# US 5,708,123 A · Electroactive materials, a process for their preparation as well as the use thereof

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- Number: US 5,708,123 A
- Document ID: US5708123A
- Status: Granted
- Kind: A
- Application number: 08/553,691
- Filed: 1995-06-26
- Granted: 1998-01-13
- Earliest claimed: 1993-06-11
- Assignees: NKT Research Center A/S
- Inventors: Ib Johannsen; Mikkel J.o slashed.rgensen
- Web page: https://patentgrep.com/patent/US5708123A

## CPC

- C07D 487/04: Ortho-condensed systems
- C07D 513/04: Ortho-condensed systems
- C09K 9/02: Organic tenebrescent materials
- G02F 1/1516: comprising organic material
- G02F 1/15165: {Polymers}
- H01B 1/12: organic substances {(organic macromolecular compounds or compositions C08)}
- H01M 4/60: of organic compounds
- Y02E 60/10: Energy storage using batteries
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Stable, electroactive material which when a potential is applied from the outside is subjected to one or more reversible redox reactions, for use in devices with an electrochromic display or another electrochromic color change or in batteries. The material comprises a condensed ring structure, the oxidized form of which is of the formula ##STR1## in which R.sub.1, R.sub.2, X, and A may have any meaning with the proviso that the condensed ring structure maintains the reversible properties. The material can be prepared by various processes and it is suited for use as electrochromic material for use in devices with an electrochromic display or as coating on windows because it presents a distinct and easily visible color change when it is subjected to a potential. In addition, the material is suited for use in rechargeable batteries because is possesses an excellent capacity and reversibility.

## Claims

### Claim 1

Stable, electroactive material which when a potential is applied from the outside is subjected to one or more reversible redox reactions, for use in devices with an electrochromic display or another electrochromic colour change or in batteries, characterised by containing at least one condensed ring structure I of one of the formulas I red or I ox in the redox reaction equation: ##STR11## in which the groups X, which may be identical or different, are O, S or NR.sub.3, at least one of the groups being NR.sub.3,
where the structures A, which may be identical or different, may be any molecular structure not blocking the redox reaction, and, optionally, may carry one or more identical or different substituents R.sub.4,
where R.sub.1, R.sub.2, R.sub.3, and R.sub.4, which may be identical or different, may be any substituent not blocking the redox reaction, and where one or more of the substituents R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may also form part of a linker residue L, which is attached to one or more additional ring structures I, and
where L is a divalent or polyvalent group not blocking the redox reaction.

### Claim 2 (depends on 1)

Electrochromic material as claimed in claim 1, characterised by both groups X being NR.sub.3.

### Claim 3 (depends on 1)

Electroactive material as claimed in claim 1, characterised in that one or more of the groups R.sub.1, R.sub.2, R.sub.3, and R.sub.4, which may be identical or different, are a straight or branched chain group with 1 to 24 chain atoms selected among C, O, N, S, and Si.

### Claim 4 (depends on 1, 2, 3)

Electroactive material as claimed in claim 1 or 2 or 3, characterised in that one or more of the groups R.sub.1, R.sub.2, R.sub.3, and R.sub.4, which may be identical or different, are alkyl with 1 to 18 carbon atoms, thioalkyl with 1 to 18 carbon atoms, and 1 to 6 sulphur atoms, oxoalkyl with 1 to 18 carbon atoms, and 1 to 6 oxygen atoms, nitro, halogen, phenyl, alkenyl with 1 to 18 carbon atoms, cyano, hydroxy, alkoxy with 1 to 6 carbon atoms or alkylamino with 1 to 6 carbon atoms.

### Claim 5 (depends on 1)

Electroactive material as claimed in claim 1, characterised in that one or both structures A comprise a carbocyclic or heterocyclic ring condensed with ring No. 1 and/or ring No. 3, respectively, in the structure I.

### Claim 6 (depends on 5)

Electroactive material as claimed in claim 5, characterised in that the carbocyclic or heterocyclic ring is aromatic.

### Claim 7 (depends on 1)

Electroactive material as claimed in claim 1, characterised in that it is an oligomeric or polymeric material, in which the ring structure I forms part, where the polymeric structure results from linker residues L.

### Claim 8 (depends on 7)

Electroactive material as claimed in claim 7, characterised in that the linker residues L are straight chained or branched, divalent or polyvalent groups with 3 to 150 chain atoms selected among C, O, N, S, and Si.

