EP2925817A2

EP2925817A2 - Amino substituted peri-arylene dye

Info

Publication number: EP2925817A2
Application number: EP13811806.2A
Authority: EP
Inventors: Heinz Langhals; Alexander Hofer
Original assignee: Ludwig Maximilians Universitaet Muenchen LMU
Current assignee: Ludwig Maximilians Universitaet Muenchen LMU
Priority date: 2012-11-27
Filing date: 2013-11-26
Publication date: 2015-10-07
Also published as: DE102012023247A1; WO2014083011A3; WO2014083011A2

Abstract

The invention relates to peri-arylene dyes, in particular terrylene- and quaterrylene dyes, which support the amino groups. Said compounds can be produced under mild reaction conditions. Based on their absorption spectra, they can be used, amongst other things, in the solar energy field, in particular as sensitizers in dye-sensitized solar cells.

Description

Amino-substituted? -Enaric dyes

The present invention relates to Jen-arylene dyes, in particular terrylene and Quaterrylenfarbstoffe carrying amino groups. Such compounds can be prepared under mild reaction conditions. Due to their absorption spectra, they are suitable for applications in the field of solar energy, in particular as sensitizers in Grätzel solar cells.

Terrylene color substances (such as terrylene-3,4: 9,10-tetracarboxylic bisimides (1)) (see H. Langhals, A. Hofer, DE 10201 1018815) are preferred as higher homolys of the perylene dyes (see (a) H. Langhals. Molecular devices, chiral, bichromophoric silicones: ordering principles in complex molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, (b) Review: H Longhals, Helv. Chim. Acta. 2005, 88, 1309-1343. (C) H. Langhals, Heterocydes 1995, 40, 477-500) is of increasing scientific and technical interest, in particular because of its light fastness, strong fluorescence and chemical stability.

(1) (2)

The Λ'-substituents in compounds of type (1) have only insignificant effects on the UV / Vis spectra due to the presence of orbital nodes in the HOMO and LUMO on these atoms. They are suitable for controlling further properties of the substances, such as the solubility. Sec-alkyl radicals, such as the 1 -hexylheptyl radical (compare Compound 1a, FIG. 1) or the 1-nyldecyl radical have proven to be extremely effective here and lead to deep blue, strongly red fluorescent solutions of (1) in lipophilic Media. Because of their photochemical stability and strong fluorescence, the substances are basically of interest for solar applications. Here is about the Grätzel cell ((a) Grätzel, M., Nature 2001, 414, 338-344. (b) Nazeeruddin, MK et al., J. Am. Chem. Soc. 2001, 123, 1613-1624. (c) Ooyama, Y., et al., Em. J. Org. Chem. 2009, 2903-29349), which is also referred to as a dye-sensitized solar cell (DSC) for its A major disadvantage of currently used cell systems is the need to use metal complexes, such as ruthenium complexes, to allow light absorption in appropriate wavelength ranges The high price of such complexes, due to the limited availability of the platinum group metals used, and a possible environmental problem are limiting factors for a large-scale use of dye solar cells, in which metal complexes are used as sensitizers.A replacement of the metal complexes by a purely organic material would In addition, lightfast orga However, niche compounds with good preparative accessibility and suitable light absorption properties or fluorescence properties are also in demand in other fields of application.

The object of the present invention was therefore to provide organic compounds which are synthetically readily accessible and light-fast, and which exhibit efficient light absorption in a suitable wavelength range, e.g. be used as sensitizers for dye-sensitized solar cells (Grätzel cells) without having to be complexed with metals.

It has surprisingly been found within the scope of the present invention that amino / ω-arylenes, because of their absorption spectra, are well suited for use in the production of solar energy. Among others, it has been found that not only perylenetetracarboxylic bisamides but also terrylenetetracarboxylic bisimides (hereinafter also referred to as Terryl enbi simide), such as Compound (1), or quaterrylenetetracarboxylic bisimides (hereinafter also referred to as Qu aterrylenbi simide), such as Compound (2), are simple Substitute with. Amines to obtain amino-substituted dyes. The ammoeri-arylene dyes, (eg compounds (14) - (17) see Fig. 4) show advantageous absorption spectra, which allow a variety of applications. Because of the long wavelength spectral range of absorption they are of particular interest for the production of solar energy, for example in photovoltaics, for example as an adjuvant in barrier photovoltaic cells or as metal-free sensitisers for the Grätzel cell. There they can reach and even exceed the efficiency of known metal complexes.

As a solution to the above object, the present invention particularly provides the following embodiments.

An amino-pen ^' -arylene compound of the formula (I):

wherein: n is 1 or 2, X is a radical R ¹² or a radical -NR ⁵ R ⁶ , and the radicals R ¹ to R ^{18 may be the} same or different from each other and independently of one another hydrogen or linear alkyl radicals having at least one and at most 37 represent C atoms in which one to 10 CH ₂ units can be replaced independently of each other by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-Cti-CH ~ groups, in which an H unit also may be replaced by a nitrogen atom, acetylenic C = C-Grappen, 1,2-, 1, 3- or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3 , 4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4-di-substituted thiophene, 1, 2, 1, 3, 1, 4, 1 , 5-, 1-, 6-, 1-, 7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH? Groups can each be replaced independently of the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain having up to 18 carbon atoms.

In such an alkyl chain, one to 6 CH; moieties may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or R "s-CH = CH groups in which a CH moiety is also substituted by carbon atoms Nitrogen atom may be replaced, acetylcnic C = C groups. 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2 , 3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3, 1,4-, 1,5-, 1, 6-, 1, 7- , 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2, 9, 2 , 10- or 9,10-di substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CI F groups of the alkyl radicals can each independently be replaced by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains with up to 18 C atoms; also in these alkyl chains, one to 6 CH _: -F.inheiten can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or Iran - CH · C 1 1 -G-pen, in which a CH- Unit may also be replaced by a nitrogen atom, acetylenic CsC groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1, 4-, 1 , 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2, 6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Instead of carrying substituents, the free valences of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings arise, such. Cyclohexane rings.

The radicals R ⁸ to R ^{1 S} can also independently of one another denote the halogen atoms F, Cl, Br or I. Contact the radicals R ^9, R ^i0, R ¹⁵ and R ¹⁶ several times (in case of n = 2), so they may have different meanings within the definitions given above in each occurrence.

In another embodiment, amino-arylene compounds of the following formulas (IVa) and (IVb) are provided:

(Wh) wherein the radicals R ¹ to R ^{4 are} independently defined as R ^l in formula (I), and the radicals R ⁷ to R ¹⁴ and R ²³ to R ^{27 are} independently defined as R ⁸ in formula (I).

Another embodiment of the invention relates to a process for preparing a compound of formula (I) or of formulas (IVa) or (IVb), characterized in that a corresponding ene-arylene is reacted with a primary or secondary amine.

Finally, the present invention relates to the use of a compound of the formula (V)

wherein m is 0, 1 or 2, X is a radical R ¹² or a radical -NR ⁵ R ⁶ , wherein the radicals R ¹ to R ^{6 are} independently defined as R ¹ in formula (I), and the radicals R ⁸ to R ^{! 8 are} independently defined as R ⁸ in formula (I), the radicals R ⁹ , R ¹⁰ , R ¹⁵ and R ^{16 occur} several times (in the case of m = 2), they can be different for each occurrence Have meanings within the definitions given above; or a compound of formulas (IVa) or (IVb):

wherein the radicals R to R ⁴ and R are independently defined as R ¹ in formula (1), and the radicals R ⁸ to R ¹⁴ and R ^2j to R ^{27 are} independently defined as R ⁸ in formula (I); in a photovoltaic solar cell.

According to this embodiment, the invention also relates to a photovoltaic solar cell containing a compound of the formula (V), the formula (IV ⁷ a) or the formula (IVb) as defined above. The compounds of the invention having a terrylene or quaternary structure have the following formula (I):

The compounds of the formula (1) are preferably a compound selected from compounds of the formulas (IIa), (IIb), (IIIa) or (IIIb):

(IIa)

p15 p16 p17 R18 R19 R20 R21 p22

(purple)

(IIIb).

The radicals and variables in the formulas (I), (IIa), (IIb), (IIIa) and (IIIb) are defined as follows. n is 1 or 2, and X is a radical R ⁱ² or a radical -NR ⁵ R ⁶ .

The radicals R and R ^~ are identical or different, and may represent, in which one to 10 CH ₂ units may be replaced independently of one another in each case by carbonyl groups, oxygen atoms, are independently hydrogen or linear alkyl radicals having at least one and not more than 37 C -atoms Sulfur atoms, selenium atoms, tellurium atoms, cis- or trafls-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic = C groups. 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3 -, 2,4-, 2,5- or 3,4-disubstituted thiophene, 1, 2, 1, 3, 1,4, 1,5, 1,6, 1, 7, 1 , 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1,2-, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2, 6, 2, 7, 2, 9, 2, 10 or 9, 10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CTE groups can each independently be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 carbon atoms.

In such an alkyl chain, one to 6 C ^ moieties may be independently substituted by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or tran- s -CH groups in which a CH unit may also be replaced by a nitrogen atom can, acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1 , 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 1 0, 2,3, 2,6, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH groups of the alkyl radicals can each be independently replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear AI ky! chains of up to 18 C atoms; also in these alkyl chains one to six CIF units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or C ratti 'CH = CH groups, in which a CH unit is replaced by a nitrogen atom may be acetylenic C = C groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1 , 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2, 7, 2, 9, 2, 10 or 9, 10 disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. Preferred as R ¹ or R ² are alkyl radicals, in particular secondary alkyl radicals. Particularly preferred are the 1-hexylheptyl or the 1-Nylyldecylrest.

The radicals R ^J , R ^~ . R ⁵ and R ⁶ are the same or different and may independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ -einlieiten may be replaced independently by each carbonyl groups, oxygen atoms, sulfur atoms , Selenium atoms, tellurium atoms, cis- or frans -CH = C HG sip, in which a CH unit may also be replaced by a nitrogen atom, acetylenic C = C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4 disubstituted thiophrore radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2 , 7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-disubstituted anthracene radicals in which or two CH-Gru Ppen may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 carbon atoms.

In such an alkyl chain, one to 6 CH ₂ units may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans - CH = CH groups in which a CH unit is also replaced by a nitrogen atom may be acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4 - or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3, 1, 4, 1, 5 , 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1.8, 1, 9, 1, 10, 2,3, 2,6, 2, 7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH groups of the alkyl radicals can each independently be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; also in these alkyl chains, one to 6 C IE units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or in which a CH unit can also be replaced by a nitrogen atom, acetylenic C = C groups 1, 2-, 1, 3- or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5 , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3- , 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms Nitrogen atoms can be replaced, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues. in which one or two carbon atoms may be replaced by nitrogen atoms.

Instead of carrying substituents, the free valences of the methine groups or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.

R ³ and R ⁴ or R and R ⁶ are preferably alkyl radicals, or in each case one of R ³ and R ⁴ or R ⁵ and R ⁶ is an alkyl radical, and the other is hydrogen. In addition, in a further preferred embodiment in the formulas formulas (I), (IIa), (IIb), (IIIa) and (IIIb) form R ³ and R ⁴ or R ⁵ and R ⁶ together with the nitrogen atom to which they are bound, a pyrrolidine ring. Particularly preferred is the variant according to which R ³ and R ⁴ or R ³ and R ⁶ together with the nitrogen atom to which they are attached form a pyrrolidine ring.

The radicals R ^x to R ^" are identical or different and can independently of one another denote hydrogen, the halogen atoms F, CL Br or I, or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH units are independent can be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or in-methyl groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2 , 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8 -, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two (H groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1, 4-, 1 , 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2, 9, 2 , 10- or 9,10-disubstituted anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH: groups can each independently be replaced by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain having up to 18 carbon atoms.

In such an alkyl chain, one to 6 CH ₂ units may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or R-CH = CH groups in which a CH unit is also replaced by a nitrogen atom may be acetylenic C ^ C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4 or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1 , 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2, 7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; Also in this alkyl chain may have a C H to 6-healing independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or // ^• (/ "v-CH- H groups, in which a CH Unit may also be replaced by a nitrogen atom, acetylenic C ^ C groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6 , 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4 , 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3-, 2,6, 2,7, 2,9, 2, 10 or 9, 10 disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Contact the radicals R \ R '°, R ¹⁵ and R ¹⁶ in the formula (I) several times (in case of n = 2), so they may have different meanings within the definitions given above in each occurrence. Preferably, the radicals R ^' in formula (IIb), R to R ^{* ~} in formula (IIIa) and R' to R ²¹ in formula (IIIb) are not the halogen atoms F, Cl, Br or I. Particularly preferably, the radicals R to R ^{^} ~ are hydrogen.

