Electrochromic single and two-core viologens and optical articles containing them

Patent metadata

Field	Value
Publication number	US-9823534-B2
Application number	US-201415022784-A
Country	US
Kind code	B2
Filing date	Sep 16, 2014
Priority date	Sep 17, 2013
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

The present invention relates to a group of novel electrochromic materials. More specifically, it relates to electrochromic materials based on either single or two-core viologen systems and the use of these viologen systems as a variable transmittance medium for the manufacture of an optical article, such as an ophthalmic lens.

First claim

The invention claimed is:

1. A compound of formula (I):

wherein:
Z is selected from:
alkylene;
cycloalkylene; and
a bivalent groups of formula —R 7 —Y—R 8 —, wherein
R 7 and R 8 are each independently selected from single bond, alkylene and cycloalkylene, and
Y is selected from arylene, cycloalkylene, heteroarylene, arylene-arylene or arylene-CR′R″-arylene wherein R′ and R″ form together with the carbon to which they are linked a carbocyclic group;

wherein said alkylene, cycloalkylene, arylene, heteroarylene and carbocyclic groups may be substituted by one or more substituents selected from halogen, alkyl, alkoxy, alkylthio, hydroxyalkyl, acyloxy, cycloalkyl, aryl, substituted aryl, aryloxy, heteroaryl and substituted heteroaryl;
wherein said alkylene, cycloalkylene, arylene, heteroarylene and carbocyclic groups may be substituted by one or more substituents selected from halogen, alkyl, alkoxy, alkylthio, hydroxyalkyl, acyloxy, cycloalkyl, aryl, substituted aryl, aryloxy, heteroaryl and substituted heteroaryl;
m is 0 or 1;
R 1 and R 2 are each independently selected from optionally substituted phenyl of formula (II):

wherein R a , R b , R c , R d and R e are each independently selected from:
H, halogen, cyano, nitro, alkyl, haloalkyl, haloalkoxy, (haloalkoxy)alkyl, arylalkyl, cycloalkyl, (cycloalkyl)alkyl and (heterocycloalkyl)alkyl, alkenyl, alkynyl, allyl, vinyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, —N(aryl) 2 , —N(aryl)CO(aryl), —CO-aryl and —CO-substituted aryl;
—OR 9 , —SR 9 , —S(O)R 9 , —S(O 2 )R 9 , —S(O 2 )NR 9 R 10 , —NR 9 R 10 , —NR 9 COR 10 , —NR 9 CO(aryl), —NR 9 aryl, —CH 2 OR 9 , —CH 2 SR 9 , —CH 2 R 9 , —CO—R 9 and —CO 2 R 10 wherein R 9 and R 10 are independently selected from H, alkyl, haloalkyl, arylalkyl, cycloalkyl, cycloalkylalkyl and heterocycloalkylalkyl;
—S(O 2 )NR 11 R 12 and —NR 11 R 12 , wherein R 11 and R 12 form together with the nitrogen atom to which they are linked a saturated 5 to 7 membered heterocycloalkyl which may comprising in addition to the nitrogen atom one further heteroatom selected from oxygen, nitrogen and sulfur, and which may be optionally substituted by one or two groups, identical or different, selected from halogen, —R 9 , —OR 9 , and —NR 9 R 10 , wherein R 9 and R 10 are as defined above;
—V—W—R 13 wherein:
V is selected from oxygen, —N(R 9 )—, sulfur, —S(O)— and —S(O 2 )— wherein R 9 is as defined above;
W is alkylene, which may be substituted by a group selected from halogen and alkoxy; and
R 13 is selected from —OR 9 , —NR 9 (alkyl) and —SR 9 wherein R 9 is as defined above; and

OC(O)—R 14 wherein R 14 is selected from alkyl, haloalkyl, alkenyl, —W—R 13 , and aryl group which may be substituted by 1 to 4 groups selected from halogen, —R 9 , —OR 9 , —SR 9 , —NR 9 R 10 , —NR 11 R 12 , —CO—R 9 , —CO 2 R 9 wherein R 9 , R 10 , R 11 , R 12 , R 13 and W are as defined above,

with the provisions that:
when Y is arylene-arylene or arylene-alkylene-arylene, then R 1 and R 2 are not phenyl;
when m is 0, then R e is H and at least one of R a , R b R c and R d is not H and may be independently selected from cyano, nitro, hydroxyl, C 4 -C 12 alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, cycloalkyl, allyl, aryl and heteroaryl;
R 3 , R 4 , R 5 and R 6 are each independently selected from H, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, polyalkylenoxy, alkoxycarbonyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, wherein the alkyl group may be substituted by one or more substituents selected from alkoxy, cycloalkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl;
n, p, q and r are each independently an integer from 0 to 4, wherein when n, p, q and r are two or more, each of the R 3 , each of the R 4 , each of the R 5 or each of the R 6 may be identical or different; and
X − is a counterion.

