WO2008113753A1

WO2008113753A1 - Method for the production of rylene tetracarboxylic acid diimides the imide nitrogens of which carry hydrogen atoms and the use thereof

Info

Publication number: WO2008113753A1
Application number: PCT/EP2008/053063
Authority: WO
Inventors: Martin KÖNEMANN; Frank WÜRTHNER; Peter Osswald; Theo Kaiser
Original assignee: Basf Se
Priority date: 2007-03-16
Filing date: 2008-03-14
Publication date: 2008-09-25

Abstract

The present invention relates to a method for the production of rylene tetracarboxylic acid diimides, the imide nitrogens of which carry hydrogen atoms, and to the use thereof, particularly as organic semiconductors in excitonic solar cells.

Description

Process for the preparation of rylenetetracarboxylic acid diimides whose nitrogen atoms carry hydrogen atoms and their use

description

The present invention relates to a process for the preparation of rylenetetracarboximides, whose imide nitrogens carry hydrogen atoms, and to their use, in particular as organic semiconductors in excitonic solar cells.

DE 101 48 172 describes naphthalene-1, 4,5,8-tetracarboxylic bisimides of the general formula

in which the variables have the following meaning:

R ¹ and R ^{2 are} independently hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted aryl;

X and Y independently of one another are hydrogen, halogen, amino or a radical having the formula -NHR ³ , -OR ³ , where R ^{3 has} the formula -CH ₂ R ⁴ , -CHR ⁴ R ⁵ , or -CR ⁴ R ⁵ R ⁶ wherein R ⁴ , R ⁵ , R ^{6 are} independently hydrogen, substituted or unsubstituted alkyl, aryl, alkoxy, alkylthio, aryloxy, arylthio, wherein at least one of the two substituents X, Y is not hydrogen, halogen.

DE 102 33 955 describes a process for the preparation of quaterrylenetetracarboxylic diimides whose imide nitrogens can carry, inter alia, hydrogen atoms in addition to a large number of other radicals. The preparation takes place starting from perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-imides via a dimerizing decarboxylation and subsequent cyclization.

DE 10 2004 003 735 describes a process for the preparation of terrylene-3,4: 11, 12-tetracarboxylic diimides. In this case, in a first step a) a diborane reacted with ai) a 9-bromoperylene-3,4-dicarboximide or a2) a naphthalene-1, 8-dicarboximide IHb. The resulting 9- (dioxaborolan-2-yl) -perylene-3,4-dicarboximide or 4- (dioxaborolan-2-yl) naphthalene-1,8-dicarboxylic acid imide is isolated in a second step b) of a Suzuki Coupling reaction with a naphthalene-1, 8-dicarboximide (b1) or a 9-bromoperylene-3,4-dicar-bimide (b2) subjected. The 9- (4-naphthalene-1, 8-dicarboximide) -perylene-3,4-dicarboximide obtained in step b) is finally converted into a terrylene-3,4: 11, 12 by cyclodehydration in a third step c) Tetracarbonsäurediimid converted.

US 2005/0176970 A1 describes n-type semiconductors based on cyano-substituted perylene-3,4-dicarboximides and perylene-3,4,9,10-bis (dicarboximides). Of the formulaically represented compounds, those are also included in principle in which the I mid nitrogens carry hydrogen atoms. A suitable method for the preparation of these compounds and their use in excitonic solar cells is not disclosed.

WO 2005/070895 describes a process for the preparation of terrylene-3,4: 1 1, 12-tetracarboxylic diimides whose imide nitrogens can carry, inter alia, hydrogen atoms. In this case, in a one-stage reaction, a perylene-3,4-dicarboxylic acid imide is reacted with a naphthalene-1, 8-dicarboximide.

The non-prepublished WO2007 / 074137 (PCT / EP2006 / 070143) describes compounds of general formula I.

in which

at least one of R ¹ , R ² , R ³ and R ^{4 is} a substituent selected from Br, F and CN,

Y ^{1 is} O or NR ^a , where R ^{a is} hydrogen or an organyl radical,

Y ^{2 is} O or NR ^b , where R ^{b is} hydrogen or an organyl radical, Z ¹ and Z ² independently of one another are O or NR ^C , where R ^{c is} an organyl radical,

Z ³ and Z ⁴ are each independently O or NR ^d , where R ^{d is} an organyl radical,

wherein, in the event that Y ^{1 is} NR ^a and at least one of Z ¹ and Z ^{2 is} NR ^C , R ^a with a radical R ^c also together represent a bridging group having 2 to 5 atoms between the flanking bonds can, and

wherein, in the event that Y ^{2 is} NR ^b and at least one of Z ³ and Z ^{4 is} NR ^d , R ^b with a radical R ^d together also represent a bridging group having 2 to 5 atoms between the flanking bonds can

and their use as n-type semiconductors in organic field effect transistors.

The non-prepublished WO2007 / 093643 (PCT / EP2007 / 051532) describes the use of compounds of general formula I.

in which

n is 2, 3 or 4,

at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} fluorine,

optionally at least one further radical R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} a substituent which is independently selected from Cl and Br, and the other radicals are hydrogen,

Y ^{1 is} O or NR ^a , where R ^{a is} hydrogen or an organyl radical, Y ^{2 is} O or NR ^b , where R ^{b is} hydrogen or an organyl radical,

Z ¹ , Z ² , Z ³ and Z ^{4 are} O,

where, in the case where Y ^{1 is} NR ^a , one of the radicals Z ¹ and Z ^{2 may also represent} NR ^C , wherein the radicals R ^a and R ^c together represent a bridging group having 2 to 5 atoms between the flanking bonds stand, and

where, in the case where Y ^{2 is} NR ^b , one of the radicals Z ³ and Z ^{4 may also represent} NR ^d , where the radicals R ^b and R ^d together represent a bridging group having 2 to 5 atoms between the radicals flanking bonds,

as semiconductors, in particular n-semiconductors, in organic electronics, in particular for organic field-effect transistors, solar cells and organic light-emitting diodes.

There are currently generally no long-wave fluorescent dyes with high fluorescence quantum yield. Although F. Würthner, C. Thalacker, S. Diele and C. Tschierske describe in Chem. Eur. J. 2001, 7, 2245- 2253 on I mid-nitrogen substituted Perylenbisimide with long-wave shifted absorption band, but the long-wave shift is only here marginal and exclude the occurrence of a strong excitonic coupling therefore. Furthermore, these aggregates are only weakly fluorescent.

F. Würthner, Z. Chen, F.J.M. Hoeben, P. Osswald, C-C. You, P. Jonkheijm, J. van Herrikhuyzen, A.P.H. Schenning, P.P.A.M., van der Schoot, E.W. Meijer, E.H.A. Beckers, S.C. Meskers and R.A.J. Janssen describe in J. Am. Chem. Soc. 2004, 126, 1061 1-10618 show the supramolecular co-self-organization of oligo (p-phenylene vinylenes) and perylenebisimide dyes

and evidenced in these substances the ambipolar transport of n and p charge carriers, see P. Jonkheijm, N. Stutzmann, Z. Chen, DM de Leeuw, EW Meijer, APHJ Schenning, F. Würthner, J. At the. Chem. Soc. 2006, 128, 9535- 9540. These materials are not suitable for excitonic solar cells and are not fluorescent.

The object of the present invention is to provide long-wave fluorescence colorants with high fluorescence quantum yield. Such compounds would be of interest, inter alia, as fluorescent materials and exciton transport materials in electroluminescent and photovoltaic applications. The present invention is also specifically based on the object of providing rylene compounds for use in organic photovoltaics, in particular as semiconductors in excitonic solar cells.