As will be apparent to those skilled in the art, as used in this specification, a CHi moiety of an alkyl group or an alkyl chain which can be replaced by definition may also be a terminal moiety in an alkyl group of an alkyl chain, ie, a corresponding formal CH ₂ moiety a -CH ₃ group act. Accordingly, this applies to the methine groups, which can be linked in pairs so that rings are formed. These methine groups may also each be a formal CH moiety present within a CH ₂ group or CH ₃ group and additionally having a free valence to form a ring having a second corresponding group. The quaternary C atoms, which may be linked in pairs, may result if, for a CH ₂ group, a monovalent substituent has already replaced a hydrogen atom and, in addition, a free valence is present to form a ring with a second corresponding group.

Particularly preferred compounds of the formula (I) or of the formulas (IIa), (IIb), (IIIa) and (IIIb) are shown below:

(15)

As mentioned above, in another embodiment, form amino / ?i-7 arylene compounds of the following formulas (IVa) and (IVb) having an imidazoloperylene bisimide structure are provided.

The radicals in the formulas (IVa) and (IVb) are defined as follows.

The radicals R and R are identical or different and can independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms , Selenium atoms, tellurium atoms, cis or iran C H ^_ C H groups. in which a CH unit may also be replaced by a nitrogen atom, acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals. 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4 - Disubstituted thiophene, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2 , 7-disubstituted naphthalene radicals in which one or two C H groups may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7 , 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9, 10-disubstituted anthracene radicals in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain having up to 18 carbon atoms.

In such an alkyl chain, one to 6 CH; moieties may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or traf5 CH = CH groups in which a CH unit is also represented by a nitrogen atom may be substituted, acetylenic C-sC-Grappen, 1, 2, 1,3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-di-substituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2 -, 1, 3, 1,4, 1,5, 1, 6, 1,7, 1,8, 1, 9, 1, 10, 2,3, 2,6 -, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH.sub.2 groups of the alkyl radicals can each independently of one another also be replaced by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 C atoms; also in these alkyl chains, one to 6 CH ₂ units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-C HC H -glys, in which a CH unit is also replaced by a nitrogen atom acetylenic Cs groups may be 1, 2, 1,3 or 1,4-substituted phenyl, 2,3, 2,4, 2,5, 2,6, 3,4 or 3 , 5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3, 1, 4, 1, 5, 1, 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3 -, 1, 4, 1,5, 1,6, 1,7, 1,8, 1, 9, 1, 10, 2,3, 2,6, 2,7 -, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Preferred as R ¹ or R ² are alkyl radicals, in particular secondary alkyl radicals. Particularly preferred are the 1 -hexylheptyl or the 1-Nylyldecylrest.

The radicals R \ R ⁴ and R are the same or different, and can represent at least one and not more than 37 C atoms, in which one to 10 CH ₂ units may be replaced independently of one another in each case by carbonyl groups are independently hydrogen or linear alkyl, Oxygen atoms, sulfur atoms, selenium atoms. Tellurium atoms, cis- or in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals,

2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4 - disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2, 7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1,2-, 1, 3, 1,4-, 1, 5, 1, 6, 1, 7, 1 , 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear Alkvlkctte having up to 18 carbon atoms.

In such Alkvlkctte one to 6 CHi units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or / ra «5-CH = CH groups in which a CH unit also by a nitrogen atom may be replaced, acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1 , 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2, 6, 2 , 7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the (H; groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains with up to 18 C atoms: also in These alkyl chains, one to 6 CH? units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium, cis- or irans-CH ^ CH groups in which a CH unit may also be replaced by a nitrogen atom , acetylenic CsC groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5 disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals 1, 2, 3, 3, 1, 4, 1, 5, 1, 6-, 1-, 7-, 1-, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2-, 1.3-, 1, 4, i, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings.

Preferably, R ³ and R ^{4 are} alkyl radicals, or one of R ^J and R ⁴ is an alkyl radical and the other is hydrogen. In addition, in a further preferred embodiment in the formulas (IVa) and (IVb), R 'and R ⁴ together with the nitrogen atom to which they are attached form a pyrrolidine ring. Particularly preferred is the variant according to which R ³ and R ⁴ together with the nitrogen atom to which they are attached form a pyrrolidine ring. R is preferably hydrogen or an alkyl radical, in particular hydrogen.

The radicals R ⁸ to R ⁴ and R ²¹ to R ^" are identical or different and can independently of one another denote hydrogen, the halogen atoms F, Cl, Br or I, or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CU = CU groups in which a GH unit can also be replaced by a nitrogen atom, acetylenic C = C groups, 1, 2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3-, 1, 4-, 1.5-, 1,6-, 1, 7, 1, 8, 2,3, 2,6 or 2, 7-di-substituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2, 9, 2, 10 or 9, 10 disubstituted anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CHi groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or loci or the cyano group, or by a linear alkyl chain with up to 18 C atoms. in such an alkyl chain, one to 6 CH ₂ units may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or tra-s-CH = CH groups in which a CH unit is also represented by a nitrogen atom may be replaced, acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2.7 disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8-, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9, 10-di-substituted anthracene radicals in which one or two carbon atoms Nitrogen atoms can be replaced. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; also in these alkyl chains, one to 6 CH ₂ units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-I-11-fluorophenyl. in which a CH unit may also be replaced by a nitrogen atom, acetylenic C ^ C groups 1, 2-, 1, 3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5 , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3- , 1, 4, 1, 5, 1,6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals having one or two carbon atoms 1, 2, 3, 1 2,3-, 2,6-, 2,7-. 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Instead of carrying substituents, the free valencies of the methine clusters or of the quaternary C atoms can be linked in pairs, so that rings are formed, such as, for example, Cyclohexane.

The radicals R ⁸ to R ¹⁴ and R ^2j to R ² 'are preferably hydrogen.

Particularly preferred compounds of the formulas (IVa) and (IVb) are the following compounds (19) and (20):

(19) (20).

The amino substitution of the er / ^' arylenes is suitable for optimizing the absorption spectrum of the compounds, in particular with regard to their use in photovoltaic solar cells. By way of example, Fig. 6 shows that UV / Vis absorption spectrum of the terrylene bisimide Ia (see Fig. 4) compared to the spectra of amino substituted compounds. A simple substitution with a pyrrolidine unit (14) leads to a bathochromic shift with weakening of the vibrational structure; Green solutions are obtained. The second substitution to 15 causes another bathochromic shift; the substance forms deep blue solutions. The UV / Vis absorption of the quaterrylene biosimple 2a depicted in FIG. 7 (see FIG. 4) already extends into the long-wave range, and the substance forms turquoise-colored solutions. A monosubstitution of 16 leads to another bathochromic shift, which, however, is not as pronounced as in the Terrylenderivaten; wine-red solutions are obtained. A disubstitution of 17 leads only to a further shift of the maximum, and the solutions of the substance are again deep dark blue. Finally, the substitutions of the imidazolone-extended perylene bisimide 18 to 19/20 (see Fig. 5) cause a significant bathochromic shift of the absorption by well over 100 nm.

Various amino-per / ^"arylenes were tested here with the help of Grätzel solar cells on their efficiency as a sensitizer for generating electrical energy from solar energy. For the standard perylene dye S-13 (V, A ^" '-1 -llylheptylperylene-3,4: 10-tetracarboxylic bisimide, RN 1 10590-84-6), a moderate efficiency is found which is far below the efficiency of the ruthenium complex 23; See also H. Langhals, S. Kirner, Eur. J. Org. Chem., 2000, 365-380, see Figure 8, No. 1, as compared to No. 4.

By the nuclear substitution of la (see Fig. 4) with pyrrolidine residues, a substantial increase in current efficiency can be achieved. Thus, even the monosubstituted derivative 14 (see Fig. 4) provides such a large increase in performance that the cell operates much more efficiently than a cell sensilated with the comparative dye 23; Figure 8, No. 5. Substitution with another pyrrolidine moiety as in Figure 15 (see Figure 4) further increases the yield of the cell; Figure 8, No. 6. The transition from the terrylene derivatives to the quaterrylene derivatives 16 and 17 (see Figure 4) with more strongly bathochromic absorption further improves the power yield.

A further embodiment of the invention relates to the use of a compound of the following formula (V) or of the formulas (IVa) or (IVb), as defined above, in a photovoltaic solar cell.

In formula (V) m is 0, 1 or 2. The variables or radicals X and R to R are independently defined as the variables or radicals X and R ¹ to R ⁱ for compounds of formula (I). Preferably, the compound of formula (V) is a compound of formula (Γ), more preferably a compound of formula (IIa), (ITb), (Ufa) or (Ilfb) as defined above. According to particularly preferred embodiments, the compound (14), (15), (16), (17), (19) or (20) is used in a photovoltaic solar cell. Further preferred compounds of the formula (V) for use in a photovoltaic solar cell are amino-perylenebisimides of the formulas (Via) and (VIb).

The radicals and variables in the formulas (IVa) and (IVb) are defined as follows.

The radicals R ¹ and R ^" are identical or different and can be independent of one another

Mean hydrogen or linear Alkvlreste with at least one and at most 37 C-atoms, in which one to 10 CH ₂ units can be replaced independently by each carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium, cis- or trans- H - CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2, 1 or 1, 4-substituted phenyl radicals,

2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4 - Disubstituted thiophene, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2 , 7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2, 9,

2, 10 or 9,10-disubstituted anthracene residues in which one or two CH groups are replaced by

Nitrogen atoms can be replaced. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the vano group, or by a linear alkyl chain having up to 18 carbon atoms.

In such an alkyl chain, one to 6 CH; -inhciten can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or zraw, s - CH = CH groups in which a CH unit also by a Nitrogen atom may be replaced, acetylenic C = C groups. 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5 -di-substituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7 , 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1,3, 1,4- , 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2, 9 , 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; also in these alkyl chains, one to 6 CH 2 units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or in which a CH unit may also be replaced by a nitrogen atom, acetylenic Cs groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5 -di-substituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms are represented by nitrogen atoms may be replaced, 1.2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3 -, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

Preferred as R ¹ or R ^~ are alkyl radicals, in particular secondary alkyl radicals. Particular preference is given to the 1-hexylheptyl radical or the 1-nonyldecyl radical. The radicals R \ R ^4, R ⁵ and R ⁶ are the same or different, and may represent atoms in which one to 10 CE ^ units may be replaced independently of one another are each independently hydrogen or linear alkyl radicals having at least one and not more than 37 C by each carbonyl groups. Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-C HCH groups, in which a CH unit may also be replaced by a nitrogen atom, acetylenic C ^ C-Gnippcn. 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals. 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1.5, 1, 6, 1, 7, 1, 8, 2,3,

2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1 , 7-, 1.8-, 1, 9-, 1, 10-, 2,3-, 2,6,

2.7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the Ci F groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group, or by a linear alkyl chain with up to 18 ( ^" -Atomen.

In such an alkyl chain, one to 6 CH; -F.inheiten may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or in which a CH unit can also be replaced by a nitrogen atom, acetylenic CsC groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5- , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4-, 1, 5-, 1, 6-, 1, 7-, 1, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals, wherein one or zw ^r ei carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10 , 2,3-, 2,6, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the (TF groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains with up to 18 carbon atoms, even in these Alkyl chains can be replaced by one to six CH ₂ units independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis groups or groups of which a CH unit can also be replaced by a nitrogen atom , acetylenic C == C groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3, 5 -di-substituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1, 5, 1, 6, 1,7, 1,8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1 , 10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms.

R 'and R ⁴ or R ⁵ and R ⁶ are preferably alkyl radicals, or in each case one of R ³ and R ⁴ or R ^'" and R ⁶ is an alkyl radical, and the other is hydrogen in the formulas (IVa) and (IVb) R 'and R ⁴ or R ⁵ and R ⁶ together with the nitrogen atom to which they are attached form a pyrrolidine ring, particular preference is given to the variant according to which R ^J and R ⁴ and R ³ and R ⁶ together with the nitrogen atom to which they are attached form a pyrrolidine ring.

The radicals R ⁸ to R ^{! 4} are identical or different and can independently of one another denote hydrogen, the halogen atoms F, Cl, Br or 1, or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ Units can be replaced independently by each carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms. Partial atoms, cis- or iran.s-CH = H groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic ( ^" = ( ^' - groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9, 10-disubstituted Anthracene residues in which one or two CH groups can be replaced by nitrogen atoms Up to 12 individual hydrogen atoms of the CIT groups can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group , or by a linear alkyl chain with up to 18 C atoms.

