Electrochromic two-core viologen derivatives and optical articles containing them
View Patent ↗The present invention relates to a group of novel electrochromic materials. More specifically, it relates to electrochromic materials having two-core viologens and the use of these two-core viologens as a variable transmittance medium for the manufacture of an optical article, such as an ophthalmic lens.
1. A compound of formula (I-1):
wherein:
Z is phenylene
A and B are respectively selected from nitrogen and —N + (R 7a )—, and from nitrogen and —N(R 7b )—, wherein R 7a and R 7b are independently selected from:
alkyl which may be substituted by one or more groups independently selected from halogen, alkoxy, cycloalkyl, vinyl, allyl, aryl, and substituted aryl;
aryl may be substituted by one or more groups independently selected from:
halogen, cyano, nitro, alkyl, haloalkyl, arylalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, allyl, vinyl, aryl, substituted aryl, —N(aryl) 2 , —N(aryl)CO(aryl), —CO-aryl and —CO-substituted aryl;
—OR 8 , —SR 8 , —S(O)R 8 , —S(O 2 )R 8 , —S(O 2 )NR 8 R 9 , —NR 8 R 9 , —NR 8 COR 9 , —NR 8 CO(aryl), —CH 2 OR 8 , —CH 2 SR 8 , —CH 2 R 8 , —CO—R 8 and —CO 2 R 8 wherein R 8 and R 9 are independently selected from H, alkyl, haloalkyl, arylalkyl, cycloalkyl, and cycloalkylalkyl;
V—W—R 12 wherein:
V is selected from oxygen, —N(R 8 )—, sulfur, —S(O)— and S(O 2 )— wherein R 8 is as defined above;
W is alkylene, which may be substituted by one or more groups independently selected from halogen and alkoxy; and
R 12 is selected from —OR 8 , —NR 8 (alkyl) and —SR 8 wherein R 8 is as defined above; and
—OC(O)—R 3 wherein R 13 is selected from alkyl, haloalkyl, alkenyl, —W—R 12 , and aryl group which may be substituted by 1 to 4 groups selected from halogen, —R 8 , —OR 8 , —SR 8 , —NR 8 R 9 , —NR 10 R 11 , —CO—R 8 , —C(O)OR 8 wherein R 8 , R 9 , R 10 , R 11 , R 2 and W are as defined above;
R 1 a , R 1 b , R 1 d , R 2 a , R 2 b , R 2 c and R 2 d are selected from H, aryl, and substituted aryl, provided that at least one of R 1 a , R 1 b , R 1 c , R 1 d , R 2 a , R 2 b , R 2 c and R 2 d is not H;
X − is a counterion selected from halide, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, nitrate, methanesulfonate, trifluoromethane sulfonate, toluene sulfonate, hexachloroantimonate, bis(trifluoromethanesulfonyl)imide, perchlorate, acetate and sulfate; and
m is 2 if A and B are nitrogen, 3 if one of A and B is nitrogen and the other is —N + (R 7a )— or —N + (R 7b )—, and 4 if both A and B are —N + (R 7a )— or N + (R 7b )—.
2. The compound according to claim 1 , wherein A and B are respectively selected from nitrogen and —N + (R 7a )—, and from nitrogen and —N + (R 7b )—, wherein R 7a and R 7b are independently selected from C 6 -C 8 alkyl, phenyl and naphthyl which may be both substituted by one or more substituents selected from halogen, cyano, nitro, hydroxy, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 3 -C 7 cycloalkyl, and (C 3 -C 7 cycloalkyl)C 1 -C 4 alkyl.
3. The compound according to claim 1 , wherein said compound is represented by formula (I-3):
wherein Z, A, B, X − , m and R 1 and R 2 are as defined in claims 1 and 2 .
4. The compound according to claim 3 , wherein R 1 and R 2 are each independently selected from phenyl, m-methylphenyl and p-trifluoromethylphenyl.
5. The compound according to claim 1 , wherein said compound is selected from: