Redox-active structures and devices utilizing the same

Patent metadata

Field	Value
Publication number	US-9309274-B2
Application number	US-201414488742-A
Country	US
Kind code	B2
Filing date	Sep 17, 2014
Priority date	Feb 10, 2005
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

A device is presented having reversibly changeable and optically readable optical properties. The device comprises a substrate having an electrically conductive surface and carrying a redox-active layer structure. The redox-active layer structure may be a monolayer or a multi-layer structure and is configured to have at least one predetermined electronic property including at least one of electrodensity and oxidation state. The electronic property of the layer structure defines an optical property of the structure thereby determining an optical response of the structure to certain incident light. This at least one electronic property is changeable by subjecting the redox-active layer structure to an electric field or to a redox-active material. The device thus enables effecting a change in said electronic property that results in a detectable change in the optical response of the layer structure.

First claim

The invention claimed is:

1. A device having reversibly changeable and optically readable optical properties, the device comprising a substrate having an electrically conductive surface and a metal-based redox-active layer structure disposed thereon and configured to have at least one predetermined electronic property including at least one of electrodensity and oxidation state, said at least one electronic property being changeable by subjecting the metal-based redox-active layer structure to an electric field, wherein the electronic property of the metal-based redox-active layer structure defines an optical property of the metal-based redox-active layer structure thereby determining an optical response of the metal-based redox-active layer structure to certain incident light, the device enabling to effect a change in said electronic property that results in a detectable change in the optical response of the metal-based redox-active layer structure, wherein said metal-based redox-active layer structure comprises at least one tris-bipyridyl metal complex of the formula II:

wherein
M is a metal selected from the group consisting of Os, Ru, Fe, Cu, and Co;
n is the formal oxidation state of the metal, wherein n is 0-4;
X is a counter anion selected from the group consisting of Br − , Cl − , F − , I − , PF 6 − , BF 4 − , OH − , ClO 4 − , SO 3 − , CF 3 COO − , CN − , alkylCOO − , arylCOO − , and any combination thereof;
R 4 to R 27 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C 1 -C 10 alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, alkoxy, alkenyl, alkynyl, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, sulfonyl, substituted aryl, substituted cycloalkyl, substituted heterocycloalkyl, and group A, wherein at least one of said R 4 to R 27 is a group A:

wherein A is linked to the ring structure of the compound of general formula II via R 3 ; R 3 is selected from the group consisting of cis/trans C═C, C≡C, N═N, C═N, N═C, C—N, N—C, alkylene, arylene and any combination thereof; Y is N or C(OH); and any two vicinal R 4 -R 27 substituents, together with the carbon atoms to which they are attached, may form a fused ring system selected from the group consisting of cycloalkyl, heterocycloalkyl, heteroaryl and aryl, wherein said fused system may be substituted by one or more groups selected from the group consisting of C 1 -C 10 alkyl, aryl, azido, cycloalkyl, halogen, heterocycloalkyl, alkoxy, hydroxyl, haloalkyl, heteroaryl, alkenyl, alkynyl, nitro, cyano, amino, substituted amino, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, thiol, sulfonyl and substituted aryl; and said fused ring system may also contain at least one heteroatom selected from the group consisting of N, O and S.

2. The device of claim 1 , wherein R 3 is C═C.

3. The device of claim 1 , wherein:
(i) M is Os; n is 2; X is PF 6 − ; R 4 , R 6 to R 25 and R 27 each is hydrogen; R 5 is methyl; and R 26 is A, wherein R 3 is C═C, and Y is —N—, of the formula:

(ii) M is Ru; n is 2; X is PF 6 − ; R 4 , R 6 to R 25 and R 27 each is hydrogen; R 5 is methyl; and R 26 is A, wherein R 3 is C═C, and Y is —C(OH)—, of the formula:

4. The device of claim 1 , wherein the metal-based redox-active layer structure comprises at least one layer of said tris-bipyridyl metal complex.

5. The device of claim 4 , wherein the metal-based redox-active layer structure is configured as a ruthenium-based redox-active monolayer or as an osmium-based redox-active monolayer.

6. The device of claim 4 , wherein said metal-based redox-active layer structure comprises (i) a monolayer of metal-based redox-active complexes comprising at least one metal; or (ii) a monolayer of metal-based redox-active complexes comprising different or identical metals.

7. The device of claim 4 , wherein the metal-based redox-active layer structure comprises a plurality of different or identical layers each formed by a metal-based redox-active complex or a mixture thereof, and optionally redox-active organic molecules.

8. The device of claim 7 , wherein the metal-based redox-active layer structure comprises a plurality of different layers each layer comprising metal-based redox-active complexes having (i) at least one metal; (ii) different metals; or (iii) identical metals.

9. The device of claim 1 , wherein the metal-based redox-active layer structure further comprises redox-active organic molecules.

10. The device of claim 9 , wherein said redox-active organic molecules include thiophenes, quinones or a combination thereof.

11. The device of claim 1 , wherein said change in the electronic property is caused electrochemically by addition or withdrawal of one or more electrons to or from said metal-based redox-active layer structure, via the electrically-conductive surface and one or more electrodes coupled to the layer structure.

12. The device of claim 1 , wherein said metal-based redox-active layer structure is configured to define a predetermined pattern of electronic property regions.

13. The device of claim 12 , wherein said predetermined pattern of electronic property regions is in the form of (i) an array of the regions of said metal-based redox-active layer structure having different and distinguishable electronic properties; or (ii) an array of the space-apart regions having the certain electronic property, or wherein said predetermined pattern of electronic property regions includes a one-dimensional, two-dimensional or three-dimensional array of said electronic property regions.

14. The device of claim 1 , comprising an electrode arrangement for applying the electric field to the metal-based redox-active layer structure.

15. The device of claim 14 , wherein said electrode arrangement comprises at least one first electrode arrangement formed by the electrically-conductive surface, and at least one second electrode associated with said metal-based redox-active layer structure.

16. The device of claim 15 , wherein (i) the at least one first electrode arrangement is formed as a pattern including an array of electrically-conductive regions spaced by non-conductive regions of the substrate, thereby defining an array of regions of the metal-based redox-active layer structure to be selectively addressed to affect the electronic property of the metal-based redox-active layer structure; or (ii) the at least one second electrode is formed as an array of electrodes coupled to said metal-based redox-active layer structure, thereby defining an array of regions of the metal-based redox-active layer structure to be selectively addressed to affect the electronic property thereof.

17. The device of claim 1 , wherein the electrically-conductive surface carries a functional group capable to coordinate, or to covalently, non-covalently or by a combination thereof attach to said metal-based redox-active layer structure.

18. The device of claim 1 , wherein the substrate is a hydrophilic substrate, a

Assignees

• Yeda Res & Dev

Inventors

• Van Der Boom Milko E
• Shukla Atindra D
• Rosenblatt David
• Gupta Tarkeshwar

Classifications

• Y02E10/542

  Dye sensitized solar cells · CPC title

• C07F15/0026 Primary

  without a metal-carbon linkage · CPC title

• G02F1/15

  based on an electrochromic effect · CPC title

• G01Q80/00

  Applications, other than SPM, of scanning-probe techniques (manufacture or treatment of nanostructures B82B3/00; recording or reproducing information using near-field interaction G11B9/12, G11B11/24, G11B13/08) · CPC title

• C07F7/1836

  Chemistry & Metallurgy · mapped topic