AU2013217282A1

AU2013217282A1 - Rylene monoimide derivatives and use thereof as photosentizers in solar cells and photodetectors

Info

Publication number: AU2013217282A1
Application number: AU2013217282A
Authority: AU
Inventors: Flavio Luiz Benedito; Ingmar Bruder; Peter Erk; Chen Li; Klaus Mullen; Neil Gregory Pschirer; Robert SEND; Henrike WONNEBERGER
Original assignee: BASF SE; Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Current assignee: BASF SE; Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Priority date: 2012-02-09
Filing date: 2013-02-07
Publication date: 2014-08-14
Anticipated expiration: 2033-02-07
Also published as: JP2015516365A; KR20140134288A; WO2013118068A1; CN104245880A; EP2812412A1; AU2013217282B2; EP2812412A4

Abstract

The present invention relates to compounds of the formulae Ia,Ib and Ic in which R are identical or different aryloxy, arylthio, hetaryloxy, hetarylthio, aryl, diarylamino or dialkylamino radicals, n when m is 0: 0, 1, 2 or 3, when m is 1: 0, 1, 2, 3, 4 or 5, m is 0 or 1, A is -COOM, -SO

Description

WO 2013/118068 PCT/IB2013/050996 Rylene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors Description 5 The present invention relates to compounds of the formulae la, lb and Ic A A SN O0 N,,N 0 0 0 - - m R n~R _ m Y Y N-R 2LL R N-R2 N-R q R /R/ _q L - q (la) (Ib) (Ic) in which 10 R are identical or different aryloxy, arylthio, hetaryloxy, hetarylthio, aryl, diarylamino or dialkylamino radicals, n when m is 0: 0, 1, 2 or 3, 15 when m is 1: 0, 1, 2, 3, 4 or 5, m is 0 or 1, A is -COOM, -SO 3 M or -PO 3 M, 20 M is hydrogen, an alkali metal cation or [NR'] 4 +, R' is hydrogen or alkyl, where the R' radicals may be the same or different, 25 B is C 1 -C6-alkylene or 1,4-phenylene, where the phenylene radical may be mono- or polysubstituted by alkyl, nitro, cyano and/or halogen, WO 2013/118068 PCT/IB2013/050996 2 L is a chemical single bond or a bridge of the formula -(Het)Ar- or -(Het)Ar-(Het)Ar 5 which may be mono- or polysubstituted by phenyl, alkyl, alkoxy, alkylthio and/or -NR 4

R

5 and in which (Het)Ar is aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms, where, in the case of two (Het)Ar, these may be the same or 10 different, q is 0 or 1,

R

1 , R 2 are each independently radicals of the formula Ila, llb or Ilc 15 x R3- R PR (11a) (11b) (11c) R3 is phenyl, alkyl, alkoxy, alkylthio or -NR 6

R

7 , 20 X is C(R 8

R

9

)

2 , NR 10 , oxygen or sulfur,

R

4 to R 10 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, or aryl or hetaryl, each of which may be mono- or polysubstituted by alkyl, 25 alkoxy and/or alkylthio, p is 0, 1, 2, 3, 4 or 5, Y is NR 1 1 or sulfur, 30 and R11 is hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, or aryl, hetaryl, aralkyl or 35 hetaralkyl.

WO 2013/118068 PCT/IB2013/050996 3 The present invention further relates to the use of compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic and/or isomers thereof or mixtures of isomers of the compounds of the formulae la, lb and Ic as photosensitizers in solar cells and photodetectors, and to solar cells and photodetectors comprising 5 compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic and/or isomers thereof or mixtures of isomers of the compounds of the formulae la, lb and Ic photosensitizers. The direct conversion of solar energy to electrical energy in solar cells is based on the 10 internal photoeffect of a semiconductor material, i.e. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact. The photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power. 15 The semiconductor can absorb only those photons which have an energy which is greater than its band gap. The size of the semiconductor band gap thus determines the fraction of sunlight which can be converted to electrical energy. 20 Thin layers or films of metal oxides are known to constitute inexpensive solid semiconductor materials (n-semiconductors), but their absorption, owing to large band gaps, is typically not within the visible region of the electromagnetic spectrum. For use in solar cells, the metal oxides therefore have to be combined with a photosensitizer which absorbs in the wavelength range of sunlight, i.e. at from 300 to 2000 nm, and, in 25 the electronically excited state, injects electrons into the conduction band of the semiconductor. With the aid of a redox system which is used additionally in the cell and is reduced at the counterelectrode, electrons are recycled to the sensitizer which is thus regenerated. 30 Of particular interest for use in solar cells are the semiconductors zinc oxide, tin dioxide and especially titanium dioxide, which are used in the form of nanocrystalline porous layers. These layers have a large surface area which is coated with the sensitizer, so that high absorption of sunlight is achieved. 35 Dye-sensitized solar cells which are based on titanium dioxide as the semiconductor material are described, for example, in US-A-4 927 721, Nature 353, p. 737-740 (1991) and US-A-5 350 644, and also Nature 395, p. 583-585 (1998) and EP-A-1 176 646. These solar cells comprise monomolecular films of transition metal complexes, especially ruthenium complexes, which are bonded to the titanium dioxide layer via 40 acid groups, as sensitizers and iodine/iodide redox systems present in dissolved form or amorphous organic p-conductors based on spirobifluorenes.