Surprisingly, it has now been found that rylenetetracarboxylic diimides in which both imide nitrogens carry hydrogen atoms are particularly advantageously suitable for this use. Fluorescent rylene dyes usually lose their fluorescence upon aggregation. Therefore, it is surprising, on the one hand, that the compounds found form J aggregates and at the same time show long-wave fluorescence with high fluorescence quantum yield. Furthermore, it is also surprising that the compounds found are capable of forming J-aggregates.

A first subject of the invention is therefore the use of homo-aggregates of compounds of general formula I.

which are at least partially in the form of J-aggregates, wherein

n is 1, 2, 3 or 4,

at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is a radical other than} hydrogen selected from aryloxy, arylthio, hetaryloxy or

hetarylthio, as emitter materials, charge transport materials or exciton transport materials.

Another object of the invention is a process for the preparation of compounds of formula I

in which

n is 1, 2, 3 or 4,

at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is a radical other than} hydrogen, selected from aryloxy, arylthio, hetaryloxy or hetarylthio,

in which a diimide of the formula (IV)

wherein n is 1, 2, 3 or 4,

R ^a1 and R ^{a2 are} independently aryl, and

wherein, when R ^b1 and R ^b2 are each independently alkyl, the compound of formula IV is subjected to a reaction with a strong Lewis acid and a proton donor, and wherein in the case where R ^b1 and R ^{b2 are} hydrogen the compound of formula IV is subjected to hydrogenolysis.

The process described above is a novel advantageous process for the preparation of compounds of general formula I, regardless of whether they are in the form of homo-aggregates or especially in the form of J-aggregates.

The invention also relates to novel compounds of general formula I, regardless of whether they are in the form of homo-aggregates or especially in the form of J-aggregates.

According to the invention, the use of compounds of general formula I in the form of so-called "homo" aggregates, which are understood as supramolecular structures consisting exclusively of a compound of formula I. They differ from those of F. Würthner et al. in J. Am. Chem. Soc. 2004, 126, 1061 1-10618 described "Co" aggregates characterized by supramolecular co-self-organization of a p- and an n-type semiconductor. The term "homo" aggregates refers to the molecular level. Thus, at the macroscopic level, z. B. in a solar cell according to the invention, such a homo-aggregate with a suitable other material undergo a donor-acceptor interaction. The formation of homo-aggregates or the avoidance of amorphous phases can take place for example by oswaldripening.

Surprisingly, the compounds of the formula I are distinguished by their long-wave-shifted aggregate band, as has hitherto been unknown for prior art rylene dyes. Furthermore, the compounds of the formula I are distinguished by their strong long-wave fluorescence. They are thus suitable for. B. as an advantageous emitter in the near infrared range. Furthermore, their ability to form J-aggregates from compounds of the formula I is also surprising. This distinguishes them from the known co-aggregates in which excitonic dissociation takes place immediately in the coaggregates. The compounds of the formula I Thus, have properties such as specific emitter materials, charge transport materials or Excitontransportmaterialien z. B. in electroluminescence and photovoltaic applications are in demand.

The outstanding properties of J-aggregates result from a special packing in the aggregate, which leads to narrow absorption and emission bands, which are accompanied by a strong exciton delocalization. Such aggregates are found in the natural light harvesting systems of plants and photochromic bacteria (see, for example, BT Pullerits, V. Sundström, Acc. Chem. Res. 1996, 29, 381-389 and TS Balaban, H. Tamiaki, AR Holzwarth, Top. Curr. Chem. 2005, 258, 1-38)

Basis of chlorophylls as well as in technically used sensitizers in the silver halide photograph (see A.H. Herz, Adv. Colloid Interface Sci. 1977, 8, 237-298) based on cationic cyanine dyes. The latter have also been used extensively for photovoltaic applications (S. Dähne, Bunsen-Magazin 2002, 4, 81-92) and as sensor materials (R.M. Jones, L.D. Lu, R. Helgeson, T.S. Bergstedt, D.W.

McBranch, D.G. Whitten, Proc. Natl. Acad. Be. USA 2001, 98, 14769-14772).

The compounds of the formula I used according to the invention as emitter materials, charge transport materials or exciton transport materials are at least 50% by weight, more preferably at least 75% by weight, in particular at least 90% by weight, especially 100% by weight. in the form of J-aggregates.

The compounds of the formula (I) are preferably used as n-semiconductors. However, in combination with certain other semiconductor materials, they can also be used as p-type semiconductors.

Owing to their high order and the generally associated higher characteristic transport distances for excited states and higher charge mobilities (exciton diffusion lengths), the organic semiconductor materials used according to the invention are particularly advantageous for use in solar cells. With solar cells based on these semiconductors, very good quantum yields can generally be achieved.

In the compounds of the formula I, n denotes the number of naphthalene units linked in the peri-position, which form the skeleton of the rylene compounds according to the invention. In the individual radicals R ⁿ¹ to R ⁿ⁴ , n denotes the particular naphthalene group of the rylene skeleton to which the radicals are bonded. ^Radicals R ⁿ¹ to R ⁿ⁴ which are bonded to different naphthalene groups may each have the same or different meanings. Accordingly, the compounds of the general formula I may be naphthalene diimides, perylene diimides, terrylene diimides or Quaterrylene diimides act. The structure concept is exemplified by the following preferred compounds.

(n = 2)

(n = 4)

(For n = 1, any two of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are a radical other than} hydrogen)

Preference is given to compounds of the formula I in which n is 2, 3 or 4. Preference is given to compounds of the formula I in which n is 1 and 2 or 4 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are radicals which are different from hydrogen.

Preference is given to compounds of the formula I in which n is 2 and 1, 2, 3 or 4 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are radicals other ^than hydrogen. 2 or 4 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are particularly preferably radicals which are different from hydrogen.

Preference is given to compounds of the formula I in which n is 3 and 1, 2, 3 or 4 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are radicals other ^than hydrogen. Particularly preferred are then 4 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 radicals other than} hydrogen.

Preference is given to compounds of the formula I in which n is 4 and 1, 2, 3, 4, 5 or 6 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are radicals other ^than hydrogen. Particularly preferred are then 4 or 6 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 radicals other than} hydrogen.

In the context of the present invention, the term "alkyl" includes straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, in particular C 1 -C 20 -alkyl and very particularly preferably C 1 -C 12 -alkyl. Examples of alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2 , 3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, decyl , n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

The term alkyl also includes alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups selected from -O-, -S-, -NR ^e -, -CO- and / or -SO 2 -. R ^e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The term alkyl also includes substituted alkyl radicals.

The above statements on alkyl also apply to the alkyl moieties in alkoxy and alkylthio. Alkylene represents a linear saturated hydrocarbon chain having 1 to 10 and in particular 1 to 4 C atoms, such as ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5 diyl or hexane-1, 6-diyl.

The term "cycloalkyl" in the context of the present invention encompasses both unsubstituted and substituted cycloalkyl groups, preferably Cs-Cs-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particular Cs-Cs-cycloalkyl. In the case of a substitution, the cycloalkyl groups may carry one or more, for example one, two, three, four or five substituents. These are preferably selected from C 1 -C 30 -alkyl groups.

Cs-Cs-cycloalkyl which is unsubstituted or may carry one or more C 1 -C 6 -alkyl groups is, for example, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4- Methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and

4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4- Propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and 5-propylcyclooctyl.