In such an alkyl chain, one to 6 CH ₂ units may independently be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, or ir <mv-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C = C groups, 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2 , 3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4- disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2, 3, 2, 6 or 2, 7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8 , 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2, 10, or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each independently be replaced on the same carbon atom by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms; Also in these Aikyi chains, one to six CTF units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans -CHC H groups. in which a CH unit may also be replaced by a nitrogen atom, acetylenic C ^ C groups 1, 2, 1, 3 or 1, 4-substituted phenyl, 2,3-, 2,4-, 2,5 , 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms are represented by nitrogen atoms 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2 can be replaced , 3, 2, 6, 2, 7, 2, 9, 2, 10 or 9, 10 disubstituted anthracene radicals in which one or two carbon atoms may be replaced by nitrogen atoms.

Instead of carrying substituents, the free valences of the methine groups or of the quaternary carbon atoms can be linked in pairs, so that rings are formed, such as, for example.

Cyclohexane.

Preferably, the radicals R ^s to R ^{14 are} hydrogen.

Particularly preferred compounds of the formulas (VIa) and (VIb) for use in solar cells are the following compounds (32) to (37):

As can be seen by the person skilled in the art from the above explanations, the compounds of the formula (IVa), (IVb) and (V) in solar cells serve in particular as light absorbers. These compounds can be used as individual compounds or as a mixture of two or more of these compounds.

A photovoltaic solar cell employing a compound of the formula (IVa), (IVb) or (V) is preferably a purely organic junction cell or Grätzel cell, more preferably a Grätzcl cell, and more preferably a Grätzel cell that a layer containing titanium dioxide nanoparticles. Preferred compounds for use in a photovoltaic solar cell are the compounds of the formulas (IIa), (IIb), (IIIa), (IIIb), (Via) or (VIb) defined above, in particular one of the compounds (14) to (17) or (32) to (37), more preferably of the formulas (IIa), (IIb), (IIIa) or (IIIb), especially one of the compounds (14) to (17).

Accordingly, the invention also relates to a photovoltaic solar cell containing a compound of formula (IVa), (IVb) or (V). The solar cell is preferably a purely organic junction cell or a Grätzel cell, more preferably a Grätzel cell, and more particularly a Grätzel cell containing a layer of titanium dioxide nanoparticles. The compound of the formula (IVa), (IVb) or (V) is preferably a compound of the formula (IIa), (IIb), (IIIa), (IIIb), (Via) or (VIb), in particular one of the compounds (14) to (17) or (32) to (37), more preferably of the formulas (IIa), (IIb), (IIIa) or (IIIb), especially one of the compounds (14) to (17 ).

However, the use in particular of the novel compounds of the formulas (I), (IVa) or (IVb), in particular (IIa), (IIb), (IIIa), (IIIb), (IVa) or (IVb) is not limited to solar cells , As other fields of application in which the light absorption properties of the properties according to the invention are advantageous, the following can be mentioned: a) Use as energy genera or groups in bi-and multichromophoric compounds, for example for achieving broadband light absorption. This may be of interest, for example, in fluorescent dyes or in light-driven charge separation systems, such as in bichromophores with perylene-3, 4: 9, 10-tetracarboxylic bisimide derivatives. b) Use as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as for example glue colors, watercolor paints, water colors, colors for inkjet printers, paper inks, printing inks, inks and inks and other colors for painting and writing Z. awake and in paints. c) use as pigments in paints, preferably synthetic resin paints such as acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer) , d) use for bulk dyeing of polymers, such as materials of polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinyl butyral, polyvinylpyridine, Cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polyethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, polyacrylonitrile, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers. e) Use for coloring natural substances, for example paper, wood, straw or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such as viscose fiber, nitrate silk or copper rayon (rayon) , f) use as mordant dyes, eg for coloring natural products, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such as viscose, nitrate silk or copper rayon (Reyon). Preferred salts for pickling are aluminum, chromium and iron salts, g) use as an additive to other colors in which a certain shade of shade is to be achieved, particularly bright shades are preferred. h) Use for marking, security and display purposes, especially taking into account their fluorescence, such as dyes or fluorescent dyes for signal colors, preferably for visual highlighting lettering and drawings or other graphic products, for marking signs and other objects and in display elements , including passive display elements, traffic signs and traffic lights i) use for security markings, wherein the high chemical and photochemical stability and possibly also the fluorescence of the substances is advantageous, preferably for

Checks, check cards, banknotes, coupons, documents, or identity documents. j) use as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes. k) Use as dyes in inkjet printers in homogeneous solution, preferably as a fluorescent ink. 1) Use as dyes or fluorescent dyes in display, illumination or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for example in fluorescence displays, Braun tubes or in fluorescent tubes, m) use as a tracer, for example in biochemistry , Medicine, technology and natural sciences, here, the dyes may be covalently linked to substrates or via secondary valences, such as hydrogen bonds or hydrophobic interactions (adsorption). n) Use as dyes or fluorescent dyes in chemiluminescence systems, for example in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods. o) Use as a material for leak testing of closed systems. p) Use as functional materials, such as in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes). q) Use as pigments in electrophotography: eg for dry copying systems (Xerox process) and laser printers ("Non Impact Printing"). r) Use for the frequency conversion of light, eg to make shortwave light of longer wavelength, visible light (s) used as a starting material for superconductive organic materials, (t) used as fluorescent dyes in scintillators, (u) used as dyes or fluorescent dyes in optical light harvesting systems, such as the fluorescent solar panel or fluorescence activated displays, (v) use in liquid crystals to redirect light (w) used as dyes or fluorescent dyes in cold light sources (x) for use in light - induced polymerisation for the synthesis of plastics y) used as dyes or fluorescent dyes for materials testing, eg in the manufacture and testing of semiconductor and semiconductor devices oreszenzfarbstoffe in photoconductors. aa) Use as dyes or fluorescent dyes in photographic processes. ab) Use as dyes or fluorescent dyes as part of a semiconductor integrated circuit having dyes as such or in combination with other semiconductors, eg in the form of an epitaxy. ac) Use as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch. ad) Use as active substances for non-linear optics, eg for frequency doubling and frequency tripling of laser light.

Previous methods for the preparation of terrylene bisimides (1) were relatively expensive (FO Holtrup, GRJ Mueller, H. Quante, S. De Feyter, DeSchverver, K. Muellen, Chem. Europ. J. 1997, 3, 21 9-225 ) and limited thereby the employment possibilities of the substance class. In the meantime, based on the Sakamoto reaction as cross-coupling between the corresponding naphthalene-1, 8-dicarboxylic acid imide and the perylene-3,4-dicarboximide, the derivatives of 1 can be efficiently synthesized (H. Langhals, A. Walter, E. Rosenbaum, LB-A. Johansson, Phys. Chem. Chem. Phys. 201 1, 13, 1 1055-1 1059).

The synthesis of quaterrylenebisimides 2 was also expensive ((a) H. Quante, K. Müllen, Angew Chem 1995, 107, 1487-1489; Angew. Chem. Int. Ed. 1995, 34, 1323-1325. (B ) K. Müllen, H. Quante, (BASF AG) DE 4236885, Chem. Ahstr., 1994, 121, 303055). Thus, in the first published synthesis, the toxic Ni (cod) 2 had to be resorted to. This could be improved by the use of less toxic reagents (H. Langhals, F. Süßmeier, J. Prakt. Chem. 1999, 341, 309-31 1), but the synthesis remained laborious.

For the preparation of the compounds of the invention could be resorted to an optimized synthesis of Terrylenbisimide (1). According to the scheme illustrated in FIG. 1, the perylene-3,4: 9,1-O-tetracarboxylic bisanhydride (3), which is readily available as a technical mass product, becomes perylene-3,4-diacid anhydride (4) ((a) H. Langhals, P. von Unold, M. Speckbacher, Liebigs Ann./Recueil 1997, 467-468; (b) L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244) decarboxylated (H. Langhals, A. Hofer, DE 102012002678), condensed with 1-hexylheptylamine to the carboxylic acid imide (5) and according to the S akamoto method (T. Sakamoto, C. Pac, J. Org. Chem. 2001, 66, 94-98). with potassium ferric butylate and DBN with the corresponding naphthalene-1, 8-dicarboximide (6) implemented; this is a highly efficient synthetic route that allows terrylenebisimides. as Terrylcnbisimid la to represent under laboratory conditions in several gram quantities and which can be technically upscale (H.Langhals, A.Walter, E. Rosenbaum, LB-Ä. Johansson, Phys. Chem. Chem. Phys. 201 1, 13, 1 1055-1 1059).

Quaterrylenebisimides 2 can, as illustrated in FIG. 2, also have been prepared from the perylene-3,4: 9, 10-tetracarboxylic bisanhydride (3), which has been reacted analogously to the dicarboximide (5) to brominate (7) (L. Feiler, Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244) and then using a Pd catalyst was linked CC-. Ring closure of (8) can be achieved under the conditions of the Sakamoto reaction (supra). Here too, the corresponding perylene-3,4: 9,10-tetracarboxylic anhydride imide (9) can be C-C linked directly using decarboxylating copper. The by-produced perylene-3,4-dicarboximide (4) is brominated and then - as already described - C-C linked and cyclized. The combination of the two ways is very economical in terms of starting materials. Alternatively, as illustrated in Figure 3, perylene with N-bromosuccinimide can be brominated to the dibromo derivative (10) and reacted with bispinacol borane to give the diboron derivative (11) ((a) Y. Avlasevich, K. Müllen, J. Org. Chem. 2007, 72, 10243-10246 (b) A. Suzuki, N. Miyaura, M. Murata, T. Ishiyama, J. Am. Chem. Soc. 1993, 115, 1 1018-1 1020. (c) N. Miyaura, M. Murata, T. Ishiyama ./. Org. Chem. 1995, 60, 7508-7510). Its linkage with 4-bromonaphthalene-l, 8-dicarboximide (12) in a Suzuki cross-coupling (N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483) leads to double naphthalene-imidated perylene 13, which can then be cyclized under sakamoto conditions to a quaterrylenebisimide such as 2a.

It has surprisingly been found that terrylenebisimides, such as compound (1), or quaterrylenebisimides, such as compound (2), react with amines. For example, a smooth reaction according to Figure 4 of la and also of 2a with pyrrolidine was found at room temperature; although terrylene and Quaterrylenbisimide are chemically pronounced resistant substances, for example, against caustic soda or hydrochloric acid. Pyrrolidine units were introduced into the o-positions relative to the carbonyl groups as a result of this reaction. Although a similar reaction of perylene bisimides to 21 and 22 is known (H. Langhals, S. Christian, DE 10201 1 1 16207), however, compounds of T ps (1) and (2) are more electron-rich than perylenebisimides, and the attack of an amine would have been considered much less likely.

(21) (22)

The N R spectra of the products obtained suggest a substitution of the <. »- position for the amino groups with pyrrolidine radicals; the exact substitution pattern of the disubstitution pattern can be substantiated on the basis of analogy. Surprisingly, the Terrvlenbisimide react even faster at room temperature than the Perylenbisimide. For example, e.g. a preparative mono-substitution to 14 (Figure 4) substantially already reached after one day of reaction time, a disubstitution to 15 after five days. The quaterrylenebisimides, such as compound (2a) (see Fig. 4), react somewhat more slowly. For preparative monosubstitution of 16, 10 days are needed and 17 for disubstitution. Finally, as shown in Figure 5, imidazolo-extended pervels such as 18 can also be reacted. The reaction illustrated in the figure has resulted in a markedly smooth reaction to the mixture of two regioisomers 19 and 20. The substitution patterns given can probably be made on the basis of NMR spectroscopy.

In that regard, a further aspect of the invention relates to a process for the preparation of the compounds of the aforementioned formulas (I), (IVa) or (TVb), in particular the compounds of the above formulas (IIa), (IIb), (IIIa), (Illb ), (IVa) or (TVb), which is characterized in that a peri-arylene is reacted with a primary or secondary amine. Vn-arylenes as starting compounds for reaction with an amine are shown below by way of illustration.

The reaction of a compound of formula (He), wherein the radicals R, R ^~ and R to R are as defined for formula (IIa), and the radicals R ^{a are} independently defined as the radicals R ⁸ to R ¹⁸ in formula ( IIa), and in particular hydrogen, thus leads to compounds of the formula (IIa) or (IIb).

The reaction of a compound of formula (IIle), wherein the radicals R, R ~ and R to R ^{~ "are} as defined for formula (TTIa), and the radicals R ^{a are} independently defined as the radicals R ⁸ to R ²² in Formula (purple), and in particular are hydrogen, thus leads to compounds of the formula (IIIa) or (IIIb).

The reaction of a compound of formula (IVel) or (! Ve2), wherein the radicals R ¹ , R ² , R and R ^" to R ¹⁴ and R ²³ to R ^{: ~} as defined for formula (IVa) and (IVb) are and the radical R ^a as the radicals R ⁸ to R ¹⁴ in formula (IVa) and (IVb) is defined, and in particular hydrogen, thus leads to compounds of formula (IVa) or (IVb).