WO 2013/118068 PCT/IB2013/050996 4 Also proposed repeatedly as sensitizers, not least for reasons of cost, have been metal-free organic dyes. For example, US-A-6 359 211 describes, for this purpose, cyanine, oxazine, thiazine 5 and acridine dyes which have carboxyl groups bonded via an alkylene radical for securing to the titanium dioxide semiconductor. Dyes with naphthalene monoimide anchor groups are described in the document WO 2008/132103 Al, but these compounds absorb in the short-wave spectral region of 10 sunlight (absolute maximum at about 450 nm) and are therefore unsuitable for efficient absorption and conversion of sunlight. Perylene-3,4:9,1 0-tetracarboxylic acid derivatives as sensitizers are examined in Japanese documents JP-A-10-189065, 2000-243463, 2001-093589, 2000-100484 and 15 10-334954, and in New J. Chem. 26, p. 1155-1160 (2002). The liquid electrolyte solar cells based on these perylene derivatives, however, exhibited much lower efficiencies than a solar cell sensitized with a ruthenium complex for comparison. The document WO 2007/054470 Al and the publications by Chen Li et al. in 20 ChemSusChem, Vol. 1, 615-618, 2008 and Ute B. Cappel et al in J. of Phys. Chem. C Letters, Vol. 113, No.33, 14595-14597, 2009 describe substituted rylene and perylene derivatives for use as sensitizers. It has now been found that, surprisingly, compounds of the formulae la, lb and Ic of the 25 present invention have very good quantum efficiencies, particularly in the NIR region of the absorption spectrum. Accordingly, the compounds of the formulae la, lb and Ic detailed at the outset have been found, as has the use thereof as photosensitizers in solar cells and 30 photodetectors. In the context of the present invention, aryl is especially a radical with a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from one aromatic ring or a plurality of fused aromatic rings. Suitable base skeletons are, for 35 example, phenyl, benzyl, naphthyl, anthracenyl or phenanthrenyl. This base skeleton may be unsubstituted, which means that all carbon atoms which are substitutable bear hydrogen atoms, or substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are, for example, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl, i-propyl or t 40 butyl, aryl radicals, preferably C6-aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals, alkenyl radicals, preferably WO 2013/118068 PCT/IB2013/050996 5 alkenyl radicals which bear a double bond, more preferably alkenyl radicals with one double bond and 1 to 8 carbon atoms, or groups with donor or acceptor action. Groups with donor action are understood to mean groups which have a +1 and/or +M effect, and groups with acceptor action are understood to mean groups which have a -1 5 and/or -M effect. Suitable groups with donor or acceptor action are halogen radicals, preferably F, Cl, Br, more preferably F, alkyl radicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, amine radicals, amide radicals, CH 2 F groups, CHF 2 groups, CF 3 groups, CN groups, thio groups or SCN groups. The aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, iso 10 propyl, n-propyl, n-butyl, iso-butyl, tert-butyl, aryloxy, amine, thio groups and alkoxy, or the aryl radicals are unsubstituted. The aryl radical or the aryl group is preferably a phenyl radical which is optionally substituted by at least one of the aforementioned substituents. The phenyl radical more preferably has none, one, two or three of the aforementioned substituents. 15 In the context of the present invention, hetaryl is a radical which has 5 to 30, preferably 5 to 18, carbon atoms and heteroatoms and differs from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom. Preferred heteroatoms are N, 0 and S. Most preferably, one 20 or two carbon atoms of the base skeleton of the aryl radicals are replaced by heteroatoms. The base skeleton is especially preferably selected from systems such as pyridyl, pyrimidyl, pyrazyl and triazolyl, and five-membered heteroaromatics such as pyrrole, furan, thiophene, imidazole, pyrazole, triazole, oxazole and thiazole. The base skeleton may be substituted at one, more than one or all substitutable positions of the 25 base skeleton. Suitable substituents are the same as have already been mentioned for the aryl groups. In the context of the present invention, the aryloxy, arylthio, hetaryloxy and hetarylthio radicals derive in a formal sense from the aforementioned aryl and heteroaryl radicals 30 by attachment of an oxygen or sulfur atom to a carbon atom of the aryl or heteroaryl radical. In the context of the present invention, alkyl is especially a radical having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. This alkyl radical may be branched or 35 unbranched and optionally be interrupted by one or more -0-, -S-, -CO-, -SO- and/or SO 2 - moieties. Alkyl is more preferably selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl, i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl and sec-hexyl. 40 In the context of the present invention, aralkyl and hetaralkyl include especially aryl and hetaryl-C-C 2 o-alkyl groups. They derive from the alkyl and aryl groups detailed above by formal replacement of a hydrogen atom of the linear or branched alkyl chain WO 2013/118068 PCT/IB2013/050996 6 by an aryl or hetaryl group. For example, suitable aralkyl groups be benzyl, ethylphenyl, n-propylphenyl and n-butylphenyl, and as hetaralkyl the moiety of the formula S (CH2)t 5 in which t is especially the values of 1, 2, 3 and 4. In the context of the present invention, alkoxy and alkylthio radicals derive in a formal sense from the aforementioned alkyl radicals by attachment of an oxygen or sulfur 10 atom to a carbon atom of the alkyl radical. In the context of the present invention, halogen is preferably F, Cl or Br, more preferably F. 15 In the context of the present invention, alkali metal cation is preferably Li, Na, Cs or K, more preferably Na. When the bridge L is mono- or polysubstituted by phenyl, alkyl, alkoxy, alkylthio and/or -NR 4

R

5 , this means that these substituents are attached to suitable positions on 20 the aromatic and heteroaromatic Ar groups. When the bridge L comprises two (Het)Ar, they may be the same or different. Examples of suitable (Het)Ar include 1,4-, 1,3- and 1,2-phenylene, 1,4- and 1,8 25 naphthylene, 1,4- and 2,3-pyrrylene, 2,5-, 2,4- and 2,3-thienylene, 2,5-, 2,4- and 2,3 furanylene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinylene, 2,3-, 2,5-, 2,6-, 3,7-, 4,8-, 5,8- and 6,7-quinolinylene, 2,7-, 3,6-, 4,5-, 2,6-, 3,7-, 4,7- and 4,8-isoquinolinylene, 1,4 [2,5-di(tert-butyl)]phenylene, 1,4-(2,5-dihexyl)phenylene, 1,4-[2,5-di(tert octyl)]phenylene, 1,4-(2,5-didodecyl)phenylene and 1,4-[2,5-di(2-dodecyl)]phenylene. 30 Especially useful as (Het)Ar are 1,4-phenylene and 2,5-thienylene. Further suitable bridges L are, for example: WO 2013/118068 PCT/IB2013/050996 7 S s s S 0 S S S 0 preferably: Ss 5 Preference is given to inventive compounds in which, in the formulae la, lb and Ic: R are identical or different aryloxy or arylthio radicals, 10 n when m is 0 or m is 1: 0, 1 or 2, m is 0 or 1, 15 A is -COOM, M is hydrogen or an alkali metal cation, B is C 1 -C6-alkylene, 20 L is a chemical single bond or a bridge of the formula WO 2013/118068 PCT/IB2013/050996 8 -(Het)Ar- or -(Het)Ar-(Het)Ar which may be mono- or polysubstituted by phenyl, C 1

-C

1 2 -alkyl, C 1

-C

12 alkoxy, C 1

-C

12 -alkylthio and/or -NR 4

R

5 , and in which (Het)Ar is identical or 5 different aryl or hetaryl which may be fused to saturated or unsaturated 5 to 18-membered rings which may comprise heteroatoms, q is 0 or 1, 10 R 4 , R 5 are each independently hydrogen or C 1

-C

1 2 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties,

R

1 , R 2 are each independently radicals of the formulae ll'a, ll'b or ll'c x 15 (11'c) R3 is C 1

-C

1 2 -alkoxy, 20 p is0or1, X is C(R 8

R

9

)

2 , NR 10 , oxygen or sulfur,

R

8 , R 9 , R 1 0 are each independently hydrogen or C 1

-C

12 -alkyl whose carbon chain may 25 be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, Y is NR 1 1 or sulfur, and 30 R11 is hydrogen or C 1

-C

12 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties. Particular preference is given to inventive compounds in which, in the formulae la, lb 35 and Ic: n is 0, WO 2013/118068 PCT/IB2013/050996 9 m is 0 or 1, A is -COOM, 5 M is hydrogen or an alkali metal cation, B is C 1 -C6-alkylene, 10 L is a chemical single bond or a bridge of the formula -(Het)Ar- or -(Het)Ar-(Het)Ar in which (Het)Ar is identical or different aryl or hetaryl, 15 q is 0 or 1,

R

1 , R 2 are each independently radicals of the formulae ll'a, ll'b or ll'c x - 3 RPR 20 (11'a) (11'b) (11'c) R3 is C 1

-C

1 2 -alkoxy, p is 0 or 1, 25 X is C(R 8

R

9

)

2 or NR 10 ,

R

8 , R 9 , R 1 0 are each independently hydrogen or C 1

-C

1 2 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, 30 Y is NR 1 1 or sulfur, and 35 R 11 is hydrogen or C 1

-C

1 2 -alkyl.