### Claim 9 (depends on 7, 8)

Electroactive material as claimed in claim 7 or 8, characterised in that the linker residues are derived from one or more precursor materials (monomer or prepolymer) selected among precursor materials to polyalkene, polyether, polysulphide, polyamine, silicone or mixtures thereof.

### Claim 10 (depends on 1)

A method for the preparation of a stable electroactive material in form of a compound containing a condensed ring structure I of the formula shown in claim 1, in which the groups X, which may be identical or different, are O, S or NR.sub.3, and where A, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may have any meaning indicated in claim 1, with the proviso that none of the substituents R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can form part of a linker residue L attached to additional ring structures characterised by
a) reacting an amine of the formula II ##STR12## where A and X have the meanings stated above, with a quinone of the formula III ##STR13## where R.sub.1 and R.sub.2 have the meanings stated above, and Q.sub.1 is hydrogen or C.sub.1-4 alkyl, or
b) for the preparation of compounds of the ring structure Ib, in which Ib ox has the formula ##STR14## in which R.sub.3 and A have the meanings stated above, where R.sub.a and R.sub.b may have the same meaning as the groups R.sub.1, R.sub.3, and R.sub.4, and where each of the two groups R.sub.a/b is the same as R.sub.a and R.sub.b, respectively,
reacting 2 molecules of an o-phenylene diamine of the formula IV ##STR15## in which R.sub.a and R.sub.b have the meanings stated above, in the presence of an oxidation agent to form a compound of the formula V ##STR16## in which R.sub.a, R.sub.b, and R.sub.a/b have the meanings stated above, and then reacting the compound of the formula V with a compound of the formula VI ##STR17## in which R.sub.3 and A have the meanings stated above.

### Claim 11 (depends on 1)

A method for the preparation of a stable electroactive material as claimed in claim 1 in form of an oligomeric or polymeric material containing several ring structures I, in which X, A, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 have the meanings stated in claim 1, and in which one or more linker residues L having the meaning sated in claim 1 form part, characterised by
c) for the preparation of an electroactive polymeric material of the following structure ##STR18## in which A, R.sub.1, R.sub.2, and L have the meanings stated above, and n is the polymerisation degree, reacting a compound of the formula VII ##STR19## in wich A has the meaning stated in claim 1, and Q.sub.2 is a leaving group, with a diamine compound of the formula
H.sub.2 N-L-NH.sub.2 VIII
where L has the meaning stated in claim 1, to form a compound of the formula IX ##STR20## where A and L have the meaning stated above, reducing the compound of the formula IX to obtain a compound of the formula X ##STR21## in which A and L have the meanings stated above, and reacting the compound of formula X with a quinone of the formula III ##STR22## in which R.sub.1 and R.sub.2 have the meanings stated above, and Q.sub.1 is hydrogen or C.sub.1-4 alkyl, or
d) for the preparation of a polymeric, electroactive material with the structure Id, where Id ox has the structure ##STR23## in which R.sub.1, R.sub.2, R.sub.3, and L have the meanings stated above, n is the polymerization degree and A.sub.1 is a structure A comprising a benzene ring, reacting a compound of the formula XI ##STR24## in which A.sub.1 has the meaning stated above, and Q.sub.3 is a protecting group, with a diamine compound of the formula VIII
H.sub.2 N-L-NH.sub.2 VIII
in which L has the meaning stated above, to obtain a compound of the formula XII ##STR25## in which A.sub.1, L, and Q.sub.3 have the meanings stated above, nitrating the rings A.sub.1 in the o-position into the groups NHQ.sub.3 in the compound of the formula XII, and in arbitrary sequence or simultaneously reducing the nitro groups and removing the protecting groups Q.sub.3 to form a compound of the formula XIII ##STR26## in which A.sub.1 and L have the meanings stated above, and reacting the compound of the formula XIII with a compound of the formula III ##STR27## in which R.sub.1, R.sub.2, and Q.sub.1 have the meanings stated above, to form a polymeric compound with the structure Id, in which R.sub.3 is hydrogen and, optionally, as termination or at a suitable stage during the synthesis converting one or more hydrogen groups R.sub.3 into R.sub.3 -groups having another of the meanings stated for R.sub.3, or
e) for the preparation of a polymeric structure Ie, in which Ie ox is of the formula ##STR28## in which A, R1, L and n have the meanings stated above reacting a compound of the formula XIV ##STR29## in which A, R.sub.1, and R.sub.2 have the meanings stated in claim 1, with a compound of the formula XV
Q.sub.4 -L-Q.sub.4 XV
in which Q.sub.4 is a leaving group.