The reaction of the peri-arylene with the primary or secondary amine preferably takes place in a concentrated solution of the amine. Suitably, a liquid amine itself may also be used as the reaction solvent. Pyrrolidine is therefore particularly preferred as the amine. The reaction temperature is not particularly limited, preferably For example, the reaction takes place at temperatures between -20 and 100 ° C, more preferably at temperatures between 15 and 50 ° C, most preferably at room temperature.

Examples

General. IR Spectra: Perkin Elmer 1420 Ratio Recordmg Infrared Spectrometer, FT 1000: UV / Vis Spectra: Van to Gary 5000 and Bruins Omega 20; Fluorescence spectra: Varian Eclispe: NMR Spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95. Fluorescence quantum yields were determined analogously to H. Langhals, J. Karolin, L. B.-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922; reference dye S-13 is / V V-bis-1-hexylheptylperylene-3,4: 9, 10-tetracarboxylic bisimide, RN 1 10590-84-6.

Darsteüimgsbeispie! 1: A- (1-hexylheptyl) perylene-, 4-dicarboxylic acid-1-olide (5) (cf., L, Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244): perylene-3 , 4-dicarboxylic anhydride (Comp. (4), Fig. 1) (1 .00 g, 3.10 mmol) and 1 -hexylheptylamine (680 mg, 3.41 mmol) were heated to 140 ° C in 5 g of imidazole for 2 h, after the cooling while still warm with 2 M aqueous HCl (200 mL) like, sucked off (D4 glass frit), dried at 110 ° C in a drying oven and used without further purification for the next reactions, since he is sufficiently pure for this purpose. Y. 1.54 g (99%) of a red solid, mp 167 ° C. R _f (silica gel / chloroform): 0.85. IR (ATR): r - 3319 (w), 3069 (w), 2954 (s), 2854 (s), 1 769 (s), 1 732 (m) 1697 (s), 1657 (s), 1592 ( s). 1577 (m), 1538 (m), 1506 (w), 1455 (w), 1404 (m), 1352 (m), 13 14 (s), 1266 (m), 1 246 (m), 1 200 ( w), 1 175 (w), 1 140 (w), 1 1 23 (m), 1014 (m), 852 (w), 807 (), 750 (w), 735 (m) cm ^-1 NMR (600 MHz, CDCh, 27 ° C, TMS): δ = 0.83 (t, V (H, H) = 7.0 Hz, 6 H, 2 ^χ CH ₃ ), 1.19- 1.39 (m, 16 H, 8 ^χ CH _2), 1.84- 1.91 (m, 2H, ß-CW _2), 2:22 to 2:30 (m, 2 H, / i-CH _2), 5:16 to 5:24 (m, 1 H, NCH), 7:58 ( t, ³ J (H, H) - 7.8 Hz, 2 H, 2 CHperyien), 7.85 (d, ^J J (H, H) - 8.0 Hz, 2 H, 2 χ CH _Pery s), 8:32 (d, ^J J (H, H) - 8.1 Hz, 2 H, 2 x CH _-pyriylene ), 8.35 (d, (HH) = 7.4 Hz, 2H, CH _perylene ), 8.50 ppm (br, 2H, _CHpeiylene ).

C-NV1R (150 MHz, CDC1 ₃ , 27 ° C, TMS): S = 14.0, 22.6, 27.0, 29.3, 31.8, 32.4, 54.3, 1 19.8, 123.2, 126.7, 127.6, 128.9, 129.6, 130.5, 130.8, 131.6 , 134.0, 136.5, 164.1, 165.0 ppm. UV / Vis (CHCl3): A _max (E _rel ) - 483 (1.00), 506 nm (0.98). Fluorescence (CHCl ₃ , nm): iax (-ei) = 540 (1.00), 568 nm (0.52). MS (DEP / EI): m / z (%) = 505 (2) [M + 2H] ⁺ , 504 (9) [M + H] ⁺ , 503 (23) [f, 487 (2), 486 ( 6), 333 (2), 323 (1), 322 (6), 321 (33), 320 (100), 304 (3), 303 (2), 277 (5), 275 (1), 251 (FIG. 2), 250 (2). HRMS (C ₃₅ H ₃₇ O ₂ N): Ber. m / z 503.2824, vessel m / z: 503.2827, A = -0.0003.

Preparation Example 2: V- (l -onyldecyl) perylene-3,4-dicarboxylic acid indide: perylene-3,4-dicarboxylic anhydride (Vbdg. (4), Fig. 1) (1.00 g, 3.10 mmol) and 1-nonyldecylamine ( 967 mg, 3.41 mmol) were heated to 140 ° C. in 5 g of imidazole for 2 h, cooled with warm 2M aqueous HCl, filtered off with suction (D4 glass frit), dried at 110 ° C. in a drying oven and dried the already very high purity of the substance used without further purification for the next reactions. Y. 1.75 g (96%) of a red solid, mp 144 ° C. R _f (CHCl ₃ / where-hexane 10: 1): 0.80. Ή-NMR (CDC1 ₃ , 600 MHz, IC, TMS): δ = 0.83 (t, -V (H, H) = 7.0 Hz, 6 H, 2 x CH ₃ ), 1 .16-1 .39 (m , 28 H, 14 CH ₂ ), 1.82-1.90 (m, 2 H, β-CH ₂ ), 2.20-2.29 (m, 2 H, β-CH ₂ ), 5.16-5.22 (m, 1 H, 1 x NCH), 7.53 (t, -V (H, H) = 7.8 Hz, 2 H, 2 CHp _erylene ), 7.80 (d, V (H, H) = 8.0 Hz, 2 R 2 ^χ €: Η _Ρεΐ γ _ΐΏ1 ), 8.23 (d, ³ J (H, H) = 8.1 Hz, 2 H, 2 x CHp _iyle "), 8.26 (d, ³ J (H, H) = 7.5 Hz, 2 H, 2 χ CH _Peiylene ) , 8.47 ppm (d, br, ³ J (H, H) = 1 7.9 Hz, 2 H, 2 x CH _Pc » ₇ ien). MS (MALDI, anthracene): m / z: 588.5 [M ¹ ].

Preparation Example 3: 2- (1-Hexylhephenyl) benzo [i / e] isoquinoline-1,3-dione (6): 1 -

Hexylheptylamine (5.04 g, 25.1 mmol) and 1, 8-naphthalenedicarboxylic anhydride (5.00 g, 25.2 mmol) were heated in imidazole (12 g) under argon at 130 ° C for 3 h, allowed to cool, with 2 M aqueous HCl (500 mL). added, extracted twice with CHCh, dried (MgS0 ₄ ), evaporated in a rough vacuum and purified by column chromatography (silica gel 40-63 Lim, CHCyisohexan 1: 1). Y. 6.2 g (65%) yellow oil. R _f (silica gel, chlorofoi-m): 0.85. IR (ATR): v = 3068.0 (w), 2953.5 (s), 2921.6 (s), 2852.6 (s), 1700.8 (s), 1659.7 (s), 1628.1 (m), 1 588.5 (s), 1515.4 ( w), 1463.7 (m), 1435.6 (w), 1397.5 (m), 1372.5 (m), 1339.3 (s), 1236.0 (s), 1 176.1 (w, br), 1093.4 (w), 1071.9 (w) , 1027.7 (w), 879.7 (w), 844.8 (w), 779.9 (s), 720.9 (w), 696.1 cm ^-1 (w). Ή NMR (600 MHz, CDCl ₃ , 27 ° C, TMS) : S = 0.81 (t, V (H, H) = 7.1 Hz, 6 H, 2 x CH _3), 1:16 to 1:35 (m, 16 H, 8 x CH _2), 1.79-1.86 (m, 2 H, β-CH ₂ ), 2.18-2.26 (m, 2H, β-CH ₂ ), 5.13-5.20 (m, 1H, NCH), .7.74 (t, ³ J (H, H) = 7.7 Hz, 2 H, 2 x CH _{aroma L} ), 8.18 ppm (d, V (H, H) = 8.1 Hz, 2 H, 2 x CH _aromat. ). ^{, 3} C-NMR (150 MHz, CDCl ₃ , 27 ° C, TMS ): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 54.4, 122.7, 123.4, 126.9, 128.3, 130.8, 131.5, 133.5, 164.3, 165.4 ppm MS (DE1 70 eV): m / z (%) : 379.3 (6) [M *], 199.1 (13), 198.1 (100), 1 80.0 (12), 84.9 (14), 82.9 (23) HRMS (C ₂₅ H, N0 ₂ ): mr. 379,251 1, v / v 379,2507, Δ = + 0.0004, C25H33NO2 (379.3): calc. C 79.1 1, H 8.76, N 3. 69, items C 78.73, H 8.87, N 3.70.

Representative Example 4: 2- (1 -non-1-decyl) benzo [3 / Isoquinoline-1,3-dione: 1-Nyldecylamine (7.12 g, 25.1 mmol) and 1, 8-naphthalenedicarboxylic anhydride (5.00 g, 25.2 mmol) were heated in imidazole (12 g) under argon at 130 ° C for 3 h, allowed to cool with 2 M aqueous HCl (500 mL), extracted twice with CHCl ₃ , dried (MgSO ₄ ), in a rough vacuum evaporated and purified by column chromatography (silica gel 40-63 μηι, C HCl isohexane 1: 1). Y. 7.90 g (68%) yellow oil. R _f (silica gel, chloroform / n-hexane 1: 1): 0.81. IR (ATR): v = 3068.0 (w), 2953.5 (s), 2921.6 (s), 2852.6 (s), 1700.8 (s), 1659.7 (s), 1628.1 (m), 1588.5 (s), 1515.4 (w ), 1463.7 (m), 1435.6 (w), 1 397.5 (m), 1372.5 (m), 1339.3 (s), 1 236.0 (s), 1 1 76.1 (w, br), 1093.4 (w), 1071.9 ( w), 1027.7 (w), 879.7 (w), 844.8 (w), 779.9 (s), 720.9 (w), 696.1 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C , TMS): 6 = 0.81 (t, ³ J (H, H) - 7.1 Hz, 6 H, 2 x CH ₃ ), 1.10- 1.35 (m, 28 H, 14 x CH ₂ ), 1.90-1.70 (m, 2H, ß-CH ₂ ), 2.35-2.10 (m, 2H, ß-CH ₂ ), 5.13-5.20 (m, 1 H, NCH), 7.74 (t, V (H, H) = 7.7 Hz, 2 H, 2 x CH _aromat. ), 8.18 ppm (d, V (HH) = 8.1 Hz, 2 H, 2 x CH _aroma ) MS (DEP / EI): m / z (%): 465.7 (2) [f + 2H], 464.7 (9) ['+ H], 463.7 (24) [A \ 199.2 (14), 198.2 (100) HR MS (C, H4 ₅ N0 ₂ ): m / z: 463.3450, Gef. m / z: 463.3451, A = -0.0001.

Preparation Example 5: 2.1 1 -bis (1-hex lptl) ben / (> (13, 14 | pentapheno [, 4,5- <i '/ 1 0,9.8-i / yidiisociolin-1, 3,10 , 12 (2H, lli) -tetraoii (la): Under careful air and water

Moisture (Ar) blankets were potassium iperi-butoxide (634 mg, 5.65 mmol),

Diazabicyclo [4.3. ()] Non-5-ene (946 mg, 7.62 mmol) in toluene (10 mL) presented for 1 5 min at

Stirred 120 ° C, with 2- (l-hexylheptyl) benzo [Je] isoquinoline-L3-dione (6) (850 mg, 2.24 mmol) and 2- (l-hexylheptyl) -lH-benzo [5, 10janthra [2 , l, 9-e] isoquinoline, 3 (2 / J) -dione (5.640 mg,

1 .27 mmol) dissolved in toluene (8 mL) within 10 min dropwise added (spontaneous

Dark blue), stirred for 2 h at 120 ° C, after cooling still warm with 2 M aqueous

HCl (50 mL) precipitated, filtered off with suction (D4 glass frit), with 2 M aqueous HCl and distilled

Washed water, 16 h at 1 10 ° C in a drying oven and purified by column chromatography (silica gel particle size 40-63 μηι, chloroform). Y.

598 mg (54%) of blue solid, mp> 250 ° C. Rf (silica gel, chloroform: 0.35, IR

(ATR): v = 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s).

1505 (w), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m), 1205 (m), 1 172 (w),

1 144 ( _W ) _; 1 1 () 4 (w), 1022 (w), 954 (w), 852 (w), 840 (w), 806 (s), 790 (m), 748 (m). 723 (w).