The term "aryl" in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. The term "aryl" preferably represents phenyl, ToIyI, XyIyI, mesityl, Duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, these aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry. These substituents are preferably selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 8 -alkylthio, -C (OO) OR ^a , -OC (OO) R ^a , -C (OO) NR ^a R ^b , cyano, halo, aryl azo and heteroarylazo, wherein arylazo and heteroarylazo are in turn unsubstituted or may bear one or more radicals (eg 1, 2, 3, 4 or 5) which are independently selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 30 -alkylthio, cyano and halogen. R ^a and R ^b are preferably independently of one another hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The radicals R ^a and R ^b may in turn be unsubstituted or may carry one or more radicals (eg 1, 2, 3, 4 or 5). R ^a and R ^b which may be alkyl in the case of substitution generally have 1, 2, 3, 4 or 5, preferably carry 1, 2 or 3 substituents. These substituents are preferably selected from cyano and halogen. Radicals R ^a and R ^b which are cycloalkyl, heterocycloalkyl, aryl or hetaryl may in the case of a substitution generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents. These substituents are preferably selected from C 1 -C 30 -alkyl, Ci-C3o-alkoxy, Ci-C3o-alkylthio, cyano and halogen, in particular C4-C3o-alkyl, C ₄ -C ₃ O -alkoxy and C ₄ -C ₃ o-alkylthio.

The term "heterocycloalkyl" in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms by heteroatoms, selected from Oxygen, nitrogen, sulfur and a group -NR ^C - are replaced and which is unsubstituted or substituted with one or more, for example 1, 2, 3, 4, 5 or 6 d-Cβ-alkyl groups. Examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothien-2 -yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropy- ranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl called.

The term "heteroaryl" in the context of the present invention includes unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups containing in addition to carbon ring members 1, 2, 3 or 4 heteroatoms from the group oxygen, nitrogen or sulfur as ring members, preferably the groups Pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl, these heterocycloaromatic groups in the case of a substitution generally 1, 2 or 3 substituents can carry. The substituents are selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 30 -alkylthio, hydroxy, carboxy and cyano. The substituents are preferably selected from C ₄ -C 30 -alkyl, C ₄ -C 30 -alkoxy and C ₄ -C 30 -alkylthio.

5- to 10-membered heterocycloalkyl or heteroaryl radicals containing, in addition to carbon ring members, one to three nitrogen atoms and optionally further heteroatoms selected as ring members under oxygen and sulfur, are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imino dazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl.

Halogen is fluorine, chlorine, bromine or iodine.

Specific examples of the radicals mentioned in the following formulas and their substituents are in detail:

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, Isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (the above names isooctyl, isononyl, isodecyl and isotridecyl are trivial and derived from the alcohols obtained by the oxo process);

2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxy-propyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-di-oxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3.7 Dioxanonyl, 4,7-dioxa-octyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6, 9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthio-ethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7-dithiaoctyl, 3,7 Di-thianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-trithia-undecyl, 3,6,9-trithiadodecyl, 3,6,9, 12-tetrathiatridecyl and 3,6,9,12-tetrathiatetra-decyl;

2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-di-azaoctyl, 3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl, 3,6,9- Trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl and 3, 6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

(1-ethylethylidene) aminoethylene, (1-ethylethylidene) aminopropylene, (1-ethylethylidene) aminobutylene, (1-ethylethylidene) aminodecylene and (1-ethylethylidene) aminododecylene;

Propan-2-one-1-yl, butan-3-one-1-yl, butan-3-one-2-yl and 2-ethyl-pentan-3-one-1-yl;

2-Methylsulfoxidoethyl, 2-Ethylsulfoxidoethyl, 2-Propylsulfoxidoethyl, 2-Isopropylsulf- oxidoethyl, 2-Butylsulfoxidoethyl, 2- and 3-Methylsulfoxidopropyl, 2- and 3-Ethylsulf- oxidopropyl, 2- and 3-Propylsulfoxidopropyl, 2- and 3- Butylsulfoxidopropyl, 2- and 4-methylsulfoxidobutyl, 2- and 4-ethylsulfoxidobutyl, 2- and 4-propylsulfoxidobutyl and 4-butylsulfoxidobutyl;

2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and 4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and 4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxy-tetradecyl;

Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;

2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 3- and 4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxo-octyl;

2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl, 2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and 4,7-dimethyl-7-cyanoheptyl;

2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl, 2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl;

2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl;

Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert. Pentoxy and hexoxy;

Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio;

Ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and 4-pentynyl, 1-, 2-, 3-, 4- and 5-hexynyl, 1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9, 10 and 11 dodecinyl and 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14-, 15-, 16- and 17-octadecynyl;

Ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 1-1 -dodecenyl and 1-, 2-, 3-, A-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- and 17-octadecenyl;

Methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, pentylamino, hexylamino, dimethylamino, methylethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino; Formylamino, acetylamino, propionylamino and benzoylamino;

Carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl;

Aminosulfonyl, N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl,

N-dodecylaminosulfonyl, (N, N-dimethylamino) ethylaminosulfonyl,

N, N- (propoxyethyl) dodecylaminosulfonyl, N, N-diphenylaminosulfonyl,

N, N- (4-tert-butylphenyl) octadecylaminosulfonyl and

N, N-bis aminosulfonyl (4-chlorophenyl);

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl,

(4-tert-butylphenoxy) carbonyl and (4-chlorophenoxy) carbonyl;

Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl, isobutoxysulfonyl, tert-butoxysulfonyl, hexoxysulfonyl, dodecyloxysulfonyl, octadecyloxysulfonyl, phenoxysulfonyl, 1- and 2-naphthyloxysulfonyl, (4-tert-butylphenoxy) sulfonyl and (4-chlorophenoxy) sulfonyl;

Diphenylphosphino, di (o-tolyl) phosphino and diphenylphosphine oxido;

Fluorine, chlorine, bromine and iodine;

Phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

Cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3 - and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and

4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5- Methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl and 3-, 4- and 5-propylcyclooctyl; 3- and 4-hydroxycyclohexyl, 3- and 4-nitrocyclohexyl and 3- and 4-chlorocyclohexyl;

1-, 2- and 3-cyclopentenyl, 1-, 2-, 3- and 4-cyclohexenyl, 1-, 2- and 3-cycloheptenyl and 1-, 2-, 3- and 4-cyclooctenyl; 2-dioxanyl, 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3- and 4-piperidyl;

Phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and 5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5 -imidazolyl, 2-, 4- and 5-thiazolyl, 3- (1, 2,4-triazyl), 2- (1, 3,5-triazyl), 6-quinaldyl, 3, 5, 6 and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl, 5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;

1-, 2-, 3-, 4-, 5-, 6- and 7-indolyl, 1-, 2-, 3-, 4-, 5-, 6- and 7-isoindolyl, 5- (4-methylisoindolyl ), 5- (4-phenylisoindolyl), 1-, 2-, 4-, 6-, 7- and 8- (1,2,3,4-tetrahydroisoquinolinyl), 3- (5-phenyl) - (1, 2,3,4-tetrahydroisoquinolinyl), 5- (3-dodecyl- (1,2,3,4-tetrahydroiso-quinolinyl), 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8- (1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, 4-, 5-, 6-, 7- and 8-chromanyl, 2-, 4- and 7-quinolinyl, 2- ( 4-phenylquinolinyl) and 2- (5-ethylquinolinyl);

2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3 , 5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6- Tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4- , 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 3,5- and 2,6-diisobutylphenyl, 2,4, 6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and 2,4,6-tri-sec-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-tri-methoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4- , 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3 and 4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and 2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and 2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl; 3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamido-phenyl and 3- and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and 4-propionylaminophenyl and 3- and 4-butyluraminophenyl; 3- and 4-N-phenylaminophenyl, 3- and 4-N- (o -tolyl) aminophenyl, 3- and 4-N- (m-tolyl) aminophenyl and 3- and 4- (p-tolyl) aminophenyl; 3- and 4- (2-pyridyl) aminophenyl, 3- and 4- (3-pyridyl) aminophenyl, 3- and 4- (4-pyridyl) aminophenyl, 3- and 4- (2-pyrimidyl) aminophenyl and 4- (4-pyrimidyl) aminophenyl;

4-phenylazophenyl, 4- (1-naphthylazo) phenyl, 4- (2-naphthylazo) phenyl, 4- (4-naphthylazo) phenyl, 4- (2-pyrylazo) phenyl, 4- (3-pyridylazo) phenyl, 4- (4-pyridylazo) phenyl, 4- (2-pyrimidylazo) phenyl, 4- (4-pyrimidylazo) phenyl and 4- (5-pyrimidylazo) phenyl;

Phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and 4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyimidimidyl and 2-, 4- and 5- Pyτimidylthio.