WO 2013/118068 PCT/IB2013/050996 10 The invention shall encompass not just the compounds of the formulae la, Ib and Ic and the preferred embodiments thereof, but also mixtures thereof, isomers thereof and the mixtures of the isomers. 5 For example, the invention also includes isomeric compounds of the formula l*b shown below A NN N, 0 Rn Y L \R .. _ q (1*b) In the context of the present invention, also claimed is the use of the aforementioned 10 compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic and the preferred embodiments thereof and/or the use of isomers thereof or mixtures of the isomers of the compounds of the formulae la, lb and Ic and the preferred embodiments thereof as photosensitizers in solar cells and photodetectors. 15 In the context of the present invention, additionally claimed are solar cells and photodetectors which comprise the aforementioned compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic and the preferred embodiments thereof and/or isomers thereof or mixtures of the isomers of the compounds of the formulae la, lb and Ic and the preferred embodiments thereof as 20 photosensitizers. Examples: 1.) Synthesis of the inventive compound (PS1) WO 2013/118068 PCT/IB2013/050996 11 COOH O N 0 N (PS 1) 5 a) Synthesis of N-(2,6-diisopropylphenyl)-9-(2-nitrophenyl)-3,4 perylenedicarboximide o N 0 0 N 0 B NO 2 WO 2013/118068 PCT/IB2013/050996 12 In a Schlenk tube, 500 mg of N-(2,6-diisopropylphenyl)-9-(4,4,5,5-tetramethyl-1,3,2 dioxaborolan-2-yl)-3,4-perylenedicarboximide (0.824 mmol) and 247 mg of 1-bromo-2 nitrobenzene (1.235 mmol) were dissolved in 40 mL of toluene, and 800 mg (5.797 mmol) of potassium carbonate and 800 mg of potassium carbonate in 4 mL of 5 water and 0.4 mL of ethanol were added. After degassing the reaction solution with argon, 184 mg of tetrakis(triphenylphosphine)palladium(0) (0.165 mmol) were added, and the mixture was degassed again and stirred at 80'C under argon overnight. The reaction solution was cooled to room temperature and extracted with water and 10 dichloromethane. The reaction mixture was separated by column chromatography on silica gel by means of dichloromethane. Yield: 203 mg (41 %) of red dye. 15 b) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-1 -hexyl-1 H-indole)-3,4-perylene dicarboximide 0 N 0 0 N 0 N N02 20 The synthesis was based on syntheses known from the literature (J. of Heterocyclic Chem. 46, 1309-1317, 2009; J. Org. Chem., 70, 5014-5019, 2005; J. Org. Chem. 73, 7369-7372, 2008, Proc. Chem. Soc., 361, 1962; Chem.- and Ind., 1282, 1963). 500 mg of N-(2,6-diisopropylphenyl)-9-(2-nitrobenzyl)-3,4-perylened icarboximide 25 (0.830 mmol) and 650 mg of triphenylphosphine (2.48 mmol) were dissolved in 15 mL of o-dichlorobenzene and stirred in a microwave at 182'C and 300 W over the course of 8 h. The precipitated product was filtered off and used further without further purification.

WO 2013/118068 PCT/IB2013/050996 13 Yield (crude): 320 mg (68%) of dark violet dye c) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-1 -hexyl-1 H-indole)-3,4-perylene dicarboximide 5 O N 0 0 N 0 N N 210 mg of N-(2,6-diisopropylphenyl)-8,9-([b]-1 H-indole)-3,4-perylenedicarboximide (0.368 mmol) and 12 mg of sodium hydride (0.478 mmol) were introduced into a 10 Schlenk tube and evacuated. 15 mL of anhydrous DMF were added under argon. The solution was stirred at room temperature for 30 minutes (color change from violet to blue). After the addition of 122 mg of bromohexane (0.736 mmol), the solution was stirred for a further 3 h (color change back to violet). 15 The reaction was quenched with water, extracted with dichloromethane and water/hydrochloric acid (3:1) and dried over magnesium sulfate. The violet crude product was purified by means of column chromatography on silica gel with dichloromethane. 20 Yield: 128 mg (53%) of violet solid.

WO 2013/118068 PCT/IB2013/050996 14 d) Synthesis of 8,9-([b]-1 -hexyl-1 H-indole)-3,4-perylenedicarboxylic anhydride o N 0 0 0 0 N N 110 mg of N-(2,6-diisopropylphenyl)-8,9-([b]-1 -hexyl-1 H-indole)-3,4-perylene 5 dicarboximide (0.168 mmol) were dissolved in 10 mL of 2-methyl-2-butanol, 375 mg of potassium hydroxide (6.7 mmol) were added, and the mixture was degassed and boiled under reflux overnight. After cooling, the reaction solution was added to ice in diluted acetic acid (1:10 acetic 10 acid:water). The precipitate was filtered off, washed with water and dissolved in dichloromethane. A few drops of acetic acid were added to the solution which was stirred overnight. The anhydride formed (N-(2,6-diisopropylphenyl)-8,9-([b]-1 -hexyl-1 H indole)-3,4-dicarboxylic monoanhydride) was converted further in crude form. 15 Yield (crude): 80 mg (96%) of dark violet solid e) Synthesis of the target compound COOH 0 O O O N N

N

WO 2013/118068 PCT/IB2013/050996 15 80 mg of a crude anhydride (0.161 mmol) were introduced into a Schlenk tube with 1 g of glycine (13.4 mmol) and 2 g of imidazole (29.4 mmol). After degassing, the mixture was stirred at 140'C under argon overnight. 5 After cooling, the crude product was dissolved out of the flask by means of dilute hydrochloric acid (1:5 hydrochloric acid:water). The precipitate was filtered off and washed to neutrality. The crude product was purified by means of column chromatography on silica gel with THF and THF:acetic acid (1:1). 10 Yield: 50 mg (56%) of dark violet solid 2.) Synthesis of the inventive compound (PS2) COOH O N O N N (PS2) 15 WO 2013/118068 PCT/IB2013/050996 16 a) Synthesis of N-(2,6-diisopropylphenyl)-9-(4-chloro-2-nitrobenzyl)-3,4-perylene dicarboximide 0 N 0 0 N 0 B, NO 2 0 O CI 5 In a Schlenk tube, 1.2 g of N-(2,6-diisopropylphenyl)-9-(4,4,5,5-tetramethyl-1 ,3,2 dioxaborolan-2-yl)-3,4-perylenedicarboximide (1.98 mmol), 700 mg of 1-bromo-4 chloro-2-nitrobenzene (2.96 mmol) were dissolved in 80 mL of toluene, and 1.6 g of potassium carbonate (11.59 mmol) in 8 mL of water and 0.8 mL of ethanol were added. After the reaction solution had been degassed with argon, 330 mg of 10 tetrakis(triphenylphosphine)palladium(O) (0.296 mmol) were added, and the mixture was degassed again and stirred at 80'C for 36 h. The reaction solution was cooled to room temperature and extracted with water and dichloromethane. The reaction mixture was separated by column chromatography on 15 silica gel by means of dichloromethane. Yield: 1.0 mg (79%) of red solid b) Synthesis of N-(2,6-diisopropylphenyl)-9-(4-(bis(9,9-dimethylfluoren-2-yl)amine) 20 2-nitrophenyl)-3,4-perylenedicarboximide WO 2013/118068 PCT/IB2013/050996 17 O N 0 0 N 0