693 (w), 680 (m), 667 cm ^-1 (w), 1 H NMR (600 MHz, CDCL, 27 ° C, TMS): ό 0.84 (t, ³ J (H, H) - 7.0 Hz, 12 H, 4 CH ₃ ), 1.20-1.42 (m, 32 H, 1 6 <CH ₂ ), 1.88-1.94 (m, 4 H, β-CH ₂ ), 2.24-2.32 (m, 4H, β-CH ₂ ), 5.18-5.25 (m, 2H, NCH), 8.38-8.46 (m, 8H, CH _Terry i _eil ), 8.54-8.63 (m, 4H , CHjenyicn). ¹³ C-NMR (150 MHz, CDC1 ₃ , 27 ° C, TMS): S = 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.6, 121.3, 121.7, 122.5, 124.1, 125.9, 128.5, 129.7, 130.8 , 131.0, 131.8, 135.3, 163.8, 164.8 ppm. UV / VIS (CHC1 ₃ ): λ _ωζχ (Ε _κ] ) = 555.2 (0.16), 598.9 (0.51), 651 .8 (1 .00). Fluorescence (CHC1 _3, _{λ exc} = 599 nm):. _max (7 _re i) = 666.2 (1.00), 731.7 (0.47). Fluoreszenzquantenausb. (CHC1 ₃ , _{λ exc} = 599 nm, £ 599 um / 1 cm ^~ 0.0136, Reference: S-13 with

Φ = 1.00): 0.93. MS (DEP / EI) m / z (%): 880 (20) [AT + 2H], 879 (35) [A + H], 878 (72) [Af], 701 (32), 698 (64) , 696 (100), 85 (46), 83 (59), 67 (26), 57 (32), 55 (48), 44 (73), 43 (30), 41 (51). HRMS (CeoHööNaC): Ber. m / z: 878.5023, Gef. m / z: 878.5012, Δ = + 0.001 1. C ₆ oH66N ₂ O ₄ (878.5): Ber. C 81.97, H 7.57, N 3.19; Gef. C 81 .68, H 7.50, N 3.14.

Darstellungsbeispie! 6: 6-Broyno-2- (1-hexylheptyl) benzo [i] iso-hinoline-K3-di n (12): 1-Hexylheptylamine (2.00 g, 1.00 mol) and 4-bromo- 1, 8-naphthalenedicarboxylic acid hydride (1.85 g, 6.69 mmol) was heated at 160 ° C. in ethylene glycol (15 mL) for 12 h, allowed to cool, treated with 2 aqueous HCl (200 mL), extracted twice with CHCl ₃ , dried (MgSO ₄ ), Evaporated in a rough vacuum and purified by column chromatography (silica gel particle size 40-63 μιη, CHCla / isohexane 1: 1). Y. 1.78 g (58%) yellow oil. Rf (silica gel, chloroform): 0.88. IR (ATR): v = 2952.9 (w), 2922.0 (m), 2854.1 (m), 1701.9 (s), 1657.8 (vs), 1617.2 (w), 1587.1 (m), 1571 (m), 1506.3 (w ), 1460.3 (m), 1423.1 (w), 1404.2 (m), 1397.2 (m), 1367.4 (w), 1353.5 (m), 1339.2 (vs), 1265.0 (w), 1 237.7 (s), 1323.8 ( w), 1 265.0 (w), 1 104.9 (m), 1088.0 (m), 1042.1 (w), 973.4 (w), 915.5 (), 882.7 (w), 849.3 (m), 827.4 (w), 809.8 (w), 779.2 (vs), 750.1 (s), 723.8 (111), 686.5 (w), 664.4 (w), 652.0 cm ^" '(w). Ή NMR (600 MHz, CDC1 ₃ , 2TC, TMS ): δ = 0.77 (t, V (H, H) = 7.1 Hz, 6 H, 2 ^χ CH ₃ ), 1.1 1 -1.33 (m, 16 11. 8 CH ₂ ), 1.76- 1.84 (m, 2 IL _beta-CH2), 2:15 to 2:23 (m, 2H, _.beta.-CH2), 5:08 to 5:16 (ra, 1 H, NCH), .7.77 (dd, ³ J (H, H) = 7.3 Hz, ^~ V (H, H) - 8.5 Hz 1 H, CH _aromat j, 7.95 (d, ³ J (H, H) = 7.9 Hz, 1 H, CH _aromat.), 8:29 to 8:41 (m, 1 H, CH _aroma ), 8.44 (d, ³ J (H, H) = 8.5 Hz, 1 H, CH _aromat .), 8.55-8.65 ppm (m, _1H , CH _aromat. ). ^{, 3} C-NMR (150 MHz, CDCl ₃ , 27 ° C, TMS): δ = 14.0, 14.1, 22.5, 26.9, 29.2, 31.7, 32.3, 54.6, 128.0, 129.1, 129.7, 130.4, 130.8, 131.0, 131.6 , 132.3, 132.7, 1 63.6, 164.7 ppm. MS (DEP / El) m / z (%): 458.2 (3) [ ^f + H], 457.2 (9) [Hf], 279.0 (1 1), 278.0 (100), 277.0 (15), 276.0 (96 ). HRMS (C ₂ , H; ₂ BrNO ₂ ): Ber. m / z: 457.1616, Gef. m / z: 457.1603, Δ = + 0.0013. C ₅ H; ₂ BrN0 ₂ (457.2): Ber. C 65.50, H 7.04, N 3.06; Gef. C 65.48, H 7.24, N 2.91.

Preparation Example 7: 9-Bromo-N- (1-hexylheptyl) perylene-3,4-dicarboxylic acid imide (7)

(see L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem., 1995, 1229-1244): A suspension of / Y- (1-hexylheptyl) perylene-3,4-dicarboximide (5. 200 mg , 0.397 mmol) in chloroform was heated to 40 ° C, treated with elemental bromine (127 mg, 0.749 mmol), 2.5 h at 40 -50 ° C, extracted three times with a saturated sodium miosulfate solution, dried over magnesium sulfate, in a rough vacuum evaporated and purified by column chromatography (silica gel 40-63 μτη, chloroform). Y. 208 mg (90%) orange solid, mp 186-1 87 ° C. R _f (silica gel / chloroform): 0.75. Ή NMR (600 MHz, CDCl 2, 27 ° C, TMS): S = 0.83 (t, ³ J (H, H) - 7.0 Hz, 6 1 1. 2 C i L). 1 .20-1 .43 (m, 16 H, 8 CH ₂ ), 1.86- 1.91 (m, 2 H, 2 ^χ β-CH ₂ ), 2.23-2.31 (m, 2 H, 2 ^χ β-CH ₂ ), 5.15-5.24 (m, 1 H, NCH), 7.45 (t, ³ J (H, H) - 7.8 Hz, 1 H, CHp _ery ie "), 7.62 (d, ³ J (H, H) = 8.0 Hz, 2 H, 2 x CH ^ i «,), 7.80 (d, ³ J (H, H) = 8.0 Hz, 1 H, CH _pery ie"), 8.00 (d, ³ J (H, H) = 8.0 Hz, 1 H, CH _perylene), 8:01 (d. ³ / (H, H) = 8.4 Hz, 1 H, CH _pcr), _len), 8:08 (d, ³ J (H, H) = 8.0 Hz, 1H, CH _perylene ), 8.07 (d, J (H, H) = 8.2 Hz, 1% CHper _j -ie ,,), 8.41 ppm (in br, 2 IL 2 · CH _per> .ien) - UV / Vis (CHC1 ₃ ): _max (E _{re /} ) = 483 (0.96), 509 (1.00) nm. Fluorescence (CHCl ₃ , _{λ exc} = 483 nm): _λ _max (I _re j) = 540 (1.00) , 568 (sh, 0.54) nm. MS (DEP / El): m / z (%): 584.4 (15) [M + H], 583.4 (40) [Μ '], 582.4 (16), 581.4 (40 402.1 (43), 401.1 (100.0, 400. 1 (45), 399.1 (96). HRMS (C ₃ 5H ₃₆ BrNO ₂ ): Ber. M / z: 581.1929, Gef. M / z 581.1919, Δ = + 0.0010.

Preparation Example 8: 9,9'-Bis [3,4-dicarboxylic acid, 4- (1-hexylheptylimide)] (8)

(see H. Langhals, A. Hofer, J. Org. Chem., 2012, 77, 9585-9592):

Method 1: 9-Bromo-N- (1-hexylheptyl) perylene-3,4-dicarboximide (7, 150 mg, 0.257 mmol) in toluene (20 mL) was dissolved under air and with exclusion of moisture (Ar protective gas) to reach 70 the solution is heated ° C, with Pd (OAc) ₂ (44.4 mg, 0.198 mmol) and Bu ₄ NBr (146 mg, 0.453 mmol), heated to 100 ° C, with triethylamine (1 mL), 15 h at 120 ° C stirred, allowed to cool, treated with 2 M aqueous HCl (100 mL), extracted three times with CHCl ₃ , dried with magnesium sulfate, concentrated in a rough vacuum and purified by column chromatography (silica gel particle size 40-63 μηι, chloroform). Y. 240 mg (93%) orange-red solid.

Method 2: 9-iodo- / V- (1-hexylheptyl) perylene-3,4-dicarboximide (100 mg, 0.159 mmol) in toluene (20 mL) was dissolved under air and with exclusion of moisture (Ar protective gas), to 70 ° C heated with Pd (OAc) ₂ (27.4 mg, 0.122 mmol) and Bu ₄ NBr (90.3 mg, 0.280 mmol), heated to 100 ° C, treated with triethylamine (1 mL), stirred at 120 ° C for 15 h, allowed to cool, with 2 M aqueous HCl (100 mL), extracted three times with CHCl ₃ , dried over magnesium sulfate, concentrated in a rough vacuum and purified by column chromatography (silica gel 40-63 μιη, chloroform). Y. 152 mg (95%) orange-red solid, mp> 250 ° C. R _f (silica gel, chloroforai / hexane 3: 1): 0.31. 1 H-NMR (600 MHz, CDCl ₃ , ITC, TMS): δ = 0.81 (t, ³ J (H, H) = 6.7 Hz, 12 H, 4 χ CH ₃ ), 1 .13-1.39 (m, 32 H, 16 CH ₂ ), 1 .76-1 .93 (m, 4 H, 2 x β-CH ₂ ), 2.14-2.34 (m, 4 H, 2 x β-CH ₂ ), 5.1 1 -5.25 ( m, 2 H, 2 a-CH), 7.43-7.60 (m, 4 H, 4 χ CH _pe , .i _en ), 7.69 (d, V (H, H) = 7.8 Hz, 1 H, CH _pe. ien) _? 8.42- 8.70 ppm (m, 12H, 12 x CH _arom .). UV / Vis (CHC1 _3). A _max (E _rd) = 500 (0.67) 526.4 (1.00) nm Fluorescence (CHCl _3, _{£ XC} = 500 nm): X _MSX (7 _rel) = 596.4 nm.

(2a)

Preparation Example 9: Quaterryene-3,4: 13,14-tetracarboxylic acid 3,4: 13,14-bis (1-nonyldecylimide) (2a): Under argon and careful exclusion of oxygen and moisture, potassium fcrf-butoxide was obtained (228 mg, 2.03 mmol) and diazabicyclo [4.3.0] non-5-ene (335 mg, 2.70 mmol) in 5 mL absolute. Toluene for 0.5 h at 130 ° C, with 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4- (l -nonyldecylimid)] (8, 1 .00 g, 0.93 mmol) in dry toluene (15 mL) within 1 h dropwise added (dark color), stirred at 130 ° C for 2.5 h, allowed to cool, treated with 2 M aqueous HCl (250 mL) (black mixture), extracted three times with chloroform (40 mL), over Dried MgS0 ₄ , evaporated in a rough vacuum and column-purified by chromatography (silica gel 40-63 μιη, chloroform, second, turquoise fraction). Y. 830 mg (83%) turquoise solid, Sclimp. > 250 ° C. R _f (silica el. Chloroform): 0.23. 1R (ATR): v = 3376.9 (w), 3306.0 (w), 3056.7 (w), 2953.4 (m), 2920.2 (s), 2851.1 (m), 1930.1 (w), 1803.7 (w), 1693.5 (s ), 1649.4 (s), 1615.6 (w), 1591.7 (s), 1 570.7 (s), 1506.7 (w), 1455.8 (m), 1408.0 (m), 1391 .8 (m), 1 371.9 (w) , 1349.1 (vs), 1317.9 (m), 1242.9 (s), 1207.5 (m), 1 188.0 (m), 1 170.3 (m), 1 138.8 (w), 1 1 10.8 (m), 1045.4 (w) , 1008.8 (w), 965.1 (w), 950.3 (w), 920.4 (w), 903.2 (w), 843.9 (m), 81 1.6 (s), 791.5 (m), 752.1 (s), 719.8 (m), 697.7 (w), 669.3 cm '(w). 1 H NMR (600 MHz, CDCl 2, 27 ° C, TMS): S = 0.85 (t, ³ J (H, H) - 7.0 Hz, 12 H, 4 CLL), 1.24-1, 42 (m, 56 ii. 28 CH _2), 1.94-2.05 (m, 4 H, 2 x CH ₂ SS), 2:24 to 2:31 (m, 4H, _.beta.-CH2), 5:15 to 5:29 (m, 2 H, 2 NCH ), 7.47-8.02 (m, 12H, 12 x CH _8roro ), 8.0-8.32 ppm (m, _4H , 4 ^χ _CHPeiylen. ). ¹ C-NMR (1 50 MHz, CDCl 3, 27 ° C, TMS): S = 1 3. 1, 22.7, 27.3, 29.4, 29.7, 32.0, 32.5, 54.7, 76.8, 77.0, 77.2, 1 30.7 ppm. UV / Vis (CHCl 3): Imax (E _Cl ) = 632.3 (0.13), 684.2 (0.83), 762.2 (1.00) nm. Q ₂ H ₉₆ N ₂ O ₄ (1172.7): Calcd. C 84.06, H 8.09, N 2.39; Gef. C 84.08, H 8.18, N 2.28.

