Triangulene oligomers and polymers and their use as hole conducting material

Patent metadata

Field	Value
Publication number	US-9385326-B2
Application number	US-201414758349-A
Country	US
Kind code	B2
Filing date	Jan 14, 2014
Priority date	Jan 15, 2013
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

The present invention related to thermally stable p-conducting oligomers and polymers of triangulene of formula (I) and their use in dye sensitized solar cells.

First claim

The invention claimed is:

1. A compound of the general formula 1:

wherein
n is 1 to 100,
X 1 , X 2 , X 3 , X 4 , and X 5 are independently of one another selected from hydrogen, F, Cl, Br, I, CN, B(OR c ) 2 ,
hydroxy, mercapto, nitro, cyanato, thiocyanato, formyl, acyl, carboxy, carboxylate, alkylcarbonyloxy, carbamoyl, alkylaminocarbonyl, dialkylaminocarbonyl, sulfo, sulfonate, sulfoamino, sulfamoyl, alkylsulfonyl, arylsulfonyl, amidino, NE 1 E 2 , where E 1 and E 2 are each independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino,
wherein R c is selected from in each case unsubstituted or substituted alkyl, cycloalkyl or aryl, or wherein two radicals R c may together form a divalent bridging group selected from in each case unsubstituted or substituted C 2 -C 10 -alkylene, C 3 -C 6 -cycloalkylene and C 6 -C 14 -arylene, wherein C 2 -C 10 -alkylene, C 3 -C 6 -cycloalkylene and C 6 -C 14 -arylene may carry one or more identical or different C 1 -C 12 -alkyl radicals,

R a and R b are independently of one another selected from hydrogen and unsubstituted C 1 -C 6 -alkyl,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently of one another selected from hydrogen, and in each case unsubstituted or substituted alkyl, alkoxy, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkoxy, bicycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkyloxy, aryl, aryloxy, heteroaryl and heteroaryloxy;
and wherein said compound of the general formula (1) has a linear structure.

2. A compound according to claim 1 , wherein n is 1 to 50.

3. A compound according to claim 1 , wherein n is 5, 6, 7, 8 or 9.

4. A compound according to claim 1 , wherein n is in a range of from 16 to 100.

5. A compound according to claim 1 , wherein the radicals R a and R b are all methyl.

6. A compound according to claim 1 , wherein the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and, if present, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are all hydrogen.

7. A compound according to claim 1 , wherein the radicals X 3 are all hydrogen.

8. A compound according to claim 1 , wherein one of the radicals X 1 and X 2 is hydrogen and the other is selected from the group consisting of hydrogen and unsubstituted or substituted alkyl, alkoxy, alkylthio, cycloalkyl, aryl, aryloxy and arylthio.

9. A compound according to claim 1 , wherein one of the radicals X 4 and X 5 is hydrogen and the other is selected from the group consisting of hydrogen and unsubstituted or substituted alkyl, alkyl, alkoxy, alkylthio, cycloalkyl, aryl, aryloxy and arylthio.

10. A compound according to claim 1 , wherein the radicals X 1 , X 2 , X 4 , and X 5 are all hydrogen.

11. A compound of the formula (I.a):

12. A compound of the formula (I.b):

wherein
n is 16 to 100,
X 2 and X 4 are independently of one another selected from the group consisting of hydrogen, and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyDamino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino.

13. A composition comprising at least one compound of general formula (I) as defined in claim 1 .

14. A process for the preparation of a compound of the formula I,

wherein
is 1 to 100,
X 1 , X 2 , X 3 , X 4 , and X 5 are independently of one another selected from the group consisting of hydrogen, F, Cl, Br, I, CN, B(OR c ) 2 ,
hydroxy, mercapto, nitro, cyanato, thiocyanato, formyl, acyl, carboxy, carboxylate, alkylcarbonyloxy, carbamoyl, alkylaminocarbonyl, dialkylaminocarbonyl, sulfo, sulfonate, sulfoamino, sulfamoyl, alkylsulfonyl, arylsulfonyl, amidino, NE 1 E 2 , where E 1 and E 2 are each independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyDamino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino,
wherein R c is selected from in each case unsubstituted or substituted alkyl, cycloalkyl or aryl, or wherein two radicals R c may together form a divalent bridging group selected from in each case unsubstituted or substituted C 2 -C 10 -alkylene, C 3 -C 6 -cycloalkylene and C 6 -C 14 -arylene, wherein C 2 -C 10 -alkylene, C 3 -C 6 -cycloalkylene and C 6 -C 14 -arylene may carry one or more identical or different C 1 -C 12 -alkyl radicals,

R a and R b are independently of one another selected from the group consisting of hydrogen and unsubstituted C 1 -C 6 -alkyl,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently of one another selected from the group consisting of hydrogen, and in each case unsubstituted or substituted alkyl, alkoxy, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkoxy, bicycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkyloxy, aryl, aryloxy, heteroaryl and heteroaryloxy;
and wherein said compound of the general formula (I) has a linear structure, comprising reacting a compound of the formula (A):

wherein y is 1 to (n-z) and Hal 1 is Cl, Br or I
with a compound of the formula (B):

wherein z is 0 to (n-y) and Hal 2 is Cl, Br or I,
in the presence of a transition metal-containing catalyst,
with the proviso that the sum of y+z is n.

15. A process according to claim 14 , wherein the transition metal-containing catalyst comprises bis(1,5-cyclooctadiene)nickel(0).

16. A dye-sensitized or Perovskite-based photoelectric conversion device comprising at least one compound of the formula (I) as defined in claim 1 .

17. A dye-sensitized photoelectric conversion device according to claim 16 , comprising:
an electrically conductive layer being part of or forming the working

Assignees

• Basf Se
• Max Planck Gesellschaft
• Max Planck Gesellschaft

Inventors

• Wonneberger Henrike
• Bruder Ingmar
• Send Robert
• Schluetter Florian
• Muellen Klaus
• Kivala Milan

Classifications

• H01G9/2059 Primary

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title

• H10K85/50

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H10K85/6572

  comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• H01L51/0558

  Electricity · mapped topic