Diarylethene compounds and uses thereof

1. A compound according to Formula VIIA/B, reversibly convertible under photochromic and electrochromic conditions between a ring-open isomer A and a ring-closed isomer B:

Z is O;

each R 1 is independently selected from the group consisting of H, or halo;

each R 2 is independently selected from the group consisting of H, halo, a polymer backbone, alkyl or aryl; or, when both R 2 together form —CH═CH— and form part of a polymer backbone;

each R 4 is

X is N, O or S; and

each R 7a , R 7b , R 7c ; and each R 9a , R 9b , R 9c , R 9d , R 9e is independently selected from a group consisting of:

H, Cl, Br, F, —CF 3 , —CN, —NO 2 , methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R 11 ) 3 , thiophene, substituted thiophene, benzyl, substituted benzyl, —CH 2 —CH 2 —, —CH═CH—, —CH═CH 2 , —OCH 3 , —COH, —OH, —CO 2 H, —COCH 3 , —C(CH 3 ) 2 OH, —Si(CH 3 ) 3 , —CH 2 CH 2 OCH 3 , —CH 2 CH 2 OH, —N(CH 3 ) 2 , —CO 2 CH 3 , —OCH 2 OCH 3 , —SO 2 CH 3 , —OCH 2 C(CH 3 ) 3 , —OCH 2 CH(CH 3 ) 2 , —OC(CH 3 ) 3 , —OCH═CH 2 , —O(CH 2 ) 4 CN, —O(CH 2 ) 4 OH, —O(CH 2 ) 3 OH, —C(CH 3 ) 2 OH, —OCH 2 ) 2 OCH 3 ,

n and m are independently any integer from 0 to 20;

R 11 is independently selected from the group comprising R or —O—R, and wherein R is linear or branched, non-aromatic monocyclic or polycyclic, substituted or unsubstituted alkyl group of 1 to 20 carbons; or R is a heteroalkyl group comprising one or more of O, S, N or Si; or each R is a saturated or unsaturated alkyl that is linear or branched with 1-12 carbons; or each R is a substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl;

R 10a is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH 3 , —CN, —OH, H,

R 10b is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH 3 , —CN, —OH, H,

R 10c is selected from a group consisting of an electron donating group (EDG), an electron withdrawing group (EWG), —OCH 3 , —CN, —OH,

R 10d is selected from a group consisting of, an electron donating group (EDG), an electron withdrawing group (EWG), —OCH 3 , —CN, —OH, H,

or

R 10b and R 10c are each O and joined by —CH 2 — to form a 5-membered ring.

2. The compound according to claim 1 wherein both R 2 are —CH═CH— and form part of a polymer backbone.

3. The compound according to claim 1 wherein R 4 is

and X is S.

4. The compound according to claim 1 wherein R 4 is

5. The compound according to claim 1 wherein:

a. the electron donating group is selected from a group consisting of —OH, OR, NH 2 , NHR, NR 2 , electron-rich heteroaryl groups, electron-rich substituted aryl groups, —O − , amine, alcohol, ether, thioether, alkyl and carbamate; and

b. the electron withdrawing group is selected from a group consisting of halogen, electron-poor heteroaryl groups, electron-poor substituted aryl groups, —NO 2 , — + NR 3 , — + NH 3 , —SO 3 H, —CN, CF 3 , aldehyde, ester, carboxylic acid, carbonyl, carbonyl chloride and amide.

6. The compound according to claim 1 wherein R 9a , R 9b , R 9c , R 9d and R 9e are each independently selected from a group consisting of H, Cl, Br, F, —CF 3 , —CN, —NO 2 , methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl; and wherein

R 10a is selected from a group consisting of —OCH 3 , —CN, —OH, H,

R 10b is selected from a group consisting of —OCH 3 , —CN, —OH, H,

R 10c is selected from a group consisting of —OCH 3 , —CN, —OH,

and

R 10d is selected from a group consisting of —OCH 3 , —CN, —OH, H,

7. The compound according to claim 4 wherein R 9e is tert-butyl.

8. The compound according to claim 1 wherein R 9a , R 9b , R 9d and R 9e are H.

9. The compound according to claim 1 wherein one or more of R 10a , R 10b , R 10c and R 10d are —OCH 3 .

10. The compound according to claim 1 wherein R 10c is

11. The compound according to claim 1 wherein R is substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl.

12. The compound according to claim 1 , selected from the group consisting of

13. A compound according to Formula IA/IB, reversibly convertible under photochromic and electrochromic conditions between a ring-open isomer A and a ring-closed isomer B:

wherein

Z is N, O or S;

each R 1 is independently selected from the group consisting of H, or halo;

each R 2 is independently selected from the group consisting of H, halo, a polymer backbone, alkyl or aryl; or, when both R 2 together form —CH═CH— and form part of a polymer backbone;

each R 3 is

both R 4 are

or both R 4 are

and R 6a and R 7a are not methyl;

X=S;

each R 5 is H;

each R 6a , R 6b , R 6c ;

each R 7a , R 7b , R 7c ; and

each R 9a , R 9b , R 9c , R 9d , R 9e

is independently selected from a group comprising:

H, Cl, Br, F, —CF 3 , —CN, —NO 2 , methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R 11 ) 3 , thiophene, substituted thiophene, benzyl, substituted benzyl, —CH 2 —CH 2 —, —CH═CH—, —CH═CH 2 , —OCH 3 , —COH, —OH, —CO 2 H, —COCH 3 , —C(CH 3 ) 2 OH, —Si(CH 3 ) 3 , —CH 2 CH 2 OCH 3 , —CH 2 CH 2 OH, —N(CH 3 ) 2 , —CO 2 CH 3 , —OCH 2 OCH 3 , —SO 2 CH 3 , —OCH 2 C(CH 3 ) 3 , —OCH 2 CH(CH 3 ) 2 , —OC(CH 3 ) 3 , —OCH—CH 2 , —O(CH 2 ) 4 CN, —O(CH 2 ) 4 OH, —O(CH 2 ) 3 OH, —C(CH 3 ) 2 OH, —O(CH 2 ) 2 OCH 3 , —O(CH 2 ) 4 CN, —O(CH 2 ) 4 COOH

or where R 6a and R 6b are each —CH═CH— and joined to form an unsaturated ring;

wherein n and m are independently any integer from 0 to 20; and

wherein R 11 is independently selected from the group comprising R or —O—R, and wherein R is linear or branched, non-aromatic monocyclic or polycyclic, substituted or unsubstituted alkyl group of 1 to 20 carbons; or R is a heteroalkyl group comprising one or more of O, S, N or Si; or each R is a saturated or unsaturated alkyl that is linear or branched with 1-12 carbons; or each R is a substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl; and

at least one of R 6a , R 6b , R 6c is not H;

at least one of R 7a , R 7b , R 7c is not H; and

at least one of R 9a , R 9b , R 9c , R 9d , R 9e is not H.

14. The compound according to claim 13 wherein both R 2 are —CH═CH— and form part of a polymer backbone.

15. The compound according to claim 13 wherein:

each R 6a is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R 11 ) 3 , thiophene, substituted thiophene, —CO 2 H, —COCH 3 , —Si(CH 3 ) 3 ;

each R 6b is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R 11 ) 3 , thiophene, substituted thiophene, —CO 2 H, —COCH 3 , —Si(CH 3 ) 3 ;

each R 6c is independently selected from a group consisting of H, Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R 11 ) 3 , thiophene, substituted thiophene, —CO 2 H, —COCH 3 , —Si(CH 3 ) 3 ;

R 11 is R, and R is a heteroalkyl group of from 1 to 10 carbons, comprising one or more of O, S;

and

at least one of R 6a , R 6b , R 6c is not H.

16. The compound according to claim 13 wherein the substituted thiophene of R 6a , R 6b or R 6c is

17. The compound according to claim 13 wherein

R 6a is selected from a group consisting of Cl, —CN, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, —Si(R 11 ) 3 , thiophene, substituted thiophene, methyl thiophene, —CO 2 H, —COCH 3 , —Si(CH 3 ) 3 , and wherein R 11 is R, and R is a heteroalkyl group of from 1 to 10 carbons, comprising one or more O, S;

R 6b is H or CH 3 ; and

R 6c is H or CH 3 .

18. The compound according to claim 13 wherein R 11 is —CH 3 or —(CH 2 ) 1-10 —OCH 3 .

19. The compound according to claim 13 wherein both R 4

are

20. The compound according to claim 13 wherein both R 4 are

21. The compound according to claim 13 wherein R 9c is —OCH 3 , —OH, —O(CH 2 ) 4 CN, —O(CH 2 ) 4 COOH, —O(CH 2 ) 3 OH,

22. The compound according to claim 13 selected from the group consisting

of:

23. The compound according to claim 13 wherein R 7a is H, Cl, Br, F, —CF 3 , —CN, —NO 2 , methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, saturated or unsaturated alkyl that is linear or branched with 5-12 carbons, —Si(R 11 ) 3 , thiophene, substituted thiophene, benzyl, substituted benzyl, —CH 2 —CH 2 —, —CH═CH—, —CH═CH 2 , —OCH 3 , —COH, —OH, —CO 2 H, —COCH 3 , —C(CH 3 ) 2 OH, —Si(CH 3 ) 3 , —CH 2 CH 2 OCH 3 , —CH 2 CH 2 OH, —N(CH 3 ) 2 , —CO 2 CH 3 , —OCH 2 OCH 3 , —SO 2 CH 3 , —OCH 2 C(CH 3 ) 3 , —OCH 2 CH(CH 3 ) 2 , —OC(CH 3 ) 3 , —OCH—CH 2 , —O(CH 2 ) 4 CN, —O(CH 2 ) 4 OH, —O(CH 2 ) 3 OH, —C(CH 3 ) 2 OH, —O(CH 2 ) 2 OCH 3 , —O(CH 2 ) 4 CN, —O(CH 2 ) 4 COOH,

24. The compound according to claim 23 wherein R 11 is —CH 3 or —(CH 2 ) 1-10 —OCH 3 .

25. The compound according to claim 13 wherein R is substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or hexyl.