In the process according to the invention for the preparation of compounds of the formula I, preference is given to using a diimide of the formula (IV) in which at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} a radical which is different from hydrogen and is selected from Alkylamino, dialkylamino, aryloxy, arylthio, hetaryloxy or Heta- rylthio.

In the compounds of the formula I used according to the invention as emitter materials, charge transport materials or exciton transport materials, at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is a radical other than} hydrogen, selected from aryloxy, arylthio, hetaryloxy or hetarylthio ,

In a preferred embodiment, at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 has} as structural element an aryloxy group or hetaryloxy group which bears at least 2 substituents each independently selected from C 4 -C 30 -alkyl, C 4 C3o-alkoxy and C4-C3o-alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s). Such compounds are new and also the subject of the invention. Preferably, at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 has} an aryl group or hetaryl group carrying at least 3 such substituents.

In a first preferred embodiment, at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is then} aryloxy, arylthio, hetaryloxy or hetarylthio which bears at least 2 substituents, each of which is independently selected from among

C ₄ -C ₃ O-AlkVl, C ₄ -C ₃ O-alkoxy and C ₄ -C ₃₀ -alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents interrupted by one or more non-adjacent oxygen atom (s) could be. Specifically, then at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} aryloxy, arylthio, hetaryloxy or hetarylthio, which carries at least 3 of these substituents.

In a second preferred embodiment, at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} aryloxy, arylthio, hetaryloxy or hetarylthio and has as an additional structural element an aryl group or hetaryl group which carries at least 2 substituents, each independently are selected from among C ₄ -C ₃ O-alkyl, C ₄ -C ₃ o-alkoxy and C ₄ -C ₃ o-alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents by one or more non-adjacent oxygen atom ( e) can be interrupted. The additional aryl group or hetaryl group may be bonded directly or via a bridging group to the aryloxy, arylthio, hetaryloxy or het arylthio group.

Preferred radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are the following:

(11.1) (II.2)

(H.3) _{(I L4)}

(II.5) (II.6)

(II.7) (H.8)

(II.9) (11-10)

(11.11) (11.12) where

# represents the point of attachment to the rylene skeleton,

x is 2 or 3, where in the compounds of the formulas 11.10, 11.1 1 and 11.12 x stands for 2, A is a divalent bridging group which is selected from -O-, -S-, -O-arylene-, -S-arylene-, -O-arylene-C (= O) O-, -S-arylene- C (= O) O-, -O-arylene-OC (= O) - and -S-arylene-OC (= O) -, and

R ^{1 are} each independently selected from C ₄ -C 30 -alkyl, C ₄ -C ₃ O-

Alkoxy and C4-C3o-alkylthio, wherein the alkyl chains of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s).

Arylene is preferably phenylene, particularly preferably 1, 4-phenylene.

The bridging group A preferably represents a bridging group (III)

where # represents the point of attachment to the rylene skeleton.

The bridging group A particularly preferably represents a group of the formula (III.1))

Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are radicals of the formulas (II.A1) and (II.A2)

(II.A1) (II.A2)

wherein # is the point of attachment to the rylene skeleton, A ^{1 is} O or S and R is C ₄ -C ₃ O-AlkVl, C ₄ -C ₃ o-alkylthio or C ₄ -C ₃ o-alkoxy. In the radicals of the formula (II.A1) and (II.A2) are the groups

preferably for:

3,4,5-tri (n-butyl) phenyl, 3,4,5-tri (n-pentyl) phenyl, 3,4,5-tri (n-hexyl) phenyl, 3,4,5-tri ( n-heptyl) phenyl, 3,4,5-tri (n-octyl) phenyl, 3,4,5-tri (n-nonyl) phenyl, 3,4,5-tri (n-decyl) phenyl, 3, 4,5-Tri (n-undecyl) phenyl, 3,4,5-tri (n-dodecyl) phenyl,

3,4,5-tri (n-tridecyl) phenyl, 3,4,5-tri (n-tetradecyl) phenyl, 3,4,5-tri (n-pentadecyl) phenyl, 3,4,5-tri ( n-hexadecyl) phenyl, 3,4,5-tri (n-heptadecyl) phenyl, 3,4,5-tri (n-octadecyl) phenyl, 3,4,5-tri (nonadecyl) phenyl, 3,4, 5-Tri (eicosyl) phenyl, 3,4,5-tri (docosanyl) phenyl, 3,4,5-tri (tricosanyl) phenyl, 3,4,5-tri (tetracosanyl) phenyl, 3,4,5- tri (octacosanyl) phenyl;

3,4,5-tri (n-butyloxy) phenyl, 3,4,5-tri (n-pentyloxy) phenyl, 3,4,5-tri (n-hexyloxy) phenyl, 3,4,5-tri ( n-heptyloxy) phenyl, 3,4,5-tri (n-octyloxy) phenyl, 3,4,5-tri (n-nonyloxy) phenyl, 3,4,5-tri (n-decyloxy) phenyl, 3, 4,5-Tri (n-undecyloxy) phenyl, 3,4,5-tri (n-dodecyloxy) phenyl, 3,4,5-tri (n-tridecyloxy) phenyl,

3,4,5-tri (n-tetradecyloxy) phenyl, 3,4,5-tri (n-pentadecyloxy) phenyl, 3,4,5-tri (n-hexadecyloxy) phenyl, 3,4,5-tri ( n -heptadecyloxy) phenyl, 3,4,5-tri (n-octadecyloxy) phenyl, 3,4,5-tri (nonadecyloxy) phenyl, 3,4,5-tri (eicosyloxy) phenyl, 3,4,5- Tri (docosanyloxy) phenyl, 3,4,5-tri (tricosanyloxy) phenyl, 3,4,5-tri (tetracosanyloxy) phenyl, 3,4,5-tri (octacosanyloxy) phenyl;

3,4,5-Tri (n-butylthio) phenyl, 3,4,5-tri (n-pentylthio) phenyl, 3,4,5-tri (n-hexylthio) phenyl, 3,4,5-tri ( n-heptylthio) phenyl, 3,4,5-tri (n-octylthio) phenyl, 3,4,5-tri (n-nonylthio) phenyl, 3,4,5-tri (n-decylthio) phenyl, 3, 4,5-Tri (n-undecylthio) phenyl, 3,4,5-tri (n-dodecylthio) phenyl, 3,4,5-tri (n-tridecylthio) phenyl, 3,4,5-tri (n- tetradecylthio) phenyl, 3,4,5-tri (n-pentadecylthio) phenyl, 3,4,5-tri (n-hexadecylthio) phenyl, 3,4,5-tri (n-heptadecylthio) phenyl, 3,4, 5-Tri (n-octadecylthio) phenyl, 3,4,5-tri (nonadecylthio) phenyl, 3,4,5-tri (eicosylthio) phenyl, 3,4,5-tri (docosanylthio) phenyl,

3,4,5-Tri (tricosanylthio) phenyl, 3,4,5-tri (tetracosanylthio) phenyl, 3,4,5-tri (octacosanylthio) phenyl. Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are furthermore radicals of the formulas (II.B1) and (II.B2)

(II.B1) (II.B2)

in which # represents the point of attachment to the rylene skeleton, A ¹ is O or S and R ₄ is -C ₃ alkylthio or C _o-4 is -C ₃ -alkoxy is C ₄ -C ₃ -alkyl, C.

