Redox-active structures and devices utilizing the same

A display device comprising a substrate carrying a redox-active layer structure, the redox-active layer structure comprising at least one layer including ink particles, each particle having a core coated with a metal-based redox-active material which is 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 layer structure to an electric field, said at least one electronic property of the metal-based redox-active layer structure defining a certain optical property of the structure thereby determining an optical response of the redox-active layer structure to certain incident light, the device thereby enabling to effect a change in said electronic property that results in a change in the optical response of the 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−, PF6−, BF4−, OH−, ClO4−, SO3−, CF3COO−, CN−, alkylCOO−, arylCOO−, and any combination thereof;
• R4 to R27 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C1-C10 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 R4 to R27 is a group A:
• wherein A is linked to the ring structure of the compound of general formula II via R3;
• R3 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 R4-R27 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 C1-C10 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.

A method for fabricating an electro-optical device, the method comprising chemically binding a metal-based redox-active layer structure to an electrically conductive surface of a substrate, said metal-based redox-active layer structure comprising at least one metal selected in accordance with the device intended operation, said metal-based redox-active layer structure being configured to have at least one predetermined electronic property defined by at least one of electrodensity and oxidation state changeable by subjecting the metal-based redox-active layer structure to an electric field, the electronic property of the metal-based redox-active layer structure defining a certain optical property of the metal-based redox-active layer structure thereby determining a certain optical response of the metal-based redox-active layer structure to certain incident light, effecting a change in the electronic property resulting in a reversible 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−, PF6−, BF4−, OH−, ClO4−, SO331 , CF3COO−, CN−, alkylCOO−, arylCOO−, and any combination thereof;
• R4 to R27 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C1-C10 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 R4 to R27 is a group A:
• wherein A is linked to the ring structure of the compound of general formula II via R3;
• R3 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 R4-R27 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 C1-C10 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.

A sensor device configured and operable for sensing at least one predetermined liquid or gas substance, the device comprising a metal-based redox-active layer structure selected to be capable of changing its oxidation state in response to a reaction with said at least one predetermined liquid or gas substance, thereby causing a change in optical properties of said metal-based redox-active layer structure, said change being reversible and optically readable, 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−, PF6−, BF4−, OH−, ClO4−, SO3−, CF3COO−, CN−, alkylCOO−, arylCOO−, and any combination thereof;
• R4 to R27 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C1-C10 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 R4 to R27 is a group A:
• wherein A is linked to the ring structure of the compound of general formula II via R3;
• R3 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 R4-R27 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 C1-C10 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.

A method for writing/reading non-binary data in a memory device, which comprises 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, changeable by subjecting the metal-based redox-active layer structure to an electric field, the method comprising scanning the metal-based redox-active layer structure with a tip of an atomic force microscope operable to apply voltages corresponding to various conditions of said at least one predetermined electronic property, thereby creating/detecting a non-binary data pattern in 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−, PF6−, BF4−, OH−, ClO4−, SO3−, CF3COO−, CN−, alkylCOO−, arylCOO−, and any combination thereof;
• R4 to R27 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C1-C10 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 R4 to R27 is a group A:
• wherein A is linked to the ring structure of the compound of general formula II via R3;
• R3 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 R4-R27 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 C1-C10 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.