NO

2 NO 2 CI N / \\ 750 mg of N-(2,6-diisopropylphenyl)-9-(4-chloro-2-nitrobenzyl)-3,4 perylenedicarboximide (1.18 mmol), 700 mg of bis(9,9-dimethylfluoren-2-yl)amine 5 (1.75 mmol), 760 mg of cesium carbonate (2.33 mmol), 110 mg of tris(dibenzylideneacetone)dipalladium(O) (0.120 mmol) and 145 mg of 2,2' bis(diphenylphosphino)-1,1'-binaphthyl (0.228 mmol) were dissolved in 30 mL of dry toluene under argon and stirred at 1 00 0 C under argon for 16 h. 10 The crude mixture was purified by means of column chromatography on silica gel with dichloromethane. Yield: 770 mg of red solid (65%) 15 c) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2 yl)-1 H-indol-6-amine)-3,4-perylenedicarboximide WO 2013/118068 PCT/IB2013/050996 18 O N O O N O N NO2 N \ N 350 mg of N-(2,6-diisopropylphenyl)-9-(4-(bis(9,9-dimethylfluoren-2-yl)amine)-2 nitrobenzyl)-3,4-perylenedicarboximide (0.349 mmol) and 275 mg of triphenylphoshine 5 (1.05 mmol) were dissolved in 10 mL of o-dichlorobenzene and stirred in a microwave at 182'C and 300 W over the course of 8 h. Workup A: 10 The solvent was removed by means of a Kugelrohr still and the reaction mixture was purified by means of column chromatography on silica gel with dichloromethane. Workup B: 15 Alternatively, the mixture, after the treatment in the microwave, was precipitated in petroleum ether and stirred at 50'C for 2 h. The blue precipitate formed was filtered off through a D4 glass frit and washed with petroleum ether until the filtrate became clear. The product formed was clean and could be converted further without purification. 20 Yield: blue solid: 90% WO 2013/118068 PCT/IB2013/050996 19 d) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2 yl)-l -hexyl-1 H-indol-6-amine)-3,4-perylenedicarboximide o o o N 0 N 5 Method A: 85 mg of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 H indol-6-amine)-3,4-perylenedicarboximide (0.087 mmol) and 3 mg of sodium hydride 10 (0.125 mmol) were introduced into a Schlenk tube and evacuated. 15 mL of anhydrous DMF were added under argon. The solution was stirred at room temperature for 20 minutes. After the addition of 60 mg of bromohexane (0.242 mmol), the solution was stirred for a further 3 h. 15 The solvent was removed using a Kugelrohr still and the reaction mixture was purified by means of column chromatography on silica gel with dichloromethane. Yield: 85 mg (92%) 20 Method B: In an argon-purged flask, 0.54 g of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9 dimethyl-9H-fluoren-2-yl)-1 H-indol-6-amine)-3,4-perylenedicarboximide (0.56 mmol) was dissolved in 25 mL of dichloromethane, 0.04 g of sodium hydroxide (1.11 mmol) in 25 10 mL of acetone was added and the mixture was stirred at room temperature for 5 minutes. Finally, 0.18 g of bromohexane (1.11 mmol) was introduced and the mixture was stirred at reflux under argon overnight.

WO 2013/118068 PCT/IB2013/050996 20 The reaction mixture was extracted by shaking with water/dichloromethane and purified by means of column chromatography on silica gel in dichloromethane. Yield: blue solid 0.42 g (71 %) 5 e) Synthesis of 8,9-([b]-N,N-bis(9,9-dimethyl-9 H-fluoren-2-yl)-1 -hexyl-1 H-indol-6 amine)-3,4-perylenedicarboxylic anhydride 0 N 0 0 0 0 N - N N. N N 10 200 mg of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 hexyl-1 H-indol-6-amine)-3,4-perylenedicarboximide (0.189 mmol) were dissolved in 15 mL of 2-methyl-2-butanol, 425 mg of potassium hydroxide (7.59 mmol) were added, and the mixture was degassed and boiled under reflux overnight. 15 After cooling, the reaction solution was added to ice in dilute acetic acid (1:10 acetic acid:water). The precipitate was filtered off, washed with water and dissolved in dichloromethane. A few drops of acetic acid were added to the solution, which was stirred overnight. The resulting anhydride (N-(2,6-diisopropylphenyl)-8,9-([b]-N,N 20 bis(9,9-dimethyl-9H-fluoren-2-yl)-1-hexyl-1 H-indol-6-amine)-3,4-perylenedicarboxylic monoanhydride) was converted further in crude form. Yield (crude): 160 mg (94%) of blue solid 25 WO 2013/118068 PCT/IB2013/050996 21 f) Synthesis of the target compound COOH N o 0 NrNo N N 5 160 mg of the crude anhydride (0.076 mmol) were introduced together with 2 g of glycine (26.8 mmol) and 3 g of imidazole (44.1 mmol) into a Schlenk tube. After degassing, the mixture was stirred at 140'C under argon overnight. After cooling, the crude product was dissolved from the flask by dilute hydrochloric acid 10 (1:5 hydrochloric acid:water). The precipitate was filtered off and washed to neutrality, and the crude product was purified by means of column chromatography on silica gel with THF and THF:acetic acid (1:1). Yield: 100 mg (58%) of blue solid 15 WO 2013/118068 PCT/IB2013/050996 22 3.) Synthesis of the inventive compound (PS3) The compound was prepared analogously to the synthesis of compound ID1216 using bis(9,9-dibutylfluoren-2-yl)amine rather than bis(9,9-dimethylfluoren-2-yl)amine. 5 COOH O N O HgC 4

C

4

H

9 HC4

C

4

H

9 N (PS3) WO 2013/118068 PCT/IB2013/050996 23 4.) Synthesis of the inventive compound (PS4) 0 O o N 0 N N (PS4) 5 a) Synthesis of N-(2,6-diisopropylphenyl)-9-(4-(bis(9,9-dimethylfluoren-2-yl)-amine) 2-nitrobiphenyl)-3,4-perylenedicarboximide WO 2013/118068 PCT/IB2013/050996 24 0 N 0 0 N 0 O' B'O0 +N NO 2

NO

2 N Ni N N02 1.5 g of N-(2,6-diisopropylphenyl)-9-(4-chloro-2-nitrobiphenyl)-3,4-perylene dicarboximide (2.4 mmol) were dissolved in 50 mL of dioxane, and 1.4 ml of 5M sodium 5 hydroxide solution (7.1 mmol) were added. After degassing with argon for 30 min, 0.04 g of bis(tri-tert-butylphosphine)palladium(0) (0.08 mmol) and 1.7 g of bis(9,9 dimethyl-9H-fluoren-2-yl)-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]amine (2.8 mmol) were introduced successively. The reaction proceeds at 85'C, generally over a period of 3 to 4 days. 10 Thereafter, the solvent was drawn off on a rotary evaporator. The purification was effected by column chromatography on silica gel in methylene chloride. Yield: 1.6 g (64%) of red solid 15 b) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2 yl)-1 H-indol-6-amine)-4-phenyl-3,4-perylenedicarboximide WO 2013/118068 PCT/IB2013/050996 25 0 N 0 0 N 0 N