In the residues (II.B1) and (II.B2) are the groups

preferably for:

3,5-di (n-butyl) phenyl, 3,5-di (n-pentyl) phenyl, 3,5-di (n-hexyl) phenyl, 3,5-di (n-heptyl) phenyl, 3, 5-di (n-octyl) phenyl, 3,5-di (n-nonyl) phenyl, 3,5-di (n-decyl) phenyl, 3,5-di (n-undecyl) phenyl, 3,5- Di (n-dodecyl) phenyl, 3,5-di (n-tridecyl) phenyl, 3,5-di (n-tetradecyl) phenyl, 3,5-di (n-pentadecyl) phenyl, 3,5-di ( n-hexadecyl) phenyl, 3,5-di (n-heptadecyl) phenyl, 3,5-di (n-octadecyl) phenyl, 3,5-di (nonadecyl) phenyl, 3,5-di (eicosyl) phenyl, 3,5-di (docosanyl) phenyl,

3,5-di (tricosanyl) phenyl, 3,5-di (tetracosanyl) phenyl, 3,5-di (octacosanyl) phenyl;

3,5-di (n-butyloxy) phenyl, 3,5-di (n-pentyloxy) phenyl, 3,5-di (n-hexyloxy) phenyl, 3,4,5-di (n-heptyloxy) phenyl, 3,5-di (n-octyloxy) phenyl, 3,5-di (n-nonyloxy) phenyl, 3,5-di (n-decyloxy) phenyl, 3,5-di (n-undecoxy) phenyl, 3, 5-Di (n-dodecyloxy) phenyl, 3,5-di (n-tridecyloxy) phenyl, 3,5-di (n-tetradecyloxy) phenyl, 3,5-di (n-pentadecyloxy) phenyl, 3,5- Di (n-hexadecyloxy) phenyl, 3,5-di (n-heptadecyloxy) phenyl, 3,5-di (n-octadecyloxy) phenyl, 3,5-di (nonadecyloxy) phenyl, 3,5-di (eicosyloxy) phenyl, 3,5-di (docosanyloxy) phenyl, 3,5-di (tricosanyloxy) phenyl, 3,5-di (tetracosanyloxy) phenyl, 3,5-di (octacosanyloxy) phenyl;

3,5-di (n-butylthio) phenyl, 3,5-di (n-pentylthio) phenyl, 3,5-di (n-hexylthio) phenyl, 3,5-di (n-heptylthio) phenyl, 3, 5-Di (n-octylthio) phenyl, 3,5-di (n-nonylthio) phenyl, 3,5-di (n-decylthio) phenyl, 3,5-di (n-undecithio) phenyl, 3,5- Di (n-dodecylthio) phenyl, 3,5-di (n-tridecylthio) phenyl, 3,5-di (n-tetradecylthio) phenyl, 3,5-di (n-pentadecylthio) phenyl, 3,5-di ( n-hexadecyolthio) phenyl, 3,5-di (n-heptadecylthio) phenyl, 3,5-di (n-octadecylthio) phenyl, 3,5-di (nonadecylthio) phenyl, 3,5-di (eicosylthio) phenyl, 3,5-di (docosanylthio) phenyl, 3,5-di (tricosanylthio) phenyl, 3,5-di (tetracosanylthio) phenyl, 3,5-di (octacosanylthio) phenyl.

Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are furthermore radicals of the formulas (II.C1) and (II.C2)

I.C1) (II.C2)

In the radicals of the formulas (II.C1) and (II.C2) are the groups

preferably for:

2,6-di (n-butyl) -pyridin-4-yl, 2,6-di (n-pentyl) -pyridin-4-yl, 2,6-di (n-hexyl) -pyridin-4-yl , 2,6-di (n-heptyl) -pyridin-4-yl, 2,6-di (n-octyl) -pyridin-4-yl, 2,6-di (n-nonyl) -pyridine-4-yl yl, 2,6-di (n-decyl) -pyridin-4-yl, 2,6-di (n-undecy) -pyridin-4-yl, 2,6-di (n-dodecyl) -pyridine-4 -yl, 2,6-di (n-tridecyl) -pyridin-4-yl,

2,6-di (n-tetradecyl) -pyridin-4-yl, 2,6-di (n-pentadecyl) -pyridin-4-yl, 2,6-Di (n-hexadecyl) -py-4-yl, 2,6-di (n-heptadecyl) -py-4-yl, 2,6-di (n-octadecyl) -pyridin-4-yl , 2,6-di (nonadecyl) -pyridin-4-yl, 2,6-di (eicosyl) -pyridin-4-yl, 2,6-di (docosanyl) -pyridin-4-yl, 2,6- Di (tricosanyl) -pyridin-4-yl, 2,6-di (tetracosanyl) -pyridin-4-yl, 2,6-di (octacosanyl) -pyridin-4-yl.

Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are furthermore radicals of the formulas (II.D1) and (II. D2)

(M.UI) (II.D2)

In the radicals of the formulas (II. D1) and (II. D2) are the groups

preferably for:

4,6-di (n-butyl) -pyrimidin-2-yl, 4,6-di (n-pentyl) -pyrimidin-2-yl, 4,6-di (n-hexyl) -pyrimidin-2-yl , 4,6-di (n-heptyl) -pyrimidin-2-yl, 4,6-di (n-octyl) -pyrimidin-2-yl, 4,6-di (n-nonyl) -pyrimidine-2-yl yl, 4,6-di (n-decyl) -pyrimidin-2-yl, 4,6-di (n-undecyl) -pyrimidin-2-yl, 4,6-di (n-dodecyl) -pyrimidine-2 -yl, 4,6-di (n-tridecyl) -pyrimidin-2-yl, 4,6-di (n-tetradecyl) -pyrimidin-2-yl, 4,6-di (n-pentadecyl) -pyrimidine 2-yl, 4,6-di (n-hexadecyl) -pyrimidin-2-yl, 4,6-di (n-heptadecyl) -pyrimidin-2-yl, 4,6-di (n-octadecyl) -pyrimidine 2-yl, 4,6-di (nonadecyl) -pyrimidin-2-yl, 4,6-di (eicosyl) -pyrimidin-2-yl, 4,6-di (docosanyl) -pyrimidin-2-yl, 4,6-Di (tricosanyl) -pyrimidin-2-yl, 4,6-di (tetracosanyl) -pyrimidin-2-yl, 4,6-di (octacosanyl) -pyrimidin-2-yl. Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are furthermore radicals of the formulas (II.E1) and (II-E2)

(II.E1) I.E2)

In the radicals of the formulas (II. E1) and (II. E2) are the groups

preferably for:

4,5,6-tri (n-butyl) -pyrimidin-2-yl, 4,5,6-tri (n-pentyl) -pyrimidin-2-yl, 4,5,6-tri (n-hexyl) -pyrimidin-2-yl, 4,5,6-tri (n-heptyl) -pyrimidin-2-yl, 4,5,6-tri (n-octyl) -pyrimidin-2-yl, 4,5,6 Tri (n-nonyl) -pyrimidin-2-yl, 4,5,6-trii (n-decyl) -pyrimidin-2-yl, 4,5,6-tri (n-undecy) -pyrimidine-2-yl yl, 4,5,6-tri (n-dodecyl) -pyrimidin-2-yl, 4,5,6-tri (n-tridecyl) -pyrimidin-2-yl, 4,5,6-tri (n- tetradecyl) -pyrimidin-2-yl, 4,5,6-tri (n-pentadecyl) -pyrimidin-2-yl, 4,5,6-tri (n-hexadecyl) -pyrimidin-2-yl, 4,5 , 6-tri (n-heptadecyl) -pyrimidin-2-yl, 4,5,6-tri (n-octadecyl) -pyrimidin-2-yl, 4,5,6-tri (nonadecyl) -pyrimidine-2-yl yl, 4,5,6-tri (eicosyl) -pyrimidin-2-yl, 4,5,6-tri (docosanyl) -pyrimidin-2-yl, 4,5,6-tri (tricosanyl) -pyrimidine-2 -yl, 4,5,6-tri (tetracosanyl) -pyrimidin-2-yl, 4,5,6-tri (octacosanyl) -pyrimidin-2-yl.