Preparation Example 10: 3, 10-l) ibromiper (10): Perylene (1.00 g, 4.00 mmol) and N-bromosuccimide (1.78 g, 10.0 mmol) were dissolved in dichloromethane (100 mL) for 24 h at room temperature stirred, evaporated to dryness in a rough vacuum and extracted continuously with chloroform for 8 h to remove unreacted perylene. Y. 1 .49 g (91%) yellow solid mp> 250 ° C. IR (ATR): P ^" = 3049.1 (w), 2957.3 (w), 1932.5 (w), 1851.2 (w), 1771.9 (w), 1692.1 (m), 1599.9 (w), 1586.2 (w), 1571.7 ( m), 1509.8 (w), 1493.0 (m), 1451.0 (w), 1429.7 (w), 141 1.5 (w), 1378.0 (s), 1346.8 (m), 1306.6 (w), 1295.7 (w), 1262.8 (w), 1 193.9 (s), 1 181.6 (s), 1 150.9 (w), 1135.4 (w), 1 108.5 (m), 1057.1 (w), 1018.1 (w), 984.0 (w), 963.0 ( m), 935.0 (w), 889.2 (w), 856.0 (m), 816.7 (vs), 798.3 (vs), 781.5 (s), 757.9 (vs), 667.4 (m), MS (DEP / EI) m / z (%): 409.9 (55) [M + 2H] _: 407.9 (29) [Af], 330.0 (88), 251.1 (29), 250.1 (100), 249.1 (33), 248.1 (35), 125.5 (85), 124.0 (32), 84.9 (52), 82.9 (75), 47.0 (36), 44.0 (59), 43.0 (24) HR MS (C ₂ oHioBr ₂ ): m. 407.9149, Gef m / z: 407.9146, Δ = + 0.0003.

(11) Preparation Example 11: Bis (4,4,5,5-tetramethyl-2-perylene-3,10-yl [l, 3,2] dioxaborolane) (11) (see Y. Avlasevich, K. Müllen, J. Org Chem. 2007, 72, 10243-10246): With exclusion of air and moisture (Ar protective gas), 1,4-dibromoperylene (10, 500 mg, 1.22 mmol), bispinacolato diboron (775 mg, 3.05 mmol) and potassium acetate (491 mg, 5.01 mmol) in 1, 4-dioxane (18 mL), treated with PdCl ₂ (dppf) (43.0 mg, 0.052 mmol), heated for 1 7 h at 70 ° C, evaporated in a rough vacuum and purified by column chromatography (silica gel 40 -63 μηι, chloroform). Y. 320 mg (52%) yellow solid, mp> 250 ° C. R _{ (silica gel / chloroform): 0.92. IR (ATR): v = 2954.5 (s), 2923.6 (vs), 2853.3 (s), 1736.6 (w), 1736.6 (w), 171 1 .5 (w), 1697.5 (w), 1 658.8 (w) , 1649.2 (w), 1588.1 (w), 1492.9 (w), 1461.4 (w), 1453.2 (w), 1433.5 (w), 1370.0 (m), 1347.7 (m), 1316.0 (w), 1294.2 ( w), 1228.8 (w), 1209.1 (w), 1 189.2 (w), 1 144.9 (w), 1 105.9 (w), 1082.4 (w), 1018.7 (w), 964.8 (), 893.8 (w), 850.8 (w), 813.8 (w), 804.4 (w), 765.3 cm ^"1 (w) MS (DEP / El) m / z (%): 505.3 (28) [h + H], 504.3 (100) [M ^1], 503.3 (48) 458.1 (62) 457.1 (32) 456.1 (68) 409.9 (47) 407.9 (23) 378.2 (31) 358.0 (25) 356.0 (29) 302.9 (26), 301.9 (21), 277.4 (39), 276.4 (32), 275.4 (38), 251.7 (36), 249.7 (64), 248.7 (21), 247.7 (23), 125.0 (34), 124.0 (22), 41 .0 (21). HRMS (CVI MU: mr. M / z: 504.2643, m.w. = 504.2635, Δ = + 0.0008.

Preparation Example 12: bis [2- (1-hexyheptyl) -6-perylene-3,10-ylbenzofi / i ^, lisoquinoline

1,3-dione (13): In the absence of air (Ar protective gas), 6-bromo-2- (1-hexylheptyl) benzo [Je] isoquinoline-1,3-dione (12, 100 mg, 0.380 mmol) and 1 , 4-Dibromoperylene (10, 83.3 mg, 0.165 mmol) in toluene (15 mL), with 2 aqueous K ₂ CO_rLsg. (5 mL) and ethanol (1 mL), heated to 80 ° C, with tetrakis (triphenylphosphine) palladium (0) (10.0 mg 8.65 μηιοΐ), stirred for 16 h at 80 ° C, allowed to cool and with the organic phase separated. The aqueous phase was washed with Extracted by shaking Tolvjol and the combined organic phases dried with magnesium sulfate, evaporated in a rough vacuum and purified by column chromatography (silica gel 40-63 μχη, chloroform) Yield. 166 mg (88%) of yellow solid, sclimp. > 250 ° C. R _f (silica gel / chloroform): 0.85. IR (ATR): v = 2952.3 (w), 2923.0 (m), 2854.5 (w), 1697.0 (s), 1655.2 (vs), 161 5.4 (w), 1586.7 (s), 151 1.6 (w), 1455.6 (w), 1398.5 (w), 1391.7 (w), 1344.5 (vs), 1266.7 (w), 1237.9 (s), 1 1 79.1 (w), 1 163.9 (w), 1 1 32.3 (w), 1 103.5 (w), 1072.2 (w), 1034.8 (w), 970.1 (w), 936.5 (w), 862.4 (w), 840.6 (w), 813.5 (m), 784.0 (vs), 771.5 (m), 759.9 (s), 723.9 (w), 701.0 (w), 689.8 cm ^-1 (w). Ή NMR (600 MHz, CDC1 ₃ , 27 ° C, TMS): δ = 0.68-0.93 (m, 1 2 H. 2 x (H 2 O, 1.12-1.46 (m, 32 H, 1 x 6 CH ₂ ), 1.78-1.95 (m, 4 H. 2 <β-CH ₂ ), 2.16-2.37 (m, 4H, 2 ^χ _.beta.-CH2), 5:14 to 5:29 (m, _aromatic 2 H, 2 NCH ^χ), 7:19 to 7:32 (m, 4 H, 4 x _CH.), 7:31 to 7:45 (m, 2 H, 2 CH _aromat. ) 7.52-7.57 (m, 1 H, CH _aromat. ), 7.58-7.64 (m, 2 H, 2 x CH _aromat ), 7.69 (dd, ³ J (H, H) = 7.4 H, ⁴ J (H, H) = 1 .1 Hz 1 H, CH _aromat ), 7.82-7.86 (m, 1 H, CH _aromat. ), 7.91 (d, V (H, H) = 8.6 H, 1 H, CH _aromat ), 8.28 (d, ³ J (H, H) = 7.7 H, 1 H, CH _aromat.), 8:33 (d, V (H, H) = 7.7 H, 1 H, CH _aromat.), 8:38 (d, V ( H, H) = 7.9 Hz, 1 H , CH _aromat. ), 8.42 (dd, 7 (HH) = 7.9 Hz, ⁴ J (H, H) = 1 .2 Hz, 1 H, CH _arom ), 8.54-8.78 ppm ( _mbr , 4H, 4 x CH _aromat j ¹³ C-NMR (150 MHz, CDCl ₃ , 27 ° C, TMS): S - 14.1, 22.6, 26.9, 27.0, 29.2, 29.3, 29.7, 31.8, 31 .9, 32.4, 54.6, 54.7, 120.0, 120.2 , 120.9, 121.1, 122.4, 123.1, 123.7, 126.2, 126.4, 127.0, 127.2, 127.3, 127.4, 128.6, 128.7, 128.8, 128.9, 130.1, 130.7, 131.1, 131.2, 1 31 .4, 131.6, 131. 7, 131.8, 1 32.4, 133.6, 1 36.3, 136.5, 142.6, 144.9, 1 64.4, 165.3 ppm MS (DEP / EI) m / z (%): 1006.6 (32) [Λ-], 756.5 ( 1 7), 643.2 (14), 575.3 (100), 394.1 (1 8), 393.1 (39), 57.1 (17), 56.1 (16), 55.1 (86), 47.0 (22), 43.0 (44), 41.0 (38). HRMS (C70H74 2O4): mr. M / z: 1006.5649, m.w.: 1006.5584, Δ = + 0.0055.

Preparation Example 13: Quaterryene-3,4: 13,14-tetracarboxylic acid-3,4: 13,14-bis (1-hexylheptylimide) (2a) (see H. Langhals, J. Büttner, P. Blanke, Synthesis, 2005 , 364-366, H. Langhals, G. Schönmann, L. Feiler, Tetrahedron Lett., 1995, 36, 6423-6424): Method 1: Under careful exclusion of air and moisture (Ar-shielding gas) potassium fcrt-butoxide (290 mg, 2.03 mmol) and diazabicyclo [4.3.0] non-5-ene (0.340 mL, 2.70 mmol) in dry toluene ( 10 mL) for 0.5 h at 130 ° C, with 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4- (l -hexylheptylimid)] (8, 670 mg, 0.680 mmol) in dry toluene (15 mL) was added dropwise over 1 h (dark color), stirred at 130 ° C for 2.5 h, allowed to cool, treated with 2 M aqueous HCl (150 mL), extracted with ChlorofonTi (3 x 40 mL), dried over MgSg " ₄ , concentrated by evaporation in a vacuum and purified by column chromatography (silica gel 40-63 μτη, chloroform, second, turquoise fraction), yielding 573 mg (84%) of turquoise solid.

Method 2: Under careful exclusion of air and moisture (Ar-shielding gas) K a 1 iu m-ft r / - butanoate (290 mg, 2.03 mmol) and diazabicyclo [4.3.0] non-5-ene (0.340 mL , 2.70 mmol) in dry toluene (10 mL) and stirred for 0.5 h at 130 ° C, with 13 (685 mg, 0.680 mmol) in dry toluene (15 mL) over 1h dropwise added (dark color), 2.5 h at 130 ° C., allowed to cool, admixed with 2 M aqueous HCl (150 ml), extracted with chloroform (3 × 40 ml _), dried over MgSO ₄ , concentrated in a rough vacuum and purified by column chromatography (silica gel 40-63 μm. Chloroform). Y. 464 mg (68%) of turquoise solid, mp> 250 ° C. R _f (silica gel, chloroform): 0.20. 1 H NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.89 (t, ³ J (H, H) = 6.6 Hz, 12 H, 6 ^χ CH ₃ ), 1.20-1.40 (m, 32 H, 16 ^χ CH ₂ ), 1.99 (m, 4 H, β-CH ₂ ), 2.31 (m, 4 H, β-CH ₂ ), 5.18 (m, 2 H, CH), 7.59 (m, 4 H 4 ^■ CH _pei _n .), 7.95 (m, 8 H, 8 x CH _perylene .), 8.27 ppm (m, 4 H, 4 CH _by yl _and J. 'ΐ-NMR (150 MHz, CDCh, 27 ° C, TMS): S = 14.1, 22.7, 27.2, 29.4, 31.9, 32.5, 54.6, 120.1, 122.2, 123.5, 127.0, 127.6, 128.9, 129.6, 131.0, 135.1 ppm UV / Vis (CHC1 ₃ ): λ _max (ε) = 628.2 (18360), 691.4 (62900), 762.2 nm (151800) MS (DEP / Ei): m / z (%): 1004.5 (9) [AT + 2H], 1 003.5 (22) [ + H], 1002.5 (28) [M 640.0 (1 1), 639.0 (27), 638.0 (42), 182.0 (23), 1 1 1.0 (12), 97.0 (30), 84.0 (25), 83.0 ( 51), 82.0 (12), 71.1 (17), 70.1 (55), 69.1 (99) 68.1 (10), 67.1 (22), 57.1 (38), 56.1 (55), 55.1 (100), 54.0 (21 ), 43.0 (47), 42.0 (17), 41.0 (67) HRMS (C70H70N2O4): m.r./m .: 1002.5336, m.w.: 1002.5349, Δ = - 0.001 3. C70H70N2O4 (1002.5): m.p. C 83.80, H 7.03, N 2.79, Gef C 83.75, H 7.02, N 2.67.

