Quinolinium dyes with fluorinated counter anion for dye sensitized solar cells

Patent metadata

Field	Value
Publication number	US-9865823-B2
Application number	US-201314385638-A
Country	US
Kind code	B2
Filing date	Mar 27, 2013
Priority date	Mar 30, 2012
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

The present invention relates to an electrode layer comprising a porous film made of oxide semiconductor fine particles sensitized with a quinolinium dye having a fluorinated counteranion. Moreover the present invention relates to a photoelectric conversion device comprising said electrode layer, a dye sensitized solar cell comprising said photoelectric conversion device and to novel quinolinium dyes having a fluorinated counteranion.

First claim

What is claimed:

1. An electrode layer comprising a porous film which comprises oxide semiconductor fine particles sensitized with a dye of formula (I),

where
n is 1, 2, 3, 4, 5 or 6;
R 1 and R 2 are independently of each other selected from the group consisting of hydrogen, C 1 -C 20 -alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof, C 6 -C 20 -aryl, heteroaryl and C 6 -C 20 -aryl which has 1, 2 or 3 substituents selected from C 1 -C 8 -alkyl, and
R 1 can additionally be a radical of formula D;
D is independently selected from a radical of formulae D.1 and D.2

where
* denotes the bond to the remaining compound of formula I,
R 17 and R 18 are independently of each other selected from unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted C 2 -C 20 -alkenyl, unsubstituted or substituted C 2 -C 20 -alkynyl, unsubstituted or substituted C 7 -C 20 -aralkyl, unsubstituted or substituted C 8 -C 20 -aralkenyl, unsubstituted or substituted C 8 -C 20 -aralkynyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C 4 -C 20 -cycloalkyl, unsubstituted or substituted C 5 -C 20 -cycloalkenyl and unsubstituted or substituted C 6 -C 20 -cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof, where R 14 is hydrogen, C 1 -C 20 -alkyl or C 6 -C 10 -aryl;
or
R 17 and R 18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;

or
R 17 and R 20 form together with the nitrogen atom to which R 17 is attached and the carbon atoms of the benzene ring to which R 20 and N—R 17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
or
R 17 and R 22 form together with the nitrogen atom to which R 17 is attached and the carbon atoms of the benzene ring to which R 22 and N—R 17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
and/or
R 18 and R 19 form with the nitrogen atom to which R 18 is attached and the carbon atoms of the benzene ring to which R 19 and N—R 18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
R 15 , R 16 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are independently of each other selected from the group consisting of hydrogen, NR 25 R 26 , OR 25 , SR 25 , NR 25 —NR 26 R 27 , NR 25 —OR 26 , O—CO—R 25 , O—CO—OR 25 , O—CO—NR 25 R 26 , NR 25 —CO—R 26 , NR 25 —CO—OR 26 , NR 25 —CO—NR 26 R 27 , CO—R 25 , CO—OR 25 , CO—NR 25 R 26 , S—CO—R 25 , CO—SR 25 , CO—NR 25 —NR 26 R 27 , CO—NR 25 —OR 26 , CO—O—CO—R 25 , CO—O—CO—OR 25 , CO—O—CO—NR 25 R 26 , CO—NR 25 —CO—R 26 , CO—NR 25 —CO—OR 26 , unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted C 2 -C 20 -alkenyl, unsubstituted or substituted C 2 -C 20 -alkynyl, unsubstituted or substituted C 7 -C 20 -aralkyl, unsubstituted or substituted C 8 -C 20 -aralkenyl, unsubstituted or substituted C 8 -C 20 -aralkynyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C 4 -C 20 -cycloalkyl, unsubstituted or substituted C 5 -C 20 -cycloalkenyl and unsubstituted or substituted C 6 -C 20 -cycloalkynyl,
wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof;