Examples of suitable radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ are furthermore radicals of the formulas (II.F1) and (II.F2)

(II.F1) (II. F2)

In the radicals of the formulas (II.F1) and (II.F2) are the groups

preferably for:

4,6-di (n-butyl) -1,3,5-triazin-2-yl, 4,6-di (n-pentyl) -1, 3,5-triazin-2-yl, 4,6- Di (n-hexyl) -1, 3,5-triazin-2-yl, 4,6-di (n-heptyl) -1, 3,5-triazin-2-yl, 4,6-di (n-butyl) octyl) -1, 3,5-triazin-2-yl, 4,6-di (n-nonyl) -1, 3,5-triazin-2-yl, 4,6-di (n-decyl) -1 , 3,5-triazin-2-yl, 4,6-di (n-undecyl) -1, 3,5-triazin-2-yl, 4,6-di (n-dodecyl) -1, 3.5 triazin-2-yl, 4,6-di (n-tridecyl) -1, 3,5-triazin-2-yl,

4,6-di (n-tetradecyl) -1,3,5-triazin-2-yl, 4,6-di (n-pentadecyl) -1, 3,5-triazin-2-yl, 4,6- Di (n-hexadecyl) -1, 3,5-triazin-2-yl, 4,6-di (n-heptadecyl) -1, 3,5-triazin-2-yl, 4,6-di (n-) octadecyl) -1,3,5-triazin-2-yl, 4,6-di (nonadecyl) -1, 3,5-triazin-2-yl, 4,6-di (eicosyl) -1, 3.5 -triazin-2-yl, 4,6-di (docosanyl) -1, 3,5-triazin-2-yl, 4,6-di (tricosanyl) -1, 3,5-triazin-2-yl, 4 , 6-di (tetracosanyl) -1, 3,5-triazin-2-yl, 4,6-di (octacosanyl) -1, 3,5-triazin-2-yl.

An example of a preferred compound is 1, 6,7,12-tetrakis (4- [3,4,5-tridodecyl-oxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide (1):

(1 )

The inventive and inventively used Rylenetetracarbonsäure- diimides whose imide nitrogens carry hydrogen atoms, are usually capable of forming supramolecular structures in the form of self-assembled aggregates. This can be z. B. attributable to the ability of their imide groups to form hydrogen bonds. Surprisingly, this can lead to the formation of so-called J-aggregates or disk aggregates, which is particularly advantageous for use of these compounds in excitonic solar cells. J aggregates are characterized by highly bathchromically-shifted absorption and fluorescence bands with narrow bandwidths over monomer absorption, coupled with high fluorescence quantum efficiency. Their behavior is based on a strong intermolecular coupling of the electronic excitation associated with a high excitonic mobility. This is of paramount importance for effective use of incident light in excitonic solar cells.

FIG. 1 shows, by the example of (1), the arrangement of rylenetetracarboxylic diimides in J-type aggregates. The arrows in image section A) symbolize hydrogen bonds. Section B) shows the helical self-assembly of the rylenetetracarboxylic diimides (substituents were omitted and only the left-handed HeNx is reproduced). Section C) shows an enlarged detail of a double strand of Rylenetetracarbonsäurediimide with the J arrangement of the superimposed aggregates.

The rylenetetracarboxylic diimides according to the invention and those used according to the invention are self-complementary compounds because of their hydrogen-carrying imide nitrogens, ie they are capable, even in the absence of further compounds, of arranging themselves into chains along which excitons can migrate. Especially rylenetetracarboxylic diimides in which one or more of R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} substituted or unsubstituted aryloxy, arylthio, hetarylo- xy or hetarylthio, have a twisted π-conjugated core. By introducing suitable groups into one or more of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ , such as. B. a group of formulas (11.1) to (11.12), especially one or more 3,4,5- Trialkoxyphenylgruppen, the solubility of the compounds can also be improved in nonpolar aliphatic solvents. Rylenetetracarboxylic diimides according to the invention and used according to the invention with the ability to form superimposed molecular stacks with π-π interaction are characterized by a bathochromic shift compared with the monomeric compounds and exhibit excitonic fluorescence states. Due to their ability to form hydrogen bonds, the individual dimeric molecular stacks can form a tightly packed one-dimensional supramolecular polymer that has the typical properties of a J-aggregate. The experimental detection of superimposed molecular stacks with π-π interaction is possible, for example, on the basis of the UVA / IS spectra. The formation of hydrogen bonds (such as NH ^{· ■} O bonds between imides and carbonyl nitrogens) can be detected by concentration- and temperature-dependent FT-IR spectroscopy and ¹ H NMR. The size and shape of the aggregates can be determined by atomic force microscopy (AFM). Information about the dynamics of excitons can be found eg. B. win with time-resolved fluorescence spectroscopy. Thus, fluorescence lifetime is a sensitive parameter for describing molecular systems in their basic dynamic properties. From the decrease of the fluorescence lifetime from the monomer to the aggregate, the size of the coherent domain can be estimated in the absence of radiation-free quenching processes. This is z. B. for the compound (1) about three molecules at room temperature. At lower temperatures, a large increase in the size of the coherent domain can be expected.

Because of their properties, the rylenetetracarboxylic diimides according to the invention and those used according to the invention are particularly advantageous for use in organic photovoltaics, in particular as semiconductors in excitonic solar cells.

Surprisingly, it has been found that diimides of the formula (IV)

(IV)

wherein R ^a1 and R ^a2 independently represent aryl and R ^b1 and R ^b2 independently represent alkyl, can easily undergo a reaction to give diimides (I) in which the imide nitrogens carry hydrogen atoms.

Another object of the invention is therefore a process for the preparation of compounds of formula I.

in which

n is 1, 2, 3 or 4,

at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} a radical which is different from hydrogen and is selected from aryloxy, arylthio, hetaryloxy or hetarylthio, in which a diimide of the formula (IV)

wherein

n is 1, 2, 3 or 4,

R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 have} the meaning given above,

R ^a1 and R ^{a2 are} independently aryl, and

In the abovementioned compounds of the formula (IV), R ^a1 and R ^a2 preferably have the same meaning and, for example, both represent phenyl.

In the abovementioned compounds of the formula (IV), R ^b1 and R ^b2 preferably have the same meaning and are, for example, both C 1 -C 12 -alkyl, more preferably C 1 -C 12 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. Specifically, R ^d1 and R ^{d1 are} both methyl.

Alternatively, in the aforementioned compounds of formula (IV), R ^b1 and R ^{b2 are} preferably the same and, for example, both are hydrogen.

The deprotection is usually carried out under such reaction conditions as are known from the prior art for the removal of the respective protective group. Suitable deprotection methods are described, for example, in TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 3rd Edition, Wiley Interscience 1999, or PJ Kocienski, Protective Groups, Thieme 2000, incorporated herein by reference.

If R ^b1 and R ^{b2 are} hydrogen, the cleavage of the benzyl moiety is preferably carried out by hydrogenolysis. The hydrogenolysis is generally carried out under known conditions, for example using a suitable hydrogenation catalyst, such as palladium, palladium hydroxide or platinum.

If R ^b1 and R ^b2 are each independently alkyl, the cleavage is carried out by treating the compound IV with a Lewis acid.