Example 1: A ^{^;,} -r) i- (l-hexylheptyl) -2-pyrroIidinoterryIen-3,4: 1,12-tetracarboxylic acid bis-l dicarboximide (14): 2,1 l-bis (l-hexylheptyl ) benzo [13,14] pentapheno [3,4,5-IE / ^": 10,9.8- 'e ^ diisoquinoline-l, 3,10,12 (2H, LLH) -tetraon (la, 100 mg, 0.114 mmol) was dissolved in pyrrolidine (40 mL), stirred at room temperature for 24 h, evaporated to dryness and purified by column chromatography (silica gel, chloroform) yield 73 mg (68%) of a green solid, mp> 250 ° C. R _f (silica gel) Chloroform): 0.75 IR (ATR): v = 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s ), 1505 (w), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m), 1205 (m), 1172 (w), 1144 (w ), 1104 (w), 1022 (w), 954 (w), 852 (w), 840 (w), 806 (s), 790 (m), 748 (m), 723 (w), 693 (w ), 680 (m), 667 cm ^'1 (w) .11-MR (600 MHz, CDC1 ₃ , 25 ° C, TMS): ό 0.82 (t, V (H, H) = 7.0 Hz, 12H. 4 ^χ CH ₃ ), 1.13-1.39 (m, 32 H, 16 (Ή-), 1.82-1.91 (m, 4 H.2 ^χ β-C ₂ ), 1.95-2.11 (m, 4H, 2 x 2 ^χ ß- CH _{p> Trolldinyl} ), 2.21-2.32 (m, 4 H, 2 ^χ β-CH ₂ ), 2.85 (s (br), 2 H, 2 x a-CH _pyrrolidinyl ), 3.77 (s (br), 2 H, 2 x 5:19 to 5:25 (m, 2 H, 2 NCH ^χ), 7.82-7.88 (m, 1 iL CH _Te n-yien), 8.37- 8.60 ppm (m, 10 H, 10 x CH _Te rryi _{e ").} ^{, 3} C-NMR (150 MHz, CDCl ₃ , 25 ° C, TMS): δ = 14.0, 22.6, 25.7, 27.0, 29.3, 29.7, 31.8, 31.9, 32.4, 32.5, 52.0, 54.4, 118.5, 120.0, 120.3 , 122.1, 122.2, 123.7, 123.8, 124.0, 126.0, 126.2, 127.0, 127.9, 128.2, 129.5, 130.1, 131.8, 132.1, 136.2, 147.6 ppm. ÜV / 'VIS (CHC1 ₃ ): λ _max (e) = 421.3 (4130), 452.7 (7010), 472.6 (10100), 499.7 (19700), 727.2 nm (56800). MS (DEP / El) m / z (%): 949.6 (31.8) [AT + 2H], 948.6 (76.5) ['+ H], 947.6 (100) [Αί'], 766.4 (11.4), 584.2 (19.8) .583.2 (30.2), 69.1 (13.0), 55.1 (14.9), 41.0 (12.0). HRMS (C ₆₄ H ₇₃ N ₃ O ₄ ): Ber. 947.5601, Cef. m / z: 947.5588, Δ = + 0.0013. C ₆₄ H ₇₃ N ₃ O ₄ (947.6): Calcd. C 81.06, H 7.76, N 4.43; Gef. C 80.65, H 7.97, N 4.18.

Example 2: AvV-f) i- (1-hexylheptyl) -2,1,3-dipyrrolidinoterrorene-3,4: 11,12-tctracarboxylic acid bis-dicarboximide (15): 2,11 -bis (1 - hexylhcptyl) bcnzo [13.14] pentanothiopheno [3.4.5-def. 10,9,8-yl diisoquinoline-1,3,10,12 (2H, 1l) -tetraon there, 100mg, 0.114mmol) was dissolved in pyrrolidine ( 40 ml.), Stirred for 9 d at room temperature, evaporated to dryness and purified by column chromatography (silica gel, chloroform). Y. 96 mg (83%) of blue solid, mp> 250 ° C. R _f (silica gel, chloroform): 0.83. IR (ATR): v = 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s), 1505 (w ), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m). 1205 m, 1172 w, 1144 w, 1104 w, 1022 w, 954 w, 852 w, 840 w, 806 s, 790 m, 748 (m), 723 (w), 693 (w), 680 (m), 667 cm ^-1 (w) .1 H NMR (600 MHz, CDCl ₃ , 25 ° C, TMS): S = 0.82 (td , V (H, H) - 7.0 Hz, ² J (H, H) = 1.8 Hz 12 H, 4 CH ₃ ), 1.13-1.42 (m, 32 H, 16 CH ₂ ), 1.81-1.91 (m.4 H.2 ^χ β-CH ₂ ), 1.91- 2.19 (m, 8 H, 2 4 CH- _pyno- _idynyl ), 2.19-2.35 (m, 4 H.2 ^> β-C ₂ ), 2.86 (s (br) , 4 H, 4 ^χ α- CHpvrr _o ii _d myi), 3.76 (s (br), 4 Ii, 4 x a-CHpynoiidinyl), 5.13-5.30 (m, 2 H, 2 ^χ NCH), 8.38-8.46 ( m, 8 H, 8 CH _terrylene ), 8.54-8.63 ppm (m, 4 H, 4 CH _T erryien) - ¹³ C-MR (150 MHz, CDCl ₃ , 25 ° C, TMS): S = 14.0, 22.6, 25.6, 26.9, 27.0, 29.3, 31.8, 32.4, 32.5, 52.1, 54.4, 54.6, 117.8, 118.0, 118.6, 119.2, 119.4, 123.5, 125.3, 126.1, 130.6, 131.1, 131.9, 132.3, 148.8 ppm UV / VIS (CHC1 ₃ ): ") = 413.8 (8780), 468.7 (4610), 499.9 (5800), 562.2 (9800), 589.0 (10900), 777.2 nm (52120) MS (DEP / EI) m / z (%) ): 1019.6 (25) [ ⁺ + 3H], 1018.6 (51) [Af + 2H], 1017.6 (77) [Af + H], 1016.6 (100) [Μ '], 947.6 (21), 652.2 (21), 391.0 (19), 182.2 (17), 97.1 (28), 85.1 (30) .84.1 (27), 83.1 ( 54), 81.1 (19), 71.1 (40), 70.1 (39), 69.1 (84), 67.1 (23), 57.1 (68), 56.1 (50), 55.1 (84), 43.0 (57), 43.0 ( 23), 42.0 (20), 41.0 (59). HRMS (QgHgoW-i): Ber. 1016.6180, Gef 1016.6154 Δ = + 0.0026 €: Ά ₉₀ Ν ₄ Ο ₄ (1016.6): Ber. C, 80.28, H, 7.93, N, 5.51; Gef. C 80.20, H 7.90, N 5.32.

Example 3: A _v V -di (1-hexyheptyl) -2-pyrrolidinoquaterryl-3,4: 13,14-tetracarboxylic acid bis-dicarboximide (16): Quatcrrylene-3, 4: 1. 1,4-tetraearbonic acid 3.4: 1 3. 1 4-bis (1-hexylheptylimide) (2a, 100 mg, 0.100 mmol) was dissolved in pyrrolidine (40 mL), stirred at room temperature for 40 d, evaporated to dryness and column chromatographically (Silica gel, chloroform). Y. 96 mg (83%) violet solid, mp> 250 ° C. R _f (silica gel, chloroform): 0.73. IR (ATR): v = 2954.8 (m), 2924.9 (s), 2855.0 (m), 1688.7 (vs), 1650.3 (s), 1594.9 (m), 1568.6 (vs), 1542.3 (w), 1500.3 (w ), 1484.0 (w), 1457.4 (w), 1414.5 (w), 1391.1 (w), 1346.2 (vs), 1322.1 (m), 1287.6 (s), 1248.1 (w), 1230.1 (m), 1 174.2 ( w), 1 126.3 (w), 1105.6 (w), 1077.9 (w), 1052.0 (w), 946.4 (w), 908.5 (w), 840.0 (w), 807.8 (m), 751.9 (w), 732.0 (w), 668.6 cm ^-1 (w). Ή NMR (600 MHz, CDCl ₃ , 25 ° C, TMS): δ = 0.78-0.89 (m, 12 H, 4 x CH ₃ ), 1 .21 - 1 .41 (m, 32 H, 16 CH ₂ ), 1.86-1, 94 (m, 4 1 1. 2/3-CH ₂ ), 1.99-2.10 (m, 4 H, 2 2? -CH _{p> TroHdmy} i), 2.23-2.35 (m, 4 H, 2 x β-CH ₂ ), 2.84 (s (br), 2 H, 2 x a-CHpvrroiidinyl), 3.75 (s (br), 2 H, 2 x a-CH- _pyrollardyl ), 5.19-5.25 (m, 2H, 2 x NCH), 7.95-8.61 ppm (m, 15 H, 1 5 x CH _Qualerrylen ) ¹³ C-NMR (150 MHz, CDC1 ₃ , 25 ° C, TMS): δ = 14.0, 22.6, 25.5, 25.6, 27. 1, 29.3, 29.5, 29.7, 31 .9, 32.5, 32.6, 54.4, 54.5, 1 14.3, 121 .4, 123.8, 123.9, 124.2 , 126.0, 128.1, 130.0, 130.9, 131.9, 134.4, 135.7, 146.8, 147.8, 164.1, 1 64.8, 165.1 ppm. UV / VIS (CHCi ₃ ): _Η "() = 381.2 (9630), 470.2 (6270), 515.5 (9300), 546.7 (1 1200), 671.3 (14960), 81 1 .8 nm (86600). MS (FAB ⁺ ); m / z (%): 1072 (1) [M * + H], 1071 (1) [M *]. HRMS (C74H77N3O4): Ber. 1071.5914, Gef. 1071 .591 1, Δ = - 0.0003. C74H77N3O4 (1071.6): Ber. C 82.88, H 7.24, 3.92; Gef. C 82.47, H 7.60, N 3.81.

Example 4: V, VI) i- (I -hexylhepty-1) -2,15-dipyrrolidinoquatricarbonyl-3,4: 13,14-tetracarboxylic acid bis-di-maleimide (17): quaterrylene-3,4: 1 14-tetracarboxylic acid 3.4: 1. 3. 14-bis (1-hexylheptylimide) (2a, 100 mg, 0.100 mmol) is dissolved in pyrrolidine (40 mL), stirred for 14 d at room temperature, evaporated to dryness and s 1 hrom ato rap hi sc h (silica gel, chloroform). Y. 96 mg (83%) violet solid, mp> 250 ° C. R _f (silica gel, chloroform): 0.81. IR (ATR): v = 2954.8 (m), 2924.9 (s), 2855.0 (m), 1688.7 (vs), 1650.3 (s), 1594.9 (m), 1 568.6 (vs), 1542.3 (w), 1500.3 ( w), 1484.0 (w), 1457.4 (w), 1414.5 (w), 1391.1 (w), 1346.2 (vs), 1322.1 (m), 1287.6 (s), 1248.1 (w), 1230.1 (m), 1 174.2 (w), 1 126.3 (w), 1 105.6 (w), 1077.9 (w), 1052.0 (w), 946.4 (w), 908.5 (w), 840.0 (w), 807.8 (m), 751.9 ( w), 732.0 (w), 668.6 cm ^-1 (w). Ή NMR (600 MHz, CDCh 27 ° C, TMS): 0.78-0.89 (m, 12 H, 4 ^χ CH ₃ ), 1. 21 -1.41 (m, 32 H, 1 6 ^χ CH ₂ ), 1.86- 1 .94 (m, 4 H, 2 ^χ / i-CH ₂ ), 1 .99-2.1 0 (m, 4 H, 2 x 2 ^χ / ^ - CH _pyrrolidinyl ), 2.23-2.35 (m, 4 H, 2 x? -CH ₂ ), 2.84 (s (br), 2 H, 2 x a-CH _pym , iidinyl), 3.75 (s ( br), 2 H, 2 x a-CH _pyrrolidine] yi), 5.19-5.25 (m, 2H, 2NCH), 7.95-8.61 ppm (m, 15H, 15 x CH _Quaterr) , i _eil ). ^{, 3} C-NMR (150 MHz, CDC1, 27 ° C, TMS): o = 14.0, 22.6, 25.5, 25.6, 27.1, 29.3, 29.5, 29.7, 31.9, 32.5, 32.6, 54.4, 54.5, 1 14.3, 121.4, 123.8, 1 23.9, 124.2, 126.0, 128.1, 130.0, 130.9, 13.1.9, 134.4, 135.7, 146.8, 147. 8, 164.1, 164.8, 165. 1 ppm. UV / VIS (CHCl ₃ ): 1 _m ax (i?) = 463.5 (7350), 490.3 (9350), 555.6 (7610), 589.7 (8210), 851.0 nm (73390). MS (FAB ^+): m / z (%) 1 140.7 (100) [Af], HRMS (C78H84N O _4): SSER. m / z: 1 140.6493, Gef. m / r. 1 140.6497, Δ = + 0.0004.