NNO

2 N N N 800 mg of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 H indol-6-amine)-4-phenyl-3,4-perylenedicarboximide (0.74 mmol) were dissolved 5 together with 600 mg of triphenylphosphine (2.2 mmol) in 15 ml of o-dichlorobenzene and stirred at room temperature for 15 min. This was followed by the reaction in a microwave at 182'C for 8 h. The blue reaction mixture formed was precipitated in petroleum ether, stirred at 50'C 10 for 3 h and filtered with suction through a D4 glass frit. The mother liquor has a strong red color. The blue filter residue was washed with petroleum ether until the filtrate was colorless. No further purification was necessary. 15 Yield: 1.5 g (97%) of blue solid c) Synthesis of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2 yl)-1 -hexyl-1 H-indol-6-amine)-4-phenyl-3,4-perylenedicarboximide 20 WO 2013/118068 PCT/IB2013/050996 26 NN O N O0 0 N O a NIO N N N N N 1.5 g of N-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 H indol-6-amine)-4-phenyl-3,4-perylenedicarboximide (1.4 mmol) were dissolved in 5 80 mL of dichloromethane, and 0.11 g of sodium hydroxide (2.9 mmol) in 30 mL of acetone was added. After stirring at room temperature for 5 min, 0.71 g of bromohexane (4.3 mmol) was introduced. The mixture was kept at reflux for 2 days and then extracted by shaking with water/dichloromethane. The organic phase was purified by column chromatography on silica gel in dichloromethane. 10 Yield: 0.64 g (59%) of blue solid WO 2013/118068 PCT/IB2013/050996 27 d) Synthesis of 8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 -hexyl-1 H-indol-6 amine)-4-phenyl-3,4-perylenedicarboxylic anhydride O N 0 0 0 0 NN N N 5 0.95 g of N-carboxymethyl-(2,6-diisopropylphenyl)-8,9-([b]-N,N-bis(9,9-dimethyl-9H fluoren-2-yl)-1 -hexyl-1 H-indol-6-amine)-4-phenyl-3,4-perylenedicarboximide (0.84 mmol) was dissolved in 60 ml of 2-methyl-2-butanol, and 1.9 g of KOH (34 mmol) were added. The reaction proceeded under gentle reflux for 2 days. 10 After cooling to room temperature, the mixture was precipitated in ice-water with acetic acid and stirred for 1 h. The red precipitate formed was filtered off with suction and washed briefly with water. Thereafter, the presscake was dissolved in dichloromethane and the remaining water was removed in a separating funnel. The organic phase was 15 acidified again with acetic acid and stirred at room temperature overnight. After concentration on a rotary evaporator, the red-violet residue was stirred in methanol for extractive purification, filtered with suction through a glass frit and washed briefly with methanol. The filtrate was pale red in color. 20 Yield 0.58 g (70%) of red solid WO 2013/118068 PCT/IB2013/050996 28 e) Synthesis of the target compound OH 0 0 o 0 N 0 0 +

H

2 N -OH N N N N 750 mg of 8,9-([b]-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-1 -hexyl-1 H-indol-6-amine)-4 5 phenyl-3,4-perylenedicarboxylic anhydride (0.77 mmol) were weighed into a Schlenk tube together with 5 g of glycine (67 mmol) and 10 g of imidazole (147 mmol). The flask was closed with a septum and shaken gently in order to roughly mix the powders. Subsequently, reduced pressure was applied for 15 min and, finally, the mixture was heated to 140'C under argon. The flask was darkened with aluminum foil in order to 10 prevent sublimation at the flask wall. After 20 h at 140'C, the melt was cooled to 50'C and precipitated in 500 mL of dilute hydrochloric acid. The further stirring time at 60'C was 2 h. The precipitate formed was filtered off with suction using a D4 glass frit and washed with warm water until the 15 filtrate was no longer yellow but clear. The product was purified by column chromatography on silica gel. This commenced with pure dichloromethane + 2% acetic acid, with elution here only of the impurities. On addition of 1-5% methanol, the product also began to elute. 20 Yield: 75 mg (10%) of violet solid WO 2013/118068 PCT/IB2013/050996 29 5.) Synthesis of the inventive compound (PS5) COOH o N 0 N N (PS5) 5 a) Synthesis of N-cyclohexyl-4-(4-chloro-2-nitrophenyl)naphthalene-1,8 dicarboximide O N 0 0 N 0 B1 NO 2 Cl 10 In a Schlenk tube, 2 g of N-cyclohexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalene-1,8-dicarboximide (4.93 mmol), 1.75 g of 1-bromo-4-chloro-2 nitrobenzene (7.40 mmol) were dissolved in 80 mL of toluene, 1.6 g of potassium carbonate (11.6 mmol) in 8 mL of water and 0.8 mL of ethanol are added, and the mixture was thoroughly degassed. After addition of 800 mg of tetrakis(triphenyl- WO 2013/118068 PCT/IB2013/050996 30 phosphine)palladium(0) (0.717 mmol), the mixture was degassed again and stirred at 80'C under argon for 2 days. The reaction solution was cooled to room temperature and extracted with water and 5 dichloromethane. The reaction mixture was separated by column chromatography on silica gel by means of dichloromethane:petroleum ether (1:1). Yield: 700 mg (32) of pale yellow solid 10 b) Synthesis of N-cyclohexyl-4-(4-di(p-tert-octylphenyl)amino-2 nitrophenyl)naphthalene-1,8-dicarboximide O N 0 O N O

NO

2

NO

2 CI N 15 600 mg of N-cyclohexyl-4-(4-chloro-2-nitrophenyl)naphthalene-1,8-dicarboximide (1.38 mmol), 815 mg of bis(9,9-dimethylfluoren-2-yl)amine (2.07 mmol), 900 mg of cesium carbonate (2.76 mmol), 125 mg of tris(dibenzylideneacetone)dipalladium(0) (0.136 mmol) and 170 mg of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.273 mmol) were dissolved in 30 mL of dry toluene under argon and stirred at 1 00 0 C under argon 20 for 16 h. The crude mixture was purified by means of column chromatography on silica gel with dichloromethane:petroleum ether (1:1). 25 Yield: 640 mg of yellow solid (64%) WO 2013/118068 PCT/IB2013/050996 31 c) Synthesis of N-cyclohexyl-3,4-([b]-NN-bis(p-tert-octylphenyl)-1 -hexyl-1 H-indol-6 amine)-1,8-naphthalenedicarboximide O N 0 0 N 0 N