Covalent metal halides and semimetallic halides having an electron-pair gap may be considered as the Lewis acid. Such compounds are known to the person skilled in the art, for example from JP Kennedy, B. Ivan, "Designed Polymers by Carbocationic Macromolecular Engineering", Oxford University Press, New York, 1991. They are usually selected from halogen compounds of titanium, tin, of aluminum, vanadium or iron, and in particular the halogen ides of boron. Preferred Lewis acids are boron tribromide, boron trichloride, titanium tetra-chloride, tin tetrachloride, aluminum trichloride, vanadium pentachloride, iron trichloride, alkylaluminum dichlorides and dialkylaluminum chlorides. Particularly preferred Lewis acids are boron tribromide and titanium tetrachloride.

The Lewis acid is employed in an amount sufficient to react both imide groups of the compound of formula IV. The molar ratio of Lewis acid to compound of the formula IV is preferably 2: 1 to 10: 1 and more preferably 2.1: 1 to 5: 1.

The reaction is usually carried out in a solvent. Suitable solvents are those which are stable to Lewis acids. Preferred solvents are halogenated hydrocarbons, e.g. As halogenated aliphatic hydrocarbons, especially haloalkanes, such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane, 1, 1-trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane and 2-chlorobutane, and halogenated aromatic hydrocarbons, such as chlorobenzene and fluorobenzene. Also suitable are mixtures of the abovementioned solvents. Particularly preferred solvents are the abovementioned haloalkanes, especially dichloromethane.

It goes without saying that the reaction is carried out initially under largely apro- tic, especially under anhydrous, reaction conditions. The pre-cleaning or predrying of the solvent is carried out in the usual manner, preferably by treatment with solid drying agents such as molecular sieves or predried oxides such as alumina, silica, calcium oxide or barium oxide.

In general, one will carry out the method according to the invention at temperatures ranging from 60 to -140 ⁰ C, preferably in the range from 40 to -80 ⁰ C, more preferably in the range from 25 to -40 ⁰ C.

To release the compounds (I), a protic compound (proton donor) is added to the reaction mixture. The proton donor is preferably selected from water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or mixtures thereof with water. Particularly suitable are water / methanol and water / ethanol mixtures.

The isolation and optionally purification of the obtained diimide (I) is carried out by customary methods known to the person skilled in the art. This includes z. B. removing the solvent used for the reaction, for. B. by evaporation. The evaporation can be carried out under elevated temperature and / or reduced pressure. In a suitable embodiment, the solvent used for the reaction with the Lewis acid is partially or completely removed already before the addition of the proton donor. Isolation of diimide (I) may involve precipitation with a suitable precipitant. Preferably, a proton donor is used to release the diimide (I), in which the compound (I) is not or only slightly soluble. Such proton donors are water and water / alcohol mixtures with sufficient water content. The isolation of diimide (I) may further comprise at least one filtration and / or drying step.

The aforementioned compounds may be subjected to further purification. These include, for example, column chromatographic methods, sublimation, crystallization or a combination of several of these methods. For use of the products as semiconductors, it may be advantageous to subject the products to further purification. The column chromatography and the crystallization are each carried out using a suitable solvent. These include halogenated hydrocarbons, such as methylene chloride or chloroform, or aromatic solvents. For the crystallization it is also possible to use aprotic carboxylic acid amides, if appropriate in combination with water and / or an alcohol, in order to reduce the solubility. In organic solvents poorly soluble compounds can also be purified by fractionation from sulfuric acid. The cleaning by sublimation can be carried out using a temperature gradient, for. In a 3-zone sublimation device. The preparation of a perylene according to the invention is summarized in the following scheme using the example of 1,6,7,12-tetrakis (4- [3,4,5-tridodecyloxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide (1) :

Reagents and reaction conditions:

a) D, L-α-methylbenzylamine (racemic), propionic acid, reflux 20 h;

b) 4-methoxyphenol, K ₂ CO ₃ , N-methylpyrrolidone (NMP), Ar, 120 ^° C, 69 h;

c) BBr ₃ , CH 2 Cl ₂ , warm from ⁰ C to room temperature over 5 h; then 0 ⁰ C water / methanol (4: 1) d) 3,4,5-tridodecyloxybenzoic acid, N, N'-dicyclohexylcarbodiimide (DCC),

4-Dimethylaminopyridine (DMAP), 4- (dimethylamino) pyidinium-4-tosylate (DPTS), molecular sieve 4 A, dimethylformamide (DMF), CH 2 Cl 2, from 0 ⁰ C to 50 ⁰ C within 91 h.

The compounds of the formula (I) are particularly advantageous for use in organic photovoltaics (OPV). In principle, these compounds are suitable for use in dye-sensitized solar cells. However, their use in solar cells, which are characterized by a diffusion of excited states (exciton diffusion), is preferred. In this case, one or both of the semiconductor materials used is characterized by a diffusion of excited states (exciton mobility). Also suitable is the combination of at least one semiconductor material, which is characterized by a diffusion of excited states, with polymers which allow conduction of the excited states along the polymer chain. Such solar cells are referred to as excitonic solar cells within the meaning of the invention. Direct conversion of solar energy into electrical energy in solar cells relies on the internal photoelectric effect of a semiconductor material, i. H. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact. An exciton can z. B. arise when a photon penetrates into a semiconductor and an electron to excite the transition from the valence band in the conduction band. However, to generate current, the excited state created by the absorbed photons must reach a p-n junction to create a hole and an electron, which then flows to the anode and cathode. The photovoltaic voltage thus generated can cause a photocurrent in an external circuit, through which the solar cell gives off its power. In this case, only those photons can be absorbed by the semiconductor, which have an energy that is greater than its band gap. The size of the semiconductor band gap thus determines the proportion of sunlight that can be converted into electrical energy. The described excitonic solar cells usually consist of two absorbing materials with different band gaps in order to use the solar energy as effectively as possible. Most organic semiconductors have exciton diffusion lengths of up to 10 nm. Here, there is still a need for organic semiconductors, via which the excited state can be transmitted over the largest possible distances. Surprisingly, it has now been found that the compounds of general formula I described above are particularly advantageous for use in excitonic solar cells.

Suitable organic solar cells are generally layered and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers are usually on a conventional substrate. The structure of organic solar cells is z. B. in US 2005/0098726 A1 and US 2005/0224905 A1, which is incorporated herein by reference.

Suitable substrates are for. Oxidic materials (such as glass, quartz, ceramics, SiO 2, etc.), polymers (e.g., polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) acrylates, polystyrene and blends and composites thereof) and combinations thereof.

In principle, metals (preferably groups 8, 9, 10 or 11 of the Periodic Table, eg Pt, Au, Ag, Cu, Al, In, Mg, Ca), semiconductors (eg. Doped Si, doped Ge, indium tin oxide (ITO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), etc.), metal alloys (eg Based on Pt, Au, Ag, Cu, etc., especially Mg / Ag alloys), semiconductor alloys, etc. Preferably, the anode used is a material that is substantially transparent to incident light. This includes z. ITO, doped ITO, ZnO, TiO 2, Ag, Au, Pt. The cathode used is preferably a material that essentially reflects the incident light. These include z. As metal films, z. B. from Al, Ag, Au, In, Mg, Mg / Al, Ca, etc.

The photoactive layer in turn comprises at least one or consists of at least one layer which contains as organic semiconductor material at least one compound which is selected from compounds of the formulas I and II, as defined above. In one embodiment, the photoactive layer comprises at least one organic acceptor material. In addition to the photoactive layer, there may be one or more further layers, e.g. For example, a layer with electron-conducting properties (ETL) and a layer containing a hole-transporting material (HTL) that need not absorb, excitons and hole-blocking layers (eg excitation blocking layers, EBL) that are not supposed to absorb multiplication layers. Suitable excitons and holes blocking layers are z. As described in US 6,451, 415.