2. The compound according to claim 1 , wherein Z is selected from C 1 -C 12 alkylene, aryl substituted C 1 -C 12 alkylene, phenylene, naphthylene, (C 1 -C 4 alkylene)-phenylene-(C 1 -C 4 alkylene), (C 1 -C 4 alkylene)-naphthylene-(C 1 -C 4 alkylene), quinoxaline-2,3-diyl, (C 1 -C 4 alkylene)-quinoxaline-2,3-diyl-(C 1 -C 4 alkylene), phenylene-phenylene, (C 1 -C 4 alkylene)-phenylene-phenylene-(C 1 -C 4 alkylene) and phenylene-fluorenylene-phenylene, preferably Z is selected from —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —CH 2 —CH(CH 3 )—CH 2 —, —CH 2 —CH(CH 2 Phenyl)-CH 2 —, —(CH 2 ) 2 —CH(CH 3 )—CH 2 —, —(CH 2 ) 3 —CH(CH 3 )—CH 2 —, —(CH 2 ) 2 —CH(CH 3 )—(CH 2 ) 2 —,

3. The compound according to claim 1 , wherein R 3 , R 4 , R 5 and R 6 are each independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl, alkanoyl, aroyl, aryl and heteroaryl, wherein the aryl and heteroaryl may be substituted by one or more substituents selected from C 1 -C 4 alkyl and C 1 -C 4 haloalkyl, preferably, R 3 , R 4 , R 5 and R 6 are each independently selected from methyl, ethoxycarbonyl, phenyl, p-methylphenyl and p-trifluoromethylphenyl.

4. The compound according to claim 1 , wherein the counterion X − is selected from halide, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, nitrate, methanesulfonate, trifluoromethane sulfonate, toluene sulfonate, hexachloroantimonate, bis(trifluoromethanesulfonyl)imide, perchlorate, acetate and sulfate.

5. The compound according to claim 1 , wherein R a , R b , R c , R d and R e are each independently selected from H, cyano, halogen, nitro, hydroxyl, alkyl, preferably C 4 -C 12 alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, cycloalkyl, allyl, aryl and heteroaryl.

6. The compound according to claim 1 , wherein R e is H and at least one of R a , R b , R c , and R d is not H, preferably at least one of R a and R b is not H.

7. The compound according to claim 1 , wherein said compound is selected from:

8. An electrochromic composition comprising at least one compound as defined in claim 1 .

9. The electrochromic composition according to claim 8 , wherein said composition comprises a fluid, mesomorphous or gel host medium.

10. The electrochromic composition according to claim 9 , wherein the fluid or mesomorphous host medium is selected from the group consisting of organic solvents, liquid crystals, polymers, liquid crystal polymers and mixtures thereof.

11. An electrochromic device comprising a compound according to claim 1 .

12. The electrochromic device according to claim 11 , wherein said device comprises a mechanism for holding the said compound or said composition in a mechanically stable environment.

13. The electrochromic device according to claim 12 , wherein said device comprises a pair of opposed substrates having a gap there between for receiving said compound or said composition, and a frame for holding said pair of substrates adjacent one another.

14. The electrochromic device according to

Assignees

• Essilor Int

Inventors

• Aiken Stuart
• Gabbutt Christopher David
• Heron Bernard Mark
• Biver Claudine
• Archambeau Samuel
• Berit-Debat Fabien
• Duluard Sandrine

Classifications

• C09K2211/1007

  Non-condensed systems · CPC title

• C07D213/22

  containing two or more pyridine rings directly linked together, e.g. bipyridyl · CPC title

• G02C7/101

  having an electro-optical light valve (electro-optical elements per se G02F) · CPC title

• G02F1/1521 Primary

  Physics · mapped topic

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title