NO

2 N N 5 550 mg of N-cyclohexyl-4-(4-di(p-tert-octylphenyl)amino-2-nitrophenyl)naphthalene 1,8-dicarboximide (0.694 mmol) and 545 mg of triphenylphosphine (2.08 mmol) were dissolved in 10 mL of o-dichlorobenzene and stirred in a microwave at 182'C and 300 W over the course of 4 h. The solvent was removed by means of a Kugelrohr still 10 and isolated by means of column chromatography on silica gel with dichloromethane. Yield (crude): 430 mg (82%) of orange solid WO 2013/118068 PCT/IB2013/050996 32 d) Synthesis of N-cyclohexyl-3,4-([b]-N,N-bis(p-tert-octylphenyl)-1 -hexyl-1 H-indol-6 amine)-1,8-naphthalenedicarboximide 0 N 0 0 N 0 N N N N 5 350 mg of N-cyclohexyl-3,4-([b]-N,N-bis(p-tert-octylphenyl)-1 H-indol-6-amine)-1,8 naphthalenedicarboximide (0.460 mmol) and 14 mg of sodium hydride (0.583 mmol) were introduced into a Schlenk tube, which was evacuated. 15 mL of anhydrous DMF were added under argon. The solution was stirred at room temperature for 30 minutes. After the addition of 230 mg of bromohexane (1.39 mmol), the solution was stirred for a 10 further 3 h. The reaction was quenched with water, extracted with dichloromethane and water/hydrochloric acid (3:1) and dried over magnesium sulfate. The orange crude product was purified by means of column chromatography on silica gel with 15 dichloromethane. Yield: 270 mg (71 %) of orange solid WO 2013/118068 PCT/IB2013/050996 33 e) Synthesis of 3,4-([b]-N,N-bis(p-tert-octylphenyl)-1 -hexyl-1 H-indol-6-amine)-1,8 naphthalenedicarboxylic anhydride (PS6) P0 0 0 0 N 0 N~ N N (PS6) 5 170 mg of N-cyclohexyl-3,4-([b]-N,N-bis(p-tert-octylphenyl)-1 -hexyl-1 H-indol-6-amine) 1,8-naphthalenedicarboximide (0.201 mmol) were dissolved in 10 mL of 2-methyl-2 butanol, 450 mg of potassium hydroxide (8.04 mmol) were added, and the mixture was 10 degassed and boiled under reflux overnight. After cooling, the reaction solution was added to ice in dilute acetic acid (1:10 acetic acid:water). The precipitate was filtered off, washed with water and dissolved in dichloromethane. A few drops of acetic acid were added to the solution, which was 15 stirred overnight. The majority of the anhydride formed (N-cyclohexyl-3,4-([b]-N,N bis(p-tert-octylphenyl)-1 -hexyl-1 H-indol-6-amine)-1,8-naphthalenedicarboxylic monoanhydride) was converted further in crude form. A portion (60 mg) of the product was purified by column chromatography (silica gel, 4:1 20 toluene:DCM) and used as the inventive dye PS6 for the construction of the OPV cell described hereinafter. Yield (crude): 145 mg (95%) of red solid 25 WO 2013/118068 PCT/IB2013/050996 34 e) Synthesis of the target compound COOH O 0 0 O N O N N 80 mg of the crude anhydride (0.104 mmol) were introduced together with 1 g of 5 glycine (23.4 mmol) and 2 g of imidazole (29.4 mmol) into a Schlenk tube. After degassing, the mixture was stirred at 140'C under argon overnight. After cooling, the crude product was dissolved from the flask by means of dilute hydrochloric acid (1:5 hydrochloric acid:water). The precipitate was filtered off and 10 washed to neutrality. The crude product was purified by means of column chromatography on silica gel with dichloromethane, THF and dichloromethane:acetic acid (1:1). Yield: 75 mg (87%) of orange solid 15 6. Synthesis of the inventive compound (PS7) WO 2013/118068 PCT/IB2013/050996 35 0 aOH OONO O N O N - N a) Synthesis of N-(2,6-diisopropylphenyl)-9-(4-amino-2-nitrophenyl)-3,4-perylene dicarboximide (compound 2) 5 O N 0 0 N 0 B, NO2 NNH

NH

2 1 2 In a three-neck flask, 1 g of N-(2,6-diisopropylphenyl)-9-(4,4,5,5-tetramethyl-1,3,2 dioxaborolan-2-yl)-3,4-perylenedicarboximide (1.6 mmol; compound 1) and 1.4 g of 1 10 bromo-4-amino-2-nitrobenzene (6.6 mmol) were dissolved in 50 mL of toluene and 1.8 g of potassium carbonate (23 mmol) in 10 mL water and 5 mL ethanol were added. After the reaction solution had been purged with argon, 0.6 g of tetrakis(triphenylphosphine)palladium(0) (0.49 mmol) were added and the mixture was stirred at 85'C for 20 h. 15 WO 2013/118068 PCT/IB2013/050996 36 The reaction solution was cooled to room temperature and extracted with water and dichloromethane. The reaction mixture was separated by column chromatography on silica gel by means of dichloromethane. 5 Yield: 0.7 g (69%) of red solid b) Synthesis of compound 3 0 N O 0 N 0

NO

2

NO

2 NHN NH 2N 2 3 10 In a two-neck flask, 0.5 g of N-(2,6-diisopropylphenyl)-9-(4-amino-2-nitrophenyl)-3,4 perylenedicarboximide (0.8 mmol; compound 2) and 0.82 g of 7-bromo-2-tert butylpyrene (2.4 mmol) were dissolved in 25 mL of toluene. Consecutively, 0.06 g of tris(dibenzylidenacetone)dipalladium(0) (0.06 mmol), 0.2 g tri-(tert-butyl)phospine (10 15 weight-% in toluene; 0.11 mmol) and 0.16 g sodium tert-butylate (1.6 mmol) were added and the mixture was stirred at 80'C for 20 h.

WO 2013/118068 PCT/IB2013/050996 37 The reaction solution was cooled to room temperature, the solvent removed by means of a rotary evaporator and the product isolated by means of column chromatography on silica gel with dichloromethane/toluene 4:1. 5 Yield: 220 mg (24%) of violet solid c) Synthesis of compound 4 O N O 0 N O

