyl-N-pyridin-2-yl-1H-benzimidazol-2-amine;

6-methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amine;

N-Pyridin-2-yl-N-(pyridin-2-ylmethyl)pyridin-2-amine;

N-[(6-Methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

N-Methyl-N-[(1-methyl-1H-benzimidazol-2-yl)methyl]pyridin-2-amine;

6-Methyl-N-pyridin-2-ylpyridin-2-amine;

N-[(1-Methyl-1H-benzimidazol-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

6-Methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

N-(6-Methylpyridin-2-ylmethyl)pyridin-2-amine;

6-Methyl-N,N-dipyridin-2-ylpyridin-2-amine;

2-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylquinolin-8-amine;

6-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylpyridin-2-amine;

2,2′

-(1,2-Phenylene)bis(1-pentyl-1H-benzimidazole);

N,N-Dimethyl-2-pyridin-2-ylethanamine;

N-Methyl-2-pyridin-2-ylethanamine;

N,N-Dimethyl-1-pyridin-2-ylmethanamine and combinations thereof.

12. The thermochromic system of claim 1 wherein the thermochromic system comprises a halide ion.

13. A thermochromic system which comprises:

a) a transition metal ion;

b) a halide; and

c) a ligand capable of forming a Hε

MLC with the halide and the transition metal ion wherein the ligand has the following structure;

14. The thermochromic system of claim 13 wherein each

15. The thermochromic system of claim 14 wherein the ligand capable of forming a Hε

MLC is selected from the group consisting of 2,2′

-Butane-1,1-diylbis(1-propyl-1H-benzimidazole);

2,2′

-Methylenebis(1H-benzimidazole);

2,2′

-(1,2-Phenylene)bis(1-ethyl-1H-benzimidazole);

2,2′

-(1,2-Phenylene)bis(1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1-propyl-1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1H-benzimidazole);

2,2′

-Propane-2,2-diylbis(1,3-benzothiazole);

N-Pyridin-2-ylpyridin-2-amine;

2,2′

-Ethane-1,2-diyldipyridine;

2,2′

-Methylenedipyridine;

2,2′

-Propane-1,3-diyldipyridine;

2,2′

-Ethane-1,2-diylbis(1H-benzimidazole);

N-Methyl-N-pyridin-2-ylpyridin-2-amine;

N,6-Dimethyl-N-pyridin-2-ylpyridin-2-amine;

N-Octadecyl-N-pyridin-2-ylpyridin-2-amine;

N-Phenyl-N-pyridin-2-ylpyridin-2-amine;

N-Propyl-N-pyridin-2-ylpyridin-2-amine;

6-Methyl-N-(6-methylpyridin-2-yl)-N-propylpyridin-2-amine;

6-Methyl-N-(6-methylpyridin-2-yl)pyridin-2-amine;

N-(Pyridin-2-ylmethyl)pyridin-2-amine;

N-Ethyl-N-(pyridin-2-ylmethyl)pyridin-2-amine;

N-(2-Ethylphenyl)-N-pyridin-2-ylpyridin-2-amine;

2,2′

-Propane-2,2-diylbis(1-pentyl-1H-benzimidazole);

2,2′

-Methylenebis(1-benzyl-1H-benzimidazole);

2,2′

-Ethane-1,2-diylbis(1-benzyl-1H-benzimidazole);

2,2′

-Methylenebis(1,3-benzothiazole);

1-Ethyl-N-methyl-N-pyridin-2-yl-1H-benzimidazol-2-amine;

6-methyl-N-phenyl-N-pyridin-2-ylpyridin-2-amine;

N-Pyridin-2-yl-N-(pyridin-2-ylmethyl)pyridin-2-amine;

N-[(6-Methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

N-Methyl-N-[(1-methyl-1H-benzimidazol-2-yl)methyl]pyridin-2-amine;

6-Methyl-N-pyridin-2-ylpyridin-2-amine;

N-[(1-Methyl-1H-benzimidazol-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

6-Methyl-N-[(6-methylpyridin-2-yl)methyl]-N-pyridin-2-ylpyridin-2-amine;

N-(6-Methylpyridin-2-ylmethyl)pyridin-2-amine;

6-Methyl-N,N-dipyridin-2-ylpyridin-2-amine;

2-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylquinolin-8-amine;

6-Methyl-N-(6-methylpyridin-2-yl)-N-pyridin-2-ylpyridin-2-amine;

2,2′

-(1,2-Phenylene)bis(1-pentyl-1H-benzimidazole);

N,N-Dimethyl-2-pyridin-2-ylethanamine;

N-Methyl-2-pyridin-2-ylethanamine;

N,N-Dimethyl-1-pyridin-2-ylmethanamine and combinations thereof.

16. The thermochromic system of claim 15 wherein the thermochromic system exhibits a reversible change in absorbance over the range of temperatures from 25°

C. to 85°

C.

17. The thermochromic system of claim 14 wherein the thermochromic system exhibits a reversible change in absorbance over the range of temperatures from 25°

C. to 85°

C.

18. The thermochromic system of claim 13 wherein the thermochromic system exhibits a reversible change in absorbance over the range of temperatures from 25°

C. to 85°

C.