Example 5: Compounds 19/20: Compound 18 (H.Langhals et al., DE 102008061452; Chrn. Abstr. 2009, 151, 58174), (see Fig. 5, 100 mg, 0.114 mmol) was dissolved in pyrrolidine (40 mL ), stirred for 14 d at room temperature, evaporated to dryness and purified by column chromatography (silica gel, chloroform). Y. 74 mg (78%) of green solid, mp> 250 ° C. R _f (silica gel, chloroform): 0.73. IR (ATR): v = 3316.6 (w), 2951.9 (w), 2919.4 (m), 2852.1 (m), 1694.6 (m), 1669.6 (s), 1639.7 (m), 1622.8 (s), 1598.7 (s ), 1585.6 (vs), 1551.0 (s), 1529.6 (m). 1483.1 (m), 1450.7 (m), 1411.4 (m), 1332.8 (vs), 1321.1 (s), 1290.2 (s), 1235.5 (s), 1217.3 (m), 1179.9 (m), 1117.3 (m), 1088.1 (w), 1060.7 (m), 1027.8 (w), 954.1 (w), 934.3 (w), 900.0 (w), 865.3 (m), 811.9 (s), 780.6 (m), 755.0 (m),

736.5 (w), 690.5 cm ^'1 (w). Ή NMR (600 MHz, CDCl ₃ , 25 ° C, TMS): δ = 0.79-0.84 (m, 12H, 6 CH ₃ ), 1.18-1.42 (m, 32H, 16 ^χ CH ₂ ), 1.86- 1.97 (m, 4H.2β-Cft ₂ \ 1-99 (s (br), 2 H, _2β -CH- _pynomymyl ), 2.24-2.37 (m, 4 H, 2β-CH ₂ ), 5.18-5.30 (m, 2 H, 2 x NCH), 7.67-7.69 (m, 3 H, 3 CH _a .), 8.33-8.35 (m, 2 H, 2 CH _aryl ), 8.56-8.77 (m, 6 H, 6 CH _Pery i _s), 10.74 (d, ³ J = 8.2Hz, 1 H; CH _PCTy, _s), 11:52 ppm (s, 1 H, NH) ^I3 C NMR (150 MHz, CDC1 _3, 25 °. C, TMS): δ 14.0, 22.6, 25.8, 26.9, 29.3, 31.8, 32.4, 32.5, 32.6, 54.4, 122.6, 127.6, 129.3, 131.7, 148.5 ppm. UV / VIS (CHCl ₃ ): _max (e) = 436.1 (12890), 458.3 (16760) .484.3 (11530), 525.9 (8490), 592.7 (9770), 653.5 (27040), 697.3 nm (35200) MS (DER / EI) m / z (%): 942.6 (5) [A + 3H],

941.6 (26) [M * + 2H], 940.6 (65) \ M + H], 939.6 (100) [A], 576.2 (11), 575.2 (12), 97.1 (13), 83.1 (14), 70.1 (15), 69.1 (26), 57.1 (19), 56.1 (16), 55.1 (31), 43.9 (19), 42.9 (19), 40.9 (17). HRMS (CeiHfeNsO-: Ber.939.5663, Gef.939.5652, Δ = + 0.0011. Ε _6! Η ₇₃ Ν ₅ θ4 (939.6): Preparations C 77.92, H 7.83, N 7.83, Gef. C 77.51, 117.45, N 8.12 ,

Example 6 Efficacy of the compounds according to the invention as scnsibilizers for

Dye solar cells: Various Perylen-, Terrylen- or Quaterrylenverbindungen were with Help of Grätzel solar cells tested on their efficiency as a sensitizer for obtaining electrical energy from solar energy. The cells were irradiated with daylight in cloudy skies and a radiation intensity of 20,000 to 30,000 lux. As Grätzel cells, commercial nanostructured titanium dioxide coated plates from a manufacturing series were used. As a redox negative sequence system, a standard electrolyte using iodine and iodide (iodine in alium iodide solution) was used. The operating point of highest power was determined by a successive approach. The thus determined performances of the cells with different sensitizers were normalized to the performance of the commercial sensitizer 23 (ruthenium complex), which is known for its efficiency and used in practice.

The results are shown in FIG. For the standard perylene colorant S-13 (N, iV-1-hexylheptylperylene-3,4: 9, 10-tetracarboxylic bisimide, RN 1 10590-84-6), a moderate efficiency is found which is below the efficiency of the ruthenium complex 23 (See also I.I. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380); see Figure 8 No. 1 compared to No. 4. Already with an expansion of the aromatic system on the terrylene structure of la an increase in efficiency; Figure 8, no. 2. A further extension of the electron system to Quaterrylenbi simide (2a) with a significant bathochromic shift of the absorption and an increase in the electron density leads to a considerable further increase in efficiency, Figure 8, No. 3; the performance of the system, however, remains below that of the ruthenium complex 23; FIG. 8, no. 4.

By the nuclear substitution of pyrrolidine residues with la, even the monosubstituted derivative 14 provides a large increase in performance, so that the cell obtained is significantly more efficient than a cell sensitized with the comparative dye 23; Figure 8, no. 5. Substitution with another pyrrolidine moiety, as in Figure 15, further increases the yield of the cell; Figure 8, no. 6. The transition from the terrier derivatives to the Quaterrylene derivatives with more bathochromic absorption further improve performance. Derivative 16, which is monosubstituted with a pyrrolidine residue, gives the highest yield, Figure 8, No. 8, which is more than one and a half times that of the comparative dye 23. A further increase in yield by a double substitution in Figure 17, Figure 8, no .7 did not succeed, but even led to a slight reduction.

Figure 1: Synthetic scheme for the preparation of Terrylenbisimiden as

Starting substances for the preparation of compounds of the invention on the example of l a.

Figure 2: Scheme for the synthesis of Quaterrylenbisimiden as starting materials for the preparation according to the invention erfmdungs connections on the example of 2a.

Figure 3: Alternative synthetic route for the preparation of Quaterrylenbisimiden am

Example of 2a.

FIG. 4: Stepwise substitution of the terrylene bisimide Ia and the quaterrylene bisimide

2a with pyrrolidine for the preparation of exemplary compounds of the invention.

FIG. 5: Substitution of imidazole operylene 18 with pyrrolidine for the preparation of compounds according to the invention.

Figure 6: UV / Vis absorption spectra of terrylene derivatives la (comparative compound, dotted), 14 (dashed) and 15 (solid) in chloroform compared to / V, AT- bis -hexylheptylperylene-3,4: 9, 10 tetracarboxylic bisimide (comparative compound, dash-dotted).

Figure: UV / Vis absorption spectra of quaterrylene derivatives 2 a

(Comparative compound, solid), 16 (dotted) and 17 (dashed) in chloroform compared to terrylenebisimide Ia (dot-dashed) and JVJV'-bis-1-hexylheptylperylene-3,4: 9, 1 () -tetracarboxylic bisimide (comparative compound, double-dashed ). Relative performances of dye-sensitized Grätzel cells. 1: V..V ^' -Bis-! - hexylheptylperylene-3,4: 9,10-tetracarboxylic bisimide, 2: terry) enbisimide la, 3: quaterrylenebisimide 2a, 4: ruthenium complex 23 5: pyrrolidinoterrylenebisimide 14, 6: dipyrrolidinoterrylenebisimide 15, 7: dipyrrolidoquaterrylenebisimide 17, 8: pyrrolidoquaterrylenebisimide 16

Claims

claims

1. Amino-pm ^' -arylene compound of the formula (I):

in which:

n is 1 or 2, X is R ¹² or -NR ⁵ R ⁶ , and R ¹ to R ^{18 may be the} same or different and are independently hydrogen or linear alkyl having at least one and at most 37 ° C Atoms in which one to 10 CH ₂ units can be replaced independently of each other by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH-CH-G sip in which a CH unit also by a nitrogen atom may be replaced, acetylenic C = C groups 1, 2, 1, 3 or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3 , 4- or 3,5-disubstituted pyridine radicals, 2,3-, ^' 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1, 3, 1, 4, 1 , 5-, 1-, 6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10, 2, 3, 2,6-, 2,7-, 2,9-, 2, 10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms, and wherein up to 12 individual hydrogen atoms of the CH ₂ groups may each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or ir- »s-CH = CH groups in which a CH unit is also replaced by a nitrogen atom can be acetylenic C ^ groups, 1,2-, 1, 3- or 1, 4-substituted phenyl radicals, 2,3-, 2,4-,

2.5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3 -, 1, 4, 1,5, 1, 6, 1, 7, 1, 8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8, 1, 9, 1, 10 , 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene radicals in which one or two carbon atoms may be replaced by nitrogen atoms; Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH 2 units can be replaced independently by Carbonyigruppen, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or lrans CH -CH groups, in which a CH unit may also be replaced by a nitrogen atom, acetylenic C = C. Groups 1, 2, 1, 3 or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals , 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1, 3, 1, 4, 1,5, 1,6, 1, 7-, 1,8-, 2,3-,

2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1, 2, 1,3, 1,4, 1, 5, 1,6, 1,7 -, 1, 8, 1, 9, 1, 10, 2,3, 2,6, 2,7, 2,9, 2,10 or 9, 10-disubstituted Anthracenreste, at one or two carbon atoms can be replaced by nitrogen atoms,

where the free valencies of the methine groups or of the quaternary carbon atoms, instead of substituents, can be linked in pairs, so that rings are formed, and

8 18

wherein the radicals R to R can furthermore independently of one another denote the halogen atoms F, Cl, Br or I.

2. Amino-ypen ^' -Arylenverbindung according to claim 1, wherein it is a compound of formula (IIa), (IIb), (IIIa) or (Mb):

in which

R and R ^"are independently defined as R and R in approach 1,

R \ R ⁴ . R ⁵ and R ^{6 are} independently defined as R ³ , R ⁴ . R ⁵ and R ⁶ in claim 1,

8 * ^ 2 8 18

and R to R ~ are independently defined as R to R in claim 1.

3. Amino-penary ^' -Arylenverbindung according to claim 1 or 2, which is a compound of the following compounds (14) to (17):

(14)

in which

1 2 1

R and R are independently defined as R and R in claim 1,

R ^3, R ^4, and R ⁷ are independently defined as R ^3, R ^4, R ⁵ and R ⁶ in claim 1, aanndd RR 8 bbiiss R 14 and R ^'3 are as defined to R 27 independently of one another as R 8 to R 18 in claim 1.

Use of an A minirery A ry 1 cn v erb in the form of the following formula (V) photovoltaic solar cell:

where m is 0, 1 or 2 and X and R ¹ to R ^{1 S are} independently defined as X and R 1 to R 18 in claim 1 for compounds of formula (I).

Use according to Claim 6, wherein the compound of the formula (V) is compound of the formula (IIa), (IIb), (IIIa) or (IIIb):

(IIIb)

in which

R ¹ and R ^{2 are} independently defined as R and R ² in claim 1,

R ³ , R ⁴ , R ³ and R ^{6 are} independently defined as R ¹ , R ⁴ , R ⁵ and R ⁶ in claim 1, and R to R '"are independently defined as R to R in claim 1.

8. Use according to claim 6 or 7, wherein the compound used is one of the compounds (14) to (17):

9. Use according to claim 6, wherein the compound of the formula (V) is a compound of the formula (VIa) or (VIb):

in which

R 1 and R 3 are independently defined as R.1 and R 2 in claim 1,

R \ R ^4, R ⁵ and R ⁶ independently defined as R ^J, R ^4, R ⁵ and R ⁶ in claim 1, and R 8 to R 1 independently are defined from one another as R 8 to R 18 in claim. 1

10. Use according to claim 9, wherein the compound used is one of the following compounds (32) to (37):

7

11. Use of a compound of the following formula (IV a) or (IVb) in a photovoltaic solar cell: in which

R ¹ and R ^{2 are} independently defined as R ¹ and R ² in claim 1,

R ³ , R ⁴ , and R are independently defined as and R ° in claim 1 and R ⁸ to R ¹⁴ and R to R »27 27

are independently defined as R ^Ä to R ¹⁵ in

Claim 1.

12. Use according to any one of claims 6 to 11, wherein the solar cell is a Grätzel cell.

A solar cell containing a compound as defined in any one of claims 6 to 12.

14. A process for the preparation of the compounds of formulas (I), (IVa) or (IVb), characterized in that a peri-arylea is reacted with a primary or secondary amine.