NO

2 N N N 3 4 10 220 mg of compound 3 (0.19 mmol) and 118 mg triphenylphosphine (0.58 mmol) were dissolved in 2 mL of o-dichlorobenzene and stirred in a microwave at 182'C for 12 h. Using toluene the reaction mixture was transferred in a round-bottomed flask, 15 concentrated by means of a rotary evaporator to dryness and the purification was effected by column chromatography on silica gel with dichloromethane/toluene 4:1. Yield: 140 mg (65%) of a green solid WO 2013/118068 PCT/IB2013/050996 38 d) Synthesis of compound 5 O N O 0 N O N N N N 4 5 5 140 mg of compound 4 (0.13 mmol) and 8 mg of sodium hydride (60 weight-% in mineral oil; 0.19 mmol) were introduced into a Schlenk tube and the latter evacuated. Under an argon atmosphere 15 mL of dry dimethyl formamide war added. The mixture was stirred at room temperature for 20 min. 63 g (0.38 mmol) of bromohexane were added and the solution was stirred for a further 4 h. 10 The reaction solution was extracted with water and dichloromethane and the product isolated by means of column chromatography on silica gel with dichloromethane/toluene 4:1. 15 Yield: 100 mg (67%) of a green solid WO 2013/118068 PCT/IB2013/050996 39 e) Synthesis of compound 6 0 N O 0 0 0 NN N N N 4- 6 5 5 100 mg of compound 5 (0.08 mmol) were dissolved in 20 mL of 2-methyl-2-butanol, 189 mg of potassium hydroxide (3.4 mmol) added and the mixture heated under reflux over night. After cooling to room temperature, the mixture was poured on crushed ice in diluted 10 acetic acid (1:10 acetic acid: water). The precipitate formed was filtered off , washed with water and dissolved in dichloromethane. Thereafter, the solution was acidified with a few mL of acetic acid and stirred at room temperature over night. The solvent was removed by means of a rotary evaporator, the resulting residue stirred with methanol, filtered off and then dried. 15 Yield: 65 mg (75%) of green solid WO 2013/118068 PCT/IB2013/050996 40 f) Synthesis of target compound PS7 0 r-J- OH 0 0 0 O N 0 N N N N 4- 6 7 (PS7) 5 65 mg of compound 6 (0.06 mmol), 1 g of glycine (0.013 mmol) and 2 g of imidazole (0.029 mmol) were introduced into a Schlenk tube. After degassing the reaction mixture was stirred under an argon atmosphere at 140'C over night. The reaction mixture was cooled to room temperature, the reaction product rinsed out 10 of the Schlenk tube with 2 M hydrochloric acid and the precipitate filtered off and washed to neutrality. The crude product was cleaned by means of column chromatography on silica gel with dichloromethane/ethanol 9:1 with addition of 2% of triethylamine. 15 Yield: 50 mg (75%) of green solid WO 2013/118068 PCT/IB2013/050996 41 7. Synthesis of the inventive compound (PS8) O H 0-, O N 0 NN N 5 a) Synthesis of compound 8 o N 0 N 8 WO 2013/118068 PCT/IB2013/050996 42 Compound 8 was prepared analogously to steps 2.) b), 2.) c) and 2.) d) of the synthesis of compound PS2 using 4-(1,1,3,3-tetramethylbutyl)-N-[4-(1,1,3,3 tetramethylbutyl)phenyl]aniline and 3-(bromomethyl)heptane rather than bis(9,9 dimethylfluoren-2-yl)amine (step 2.) b)) and bromohexane (step 2.) d)), respectively. 5 b) Synthesis of compound 9 O N 0 0 0 0 N N N N N| | 8 9 10 70 mg of compound 8 (0.065 mmol) were dissolved in 20 mL of 2-methyl-2-butanol, 146 mg potassium hydroxide (2.6 mmol) added and the reaction mixture was stirred under reflux over night. After cooling, the reaction solution was added to ice in dilute acetic acid (1:10 acetic 15 acid:water). The precipitate was filtered off, washed with water and dissolved in dichloromethane. A few drops of acetic acid were added to the solution, which was stirred at room temperature overnight. The solvent was removed by means of a rotary evaporator, the resulting residue stirred with methanol, filtered off and dried. 20 Yield: 30 mg (51 %) of blue solid WO 2013/118068 PCT/IB2013/050996 43 c) Synthesis of target compound ID1554 O H 0 o o 0 0 N 0 N N 9' 10 (1D1554) 5 In a three-neck flask, 30 mg of compound 9 (0.03 mmol) were given to 15 mL of N methyl-2-pyrrolidone (NMP), 25 mg of glycine (0.3 mmol) and 6 mg zinc acetate (0.03 mmol) added and the reaction mixture was stirred at 130'C over night. Yield: 26 mg (81 %) of blue solid 10 Use examples: For further substance designations used, the corresponding chemical compounds are listed hereinafter: 15 1D 423: H N OH 0 20 (commercially available, for example, from Sigma-Aldrich) ID 662: H 25 N Na 00 0 N WO 2013/118068 PCT/IB2013/050996 44 The sodium salt was obtained by reaction of the commercially available hydroxamic acid with sodium hydroxide solution. ID 750: H 5N 5 N - 0*+K 0 0 The potassium salt was obtained by reaction of the commercially available hydroxamic 10 acid with potassium hydroxide solution. ID 758: H 15 N The tetrabutylammonium salt was obtained by reaction of the commercially available 20 hydroxamic acid with tetrabutylammonium hydroxide. ID 741: 25 / N 0 \I00 30 S N 35 N The compound and preparation thereof are described in the publication WO 2012/085803 Al in example 2 on page 12. 40 Construction of OPV cell: WO 2013/118068 PCT/IB2013/050996 45 The base material used was glass plates which had been coated with fluorine-doped tin oxide (FTO) and had dimensions of 25 mm x 15 mm x 3 mm (Nippon Sheet Glass), which had been treated successively with glass cleaner (RBS 35), demineralized water and acetone, in each case for 5 min in an ultrasound bath, then boiled in isopropanol 5 for 10 minutes and dried in a nitrogen stream. Step A) To produce the solid TiO 2 barrier layer, a spray pyrolysis process as described in Peng et al., Coord. Chem. Rev. 248 (2004), 1479 was used. By means of a screenprinting 10 process, a nanoporous TiO 2 layer of thickness 1.8 pm was applied to the solid TiO 2 barrier layer. The base material used for this layer was the TiO 2 paste Dyesol (from Dyesol), which consisted of TiO 2 particles with a diameter of approx. 25 nm, which were dispersed in a terpineol/ethylcellulose dispersion. After the printing process, the paste was dried at 80'C for 5 minutes. This was followed by sintering at 450'C for 30 15 minutes. Step B) After removal from the drying cabinet, the sample was cooled to 80'C, immersed into a 5 x 10-4 molar ethanol solution of the hydroxamic acid salt ID 662 for 16h, washed 20 briefly with ethanol and then placed into a 5 x 10-4 molar solution of the inventive dye in dichloromethane for 1 h. The sample removed from the solution was subsequently rinsed with the appropriate solvent and dried in a nitrogen stream. Step C) 25 Next, a p-conductor solution was spun on. For this purpose, a solution was prepared, consisting of: 0.163 M spiro-OMeTAD (Lumtec, SHT-263), 20 mM LiN(S0 2 CF3)2 (Aldrich) and 2.5 percent by weight of V 2 0 5 based on spiro-OMeTAD. 125 pl of this solution were applied to the sample and allowed to act for 60 s. Thereafter, the excess solution was spun off at 2000 rpm for 30 s. 30 The metal back electrode was applied by thermal metal vaporization under reduced pressure. For this purpose, the sample was provided with a mask, in order to apply 8 separate back electrodes with dimensions of 0.13 cm 2 to the active region by vapor deposition. The metal used was Ag, which was vaporized at a rate of 3.0-3.5 nm/s at a 35 pressure of approx. 5*10-5 mbar, so as to result in a layer thickness of 200 nm. The quantum efficiency (IPCE = Incident Photon-to-current Conversion Efficiency) was then measured with a 75 watt xenon arc lamp (LOT-Oriel), a 1/8 m monochromator (SpectraPro-21 50i; Acton Research Corporation). 40 WO 2013/118068 PCT/IB2013/050996 46 The current/voltage characteristics were measured with the aid of a 450 watt xenon arc lamp (LOT-Oriel) at an illumination intensity of 100mW/cm 2 AM 1.5 and a Keithley 2400 multimeter. 5 Tables 1 to 7 show the following parameters: Isc - short circuit current, Voc - open circuit voltage; FF - fill factor; ETA - efficiency. Table 1 - Results for PS2 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID423 -13.3 460 41 2.5 1D758 -9.3 640 52 3.0 1D750 -8.1 740 64 3.8 1D662 -7.7 780 61 3.5 ID758/ID741 -11.8 660 41 4.0 10 Table 2 - Results for PS4 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID423 -2.83 440 48 0.6 1D758 -9.14 680 57 3.6 1D662 -10.41 700 48 3.5 1D750 -10.33 680 50 3.5 Table 3 - Results for PS1 15 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID423 -6.19 480 60 1.8 1D662 -4.4 720 71 2.2 Table 4 - Results for PS5 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID662 -5.16 980 64 3.2 20 WO 2013/118068 PCT/IB2013/050996 47 Table 5 - Results for PS3 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID 662 -9.52 780 61 4.5 ID 423 -9.4 780 63 4.6 5 Table 6 - Results for PS7 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID662 -8.25 800 64 4.3 1D758 -9.12 760 61 4.3 Table 7 - Results for PS8 10 Additive Isc[mA/cm 2 ] Voc[mV] FF[%] ETA[%] ID662 -4.68 840 68 2.7 1D758 -6.08 780 67 3.2 Figures 1, 3, 6, 10, 13, 16, 18 and 21 show measurement curves for the external quantum efficiency ("EQE"), and figures 7, 8, 11, 14, 17 and 20 current-voltage characteristics of solar cells which have been produced using the inventive dyes. In the 15 case of the measurement curves of figures 2, 4, 5, 9, 12,15, 19 and 22, some show the absorptions which arise from the overall cell construction according to the above described steps A), B) and C), and some also only the absorptions for layer combinations according to the layers from steps A) and B), i.e. without hole conductor according to step C). 20 Figure 1: Influence of additives ID662, ID750 and ID423 on the EQE of the OPV cell in the case of use of PS2 Figure 2: Absorption of PS2/ID423 before ("before") and after the coating ("complete 25 cell") with a hole conductor Figure 3: Influence of additives ID423, ID758, ID662 and ID750 on the EQE of the OPV cell in the case of use of PS4 30 Figure 4: Absorption of PS4 in combination with additives ID423, ID758, ID662 and ID750 before coating with a hole conductor WO 2013/118068 PCT/IB2013/050996 48 Figure 5: Absorption of PS1 in combination with additives ID 423 and ID 662 before coating with a hole conductor Figure 6: Influence of additives ID 423 and ID 662 on the EQE of the OPV cell in the 5 case of use of PS1 Figure 7: Influence of additives ID 423 and ID 662 on the current-voltage characteristic of the OPV cell in the case of use of PS1 10 Figure 8: Influence of ID 662 on the current-voltage characteristic of the OPV cell in the case of use of PS5 Figure 9: Absorption of PS5 in combination with ID 662 before coating with a hole conductor 15 Figure 10: Influence of ID 662 on the EQE of the OPV cell in the case of use of PS5 Figure 11: Influence of additives ID 662 and ID 758 on the current-voltage characteristic of the OPV cell in the case of use of PS3 20 Figure 12: Absorption of PS3 in combination with ID 758 and ID 662 before coating with a hole conductor Figure 13: Influence of additives ID 758 and ID 662 on the EQE of the OPV cell in the 25 case of use of PS3 Figure 14: Current-voltage characteristic of the OPV cell using PS6 Figure 15: Absorption of PS6 (by the whole cell) 30 Figure 16: EQE of the OPV cell using PS6 Figure 17: Influence of additives ID 758 and ID 662 on the current-voltage characteristic of the OPV cell in the case of use of PS8 35 Figure 18: Influence of additives ID 758 and ID 662 on the EQE of the OPV cell in the case of use of PS8 Figure 19: Absorption of PS8 in combination with ID 758 and ID 662 after coating with 40 a hole transporting layer (HTL) WO 2013/118068 PCT/IB2013/050996 49 Figure 20: Influence of additives ID 758 and ID 662 on the current-voltage characteristic of the OPV cell in the case of use of PS7 Figure 21: Influence of additives ID 758 and ID 662 on the EQE of the OPV cell in the 5 case of use of PS7 Figure 22: Absorption of PS8 in combination with ID 758 and ID 662 after coating with a hole transporting layer (HTL)

