Diketopyrrolopyrole (DPP)-based sensitizers for electrochemical or optoelectronic devices

Patent metadata

Field	Value
Publication number	US-9697956-B2
Application number	US-201314425239-A
Country	US
Kind code	B2
Filing date	Aug 14, 2013
Priority date	Sep 3, 2012
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

The present invention relates to compounds of formula (I) based on DPP moiety being useful as metal-free organic sensitizers or dyes of type D-π-A in electrochemical or optoelectronic devices, their use as sensitizer or dye and an electrochemical or optoelectronic device comprising a compound of the invention.

First claim

The invention claimed is:

1. A compound of formula (I)

wherein:
m, n, p and q are independently selected from an integer from 0 to 3;
R 1 and R 2 are substituents of N atoms of the pyrrolopyrrole moiety and being independently selected from H, C1-C35 alkyl, C4-C35 aryl, C1-C35 arylalkyl, C4-C35 heteroaryl, wherein heteroatoms are selected from O, S or N;
R 1 and R 2 are substituents of the pyrrole rings and being independently selected from H, OH, S, ═O (keto group), C1-C35 alkyl, C1-C35 thioalkyl, C1-C35 alkoxy, C4-C35 aryl, C1-C35 arylalkyl, C4-C35 heteroaryl, wherein heteroatoms are selected from O, S or N;
Ar 1 and Ar 2 are different from each other and Ar 1 and Ar 2 are aromatic aryl groups independently selected from a moiety according to any one of formula (1) to (18):

wherein R 3 is selected from H, C1-C35 alkyl, C4-C35 aryl, C1-C35 arylalkyl, or C4-C35 heteroaryl, wherein the heteroatoms are selected from O, S, or N;
Π-Spacer 1 and Π-Spacer 2 are independently selected from a moiety according to any one of formula (19) to (33):

wherein R 4 is selected from H, C1-C35 alkyl, C1-C35 alkoxy, C1-C35 thioalkyl, C4-C35 aryl, C1-C35 arylalkyl or C4-C35 heteroaryl, wherein heteroatoms are selected from O, S, or N;

A is a substituent comprising an anchoring group “Anch” and an acceptor group and being selected from a moiety according to any one of formula (78) to (87):

wherein R 5 is selected from H, C1-C35 alkyl, C1-C35 alkoxy, C1-C35 thioalkyl, C4-C35 aryl, C1-C35 arylalkyl or C4-C35 heteroaryl, wherein heteroatoms are selected from O, S, or N and Anch is an anchoring group independently selected from —COOH, PO 3 H 2 , —PO 4 H 2 , —P(R 8 )O 2 H, —SO 3 H 2 , —SO 4 H 2 , —CONHOH − , 1,2-hydroxybenzene, 1-hydroxy-2-carboxybenzene, acetylacetonate, deprotonated forms of the aforementioned, organic and/or inorganic salts of said deprotonated forms, wherein R 8 is a hydrocarbon comprising from 1 to 50 carbons and 0-25 heteroatoms selected from O, N, or S, said hydrocarbon being covalently bound to the P atom of said phosphinic acid group by a carbon atom;

D is a donor group selected from a moiety according to any one of formula (44) to (55):

wherein R 6 is selected from H, C1-C35 alkyl, C1-C35 alkoxy, C1-C35 thioalkyl, C4-C35 aryl, C1-C60 arylalkyl or C4-C35 heteroaryl, wherein heteroatoms are selected from O, S, or N and wherein aryl is optionally substituted by C4-C35 arylalkyl or by C4-C35 arylalkoxy groups or by C4-C35 alkenylaryl or by C4-C35 alkenylarylalkoxy groups;

Ar 3 and Ar 4 are aromatic aryl groups independently selected from a moiety according to any one of formula (56) to (70):

wherein R 7 is selected from H, C1-C35 alkyl, C4-C35 aryl, C1-C35 arylalkyl, or C4-C35 heteroaryl, wherein the heteroatoms are selected from O, S, or N;

and wherein said C1-C35 alkyl, C1-C35 alkoxy, C1-C35 thioalkyl, C4-C35 aryl, C1-C35 arylalkyl or C4-C35 heteroaryl may be further substituted or unsubstituted by a C1-C11 hydrocarbon comprising 0 to 15 heteroatoms selected from O, N, S or halogen.

2. The compound according to claim 1 , wherein m and n are 0.

3. The compound according to claim 1 , wherein p and q are 0 or 1.

4. The compound according to claim 1 , wherein m and n are 0 and wherein p and q are 0 or 1.

5. The compound according to claim 1 , wherein p is 0 and q is 1.

6. The compound according to claim 1 , wherein m and n are 0; p is 0 and q is 1.

7. The compound according to claim 1 , wherein p is 1 and q is 0.

8. The compound according to claim 1 , wherein m and n are 0; p is 1 and q is 0.

9. The compound according to claim 1 , wherein the alkyl chain of groups of C1-C35 alkyl and C1-C35 arylalkyl of R 1 and R 2 substituents of N atoms of the pyrrolopyrrole moiety are branched C1-C35 alkyl chain.

10. The compound according to claim 1 , wherein A is selected from a moiety according to any one of formula (78), (80), (82), (83) or (84).

11. The compound according to claim 1 , wherein D is selected from a moiety according to any one of formula (45), (46), (48) and (54).

12. The compound according to claim 1 , wherein R 1 and R 2 being substituents of the pyrrole rings are selected from ═O (keto group), S, C1-C35 alkoxy, or C1-C35 thioalkyl.

13. The compound according to claim 1 , wherein Ar 1 and Ar 2 are independently selected from a moiety according to any one of formula (1), (2), (3), (7) and (13).

14. The compound according to claim 1 , wherein Ar 1 is a moiety of formula (1), (7) or (13) and Ar 2 is a moiety of formula (2) or (3).

15. An electrochemical or optoelectronic device comprising a dye being a compound of formula (I) according to claim 1 .

16. The device according to claim 15 , wherein said device is selected from an electrochemical device, a photo-electrochemical device, an optoelectronic device, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor, a biosensor, an electrochemical display and an electrochemical capacitor, or a dye sensitized solar cell.

17. The device according to claim 16 being a dye sensitized solar cell, wherein the dye is co-adsorbed with chenodeoxycholic acid.

Assignees

• Ecole Polytechnique Fed De Lausanne (Epfl)

Inventors

• Holcombe Thomas Wesley
• Yum Jun Ho
• Nazeeruddin Mohammad Khaja
• Graetzel Michael

Classifications

• C09K2211/1003

  Carbocyclic compounds · CPC title

• C09K2211/1011

  Condensed systems · CPC title

• H01L51/0068

  Electricity · mapped topic

• C09K2211/1033

  with oxygen · CPC title

• C09K2211/1037

  with sulfur · CPC title