R 25 , R 26 and R 27 are independently of each other selected from hydrogen, unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted C 2 -C 20 -alkenyl, unsubstituted or substituted C 2 -C 20 -alkynyl, unsubstituted or substituted C 7 -C 20 -aralkyl, unsubstituted or substituted C 8 -C 20 -aralkenyl, unsubstituted or substituted C 8 -C 20 -aralkynyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C 4 -C 20 -cycloalkyl, unsubstituted or substituted C 5 -C 20 -cycloalkenyl and unsubstituted or substituted C 6 -C 20 -cycloalkynyl,
wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof;

A is a radical of formulae A.1, A.2, A.3, A.4 or A.5

where
# denotes the bond to the remaining compound of formula I
R 29 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are independently of each other selected from the group consisting of a radical G, hydrogen, halogen, OR 36 , unsubstituted or substituted unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted C 2 -C 20 -alkenyl, unsubstituted or substituted C 2 -C 20 -alkynyl, unsubstituted or substituted C 7 -C 20 -aralkyl, unsubstituted or substituted C 8 -C 20 -aralkenyl, unsubstituted or substituted C 8 -C 20 -aralkynyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C 5 -C 20 -cycloalkyl, unsubstituted or substituted C 5 -C 20 -cycloalkenyl and unsubstituted or substituted C 6 -C 20 -cycloalkynyl,
wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof;

with the proviso that at least one of the radicals R 29 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 is a radical G,
where
R 36 is unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR 14 or combinations thereof;
G is selected from the group consisting of —R 28 —COOH, —R 28 —COO − Z + , —R 28 —CO(C═O)OH, —R 28 —CO(C═O)O − Z + , —R 28 —S(═O) 2 OH, —R 28 —S(═O) 2 O − Z + , —R 2 —O—S(═O) 2 OH, —R 28 —O—S(═O) 2 O − Z + , —R 28 —P(═O)(OH) 2 , —R 28 —P(═O)(O − Z + ) 2 , —R 28 —P(═O)(OH)(O − Z + ), —R 28 —O—P(═O)(OH) 2 , —R 28 —O—P(═O)(O − Z + ) 2 , —R 28 —O—P(═O)(OH)(O − Z + ), —R 28 —CO—NH—OH, —R 28 —S(═O) 2 NH—OH, —R 28 —NR 14 —S(═O) 2 OH and —R 28 —NR 14 —S(═O) 2 O − Z + ;
where

R 28 is a direct bond, C 1 -C 20 -alkylene, C 2 -C 4 -alkenylene or C 6 -C 10 -arylene;

Z + is an organic or inorganic cation equivalent;
Y − is a fluorinated organic anion selected from Y.1, Y.2, Y.3, Y.4, Y.5 and Y.6;

wherein
X − is S(═O) 2 O − , O—S(═O) 2 O − , COO − ,

Rf 1 is selected from the group consisting of halogen, unsubstituted or substituted C 1 -C 20 -alkyl, unsubstituted or substituted haloalkyl, unsubstituted or substituted C 2 -C 20 -alkenyl, unsubstituted or substituted haloalkenyl, unsubstituted or substituted C 2 -C 20 -alkynyl, unsubstituted or substituted haloalkynyl, unsubstituted or substituted C 7 -C 20 -aralkyl, unsubstituted or substituted C 8 -C 20 -aralkenyl, unsubstituted or substituted C 8 -C 20 -aralkynyl, unsubstituted or substituted C 6 -C 20 -aryl, unsubstituted o

Assignees

• Basf Se

Inventors

• Send Robert
• Bruder Ingmar
• Erk Peter
• Sens Ruediger
• Yamamoto Hiroshi
• Yamato Hitoshi
• Nakamichi Shinji
• Takahashi Ryuichi

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• Y02E10/542

  Dye sensitized solar cells · CPC title

• H01L51/0064

  Electricity · mapped topic

• C09K2211/1014

  bridged by heteroatoms, e.g. N, P, Si or B · CPC title

• H01G9/2059

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