Claims

1. A compound of the formula la, lb or Ic A A SN O0 N,N' 0 0 0 - -m Rn_ - - m MLR Rn q R 5 (Ia) (Ib) (1c) in which R are identical or different aryloxy, arylthio, hetaryloxy, hetarylthio, aryl, 10 diarylamino or dialkylamino radicals, n when m is 0: 0, 1, 2 or 3, when m is 1: 0, 1, 2, 3, 4 or 5, 15 m is0or1, A is -COOM, -SO 3 M or -PO 3 M, M is hydrogen, an alkali metal cation or [NR'] 4 +, 20 R' is hydrogen or alkyl, where the R' radicals may be the same or differ ent, B is C 1 -C6-alkylene or 1,4-phenylene, where the phenylene radical may 25 be mono- or polysubstituted by alkyl, nitro, cyano and/or halogen, WO 2013/118068 PCT/IB2013/050996 51 L is a chemical single bond or a bridge of the formula -(Het)Ar- or -(Het)Ar-(Het)Ar 5 which may be mono- or polysubstituted by phenyl, alkyl, alkoxy, al kylthio and/or -NR 4 R 5 and in which (Het)Ar is aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms, where, in the case of two (Het)Ar, 10 these may be the same or different, q is 0 or 1, R 1 , R 2 are each independently radicals of the formula Ila, llb or Ilc 15 x R3- R PR (11a) (11b) (11c) R3 is phenyl, alkyl, alkoxy, alkylthio or -NR 6 R 7 , 20 X is C(R 8 R 9 ) 2 , NR 1 0 , oxygen or sulfur, R 4 to R 1 0 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, or aryl or hetaryl, each of which may be mono- or polysubstituted by 25 alkyl, alkoxy and/or alkylthio, p is 0, 1, 2, 3, 4 or 5, Y is NR 11 or sulfur, 30 and R11 is hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties, or aryl, hetaryl, 35 aralkyl or hetaralkyl.

2. A compound according to claim 1, wherein, in formula I, WO 2013/118068 PCT/IB2013/050996 52 R are identical or different aryloxy or arylthio radicals, n when m is 0 or m is 1: 0, 1 or 2, 5 m is 0 or 1, A is -COOM, 10 M is hydrogen or an alkali metal cation, B is C 1 -C6-alkylene, L is a chemical single bond or a bridge of the formula 15 -(Het)Ar- or -(Het)Ar-(Het)Ar which may be mono- or polysubstituted by phenyl, C 1 -C 1 2 -alkyl, C 1 C 1 2 -alkoxy, C 1 -C 1 2 -alkylthio and/or -NR 4 R 5 , and in which (Het)Ar is 20 identical or different aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroa toms, q is 0 or 1, 25 R 4 , R 5 are each independently hydrogen or C 1 -C 1 2 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 moieties, 30 R 1 , R 2 are each independently radicals of the formulae ll'a, ll'b or II'c x R R3 R x \ / \ NL (11'c) R3 is C 1 -C 12 -alkoxy, 35 p is 0 or 1, WO 2013/118068 PCT/IB2013/050996 53 X is C(R 8 R 9 ) 2 , NR 1 0 , oxygen or sulfur, R 8 , R 9 , R 10 are each independently hydrogen or C 1 -C 1 2 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 5 moieties, Y is NR 11 or sulfur, and 10 R11 is hydrogen or alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 - moieties.

3. A compound according to claim 1, wherein, in the formulae la, lb and Ic, 15 n is 0, m is 0 or 1, 20 A is -COOM, M is hydrogen or an alkali metal cation, B is C 1 -C6-alkylene, 25 L is a chemical single bond or a bridge of the formula -(Het)Ar- or -(Het)Ar-(Het)Ar 30 in which (Het)Ar is identical or different aryl or hetaryl, q is 0 or 1, R 1 , R 2 are each independently radicals of the formulae ll'a, ll'b or II'c 35 x (113 ' L / \ / \NL ((I1'b) WO 2013/118068 PCT/IB2013/050996 54 R3 is C 1 -C 12 -alkoxy, p is 0 or 1, 5 X is C(R 8 R 9 ) 2 or NR 10 , R 8 , R 9 , R 10 are each independently hydrogen or C 1 -C 1 2 -alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO 2 moieties, 10 Y is N R 11 or sulfur, and 15 R1 is hydrogen or C 1 -C 1 2 -alkyl.

4. The use of compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic according to claim 1, 2 or 3 and/or isomers thereof or mixtures of isomers of the compounds of the formulae la, lb and Ic according to 20 claim 1, 2 or 3 as photosensitizers in solar cells and photodetectors.

5. A solar cell or photodetector comprising compounds of the formulae la, lb and Ic or mixtures of compounds of the formulae la, lb and Ic according to claim 1, 2 or 3 and/or isomers thereof or mixtures of isomers of the compounds of the formu 25 lae la, lb and Ic according to claim 1, 2 or 3 as photosensitizers.