Suitable Excitonenblockerschichten are z. B. Bathocuproine (BCP), 4,4 ', 4 "-Tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine (m-MTDATA) or polyethylenedioxithiophene (PEDOT), as described in US 7,026,041.

The excitonic solar cells according to the invention are based on photoactive donor-acceptor heterojunctions. If at least one compound of the formula (I) is used as HTM, the corresponding ETM must be selected such that a rapid electron transfer to the ETM takes place after excitation of the compounds. Suitable ETMs are z. B. C60 and other fullerenes, perylene-3,4: 9,10-bis (dicarboximides)

PTCDI, etc. If at least one compound of formula (I) is used as ETM, the complementary HTM must be chosen such that after excitation of the compound rapid hole transfer to the HTM takes place. The heterojunction can be carried out flatly (compare Two layer organic photovoltaic cell, CW Tang, Appl. Phys. Lett, 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzäpfel, J. Cryst., Liq., Cryst, 252, 243-258 (1994).) Or as a bulk heterojunction or interpenetrated donor-acceptor network, cf. BCJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater., 1 1 (1), 15 (2001).). The photoactive layer based on a heterojunction between at least one compound of the formula (I) and an HTL or ETL can be used in solar cells with MiM, pin, pn, mip or min structure (M = metal, p = p-doped organic or inorganic semiconductor, n = n-doped organic or inorganic semiconductor, i = intrinsically conductive system of organic layers, see, for example, J. Drechsel et al., Org. Eletron., 5 (4), 175 (2004) or Maennig et al., Appl. Phys. A 79, 1-14 (2004)). It can also be used in tandem cells as described by P. Peumnas, A. Yakimov, SR Forrest in J. Appl. Phys., 93 (7), 3693-3723 (2003) (see patents US 04461922, US 06198091 and US 06198092). It can also be used in tandem cells made of two or more stacked MiM, pin, mip or min diodes (see patent application DE 103 13 232.5) (Drechsel, J., et al., Thin Solid Films, 451452, 515-517 (2004)).

Thin layers of the compounds and of all other layers can be obtained by vapor deposition in a vacuum or inert gas atmosphere, by laser ablation or by solution or dispersion processable methods such as spin coating, knife coating, casting, spraying, dip coating or printing (eg InkJet, Flexo , Offset, gravure, gravure, nanoimprint). The layer thicknesses of the M, n, i and p layers are typically 10 to 1000 nm, preferably 10 to 400 nm.

As a substrate z. As glass, metal or polymer films are used, which are usually coated with a transparent, conductive layer (such as Snθ2: F, Snθ2: In, ZnO: Al, carbon nanotubes, thin metal layers).

In addition to the compounds of general formula (I), the following semiconductor materials are suitable for use in organic photovoltaics:

Acenes, such as anthracene, tetracene, pentacene, which may each be unsubstituted or substituted. Substituted acenes preferably comprise at least one substituent selected from electron-donating substituents (eg, alkyl, alkoxy, ester, carboxylate or thioalkoxy), electron-withdrawing substituents (eg, halogen, nitro, or cyano), and combinations thereof. These include 2,9-dialkylpentacenes and 2,10-dialkylpentacenes, 2,10-dialkoxypentacenes, 1, 4,8,11-tetraalkoxypentanes and rubrene (5,6,11,12-tetraphenylnaphthacene). Suitable substituted pentacenes are described in US 2003/0100779 and US Pat. No. 6,864,396, which is hereby incorporated by reference. train is taken. A preferred acene is rubrene (5,6,11,12-tetraphenylnaphthacene);

Phthalocyanines, for example phthalocyanines which carry at least one halogen substituent, such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, phthalocyanines containing metal-free or divalent metals or metal atom-containing groups, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, etc. Suitable phthalocyanines are in particular copper phthalocyanine, zinc phthalocyanine, metal-free phthalocyanine, hexadecachloro copper phthalocyanine, hexadecochlorozinc phthalocyanine, metal-free hexadecachlorophatho-cyanine, hexadecafluoro copper phthalocyanine, hexadecafluorophthalocyanine or metal-free hexafluorophthalocyanine;

Porphyrins, such as. 5,10,15,20-tetra (3-pyridyl) porphyrin (TpyP);

Liquid crystalline (LC) materials, for example, coronene such as hexabenzocoronene

(HBC-PhC12), coronediimides, or triphenylenes, such as

2,3,6,7,10,1 1-hexahexylthiotriphenylene (HTT6), 2,3,6,7,10,11-hexakis- (4-n-nonylphenyl) -triphenylene (PTP9) or 2,3 , 6,7,10,11-Hexakis (undecyloxy) -triphenylene (HAT11). Particularly preferred are liquid crystalline materials that are discotic;

Thiophenes, oligothiophenes and substituted derivatives thereof. Suitable oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes, α, ω-di (C 1 -C 8) -alkyloligothiophenes, such as α, ω-dihexylquaterthiophenes, α, ω-dihexylquinquethiophenes and α, ω-dihexylsexithiophenes, poly (alkylthiophenes), such as poly (3-hexylthiophene), bis (dithienothiophenes), anthradithiophenes, and dialkylanthra-dithiophenes such as dihexylanthradithiophene, phenylene-thiophene (PT) oligomers, and derivatives thereof, especially α, ω-alkyl-substituted phenylene-thiophene oligomers;

Also suitable are compounds of the type α, α'-bis (2,2-dicyanovinyl) quinquethiophene (DCV5T),

(3- (4-octylphenyl) -2,2'-bithiophene) (PTOPT),

Poly (3- (4 '- (1, 4,7-trioxaoctyl) phenyl) thiophene (PEOPT),

(Poly (3- (2'-methoxy-5'-octylphenyl) thiophene)) (POMeOPT), poly (3-octylthiophene) (P3OT), poly (pyridopyrazinovinylene) -polythiophene blends, as described

EHH-PpyPz, copolymers PTPTB, BBL, F8BT, PFMO, see Brabec C, Adv. Mater.,

2996, 18, 2884, (PCPDTBT) poly [2,6- (4,4-bis (2-ethylhexyl) -4 H -cyclopenta [2,1-b; 3,4-b '] - dithiophene) -4,7- (2,1,3-benzothiadiazole);

Paraphenylenevinylene and paraphenylenevinylene containing oligomers or polymers such. Polyparaphenylenevinylene, MEH-PPV (poly (2-methoxy-5- (2'-ethylhexyloxy) - 1, 4-phenylenevinylene, MDMO-PPV (poly (2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1, 4-phenylene-vinylene)), PPV, CN-PPV (with various alkoxy derivatives) ;

Phenylenethinylene / phenylenevinylene hybrid polymers (PPE-PPV);

Polyfluorene and alternating polyfluorene copolymers such. With 4,7-dithien-2'-yl-2,1,3-benzothiadiazole, poly (9,9'-dioctylfluorene-co-benzothiothiazole) (F ₈ BT), poly (9, 9'-dioctylfluorene-co-bis-N, N '- (4-butyl-phenyl) -bis-N, N'-phenyl-1, 4-phenylenediamine (PFB);

Polycarbazoles, d. H. Carbazole containing oligomers and polymers such as (2,7) and (3,6).

Polyanilines, d. H. Aniline-containing oligomers and polymers such as (2,7) and (3,6).

Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysiols, polyphospholes, TPD, CBP, spiro-MeOTAD.

Fullerenes, especially C60 and its derivatives such as PCBM (= [6,6] -phenyl-C6i-butyric acid methyl ester). In such cells, the fullerene derivative is a hole conductor.

Copper (I) iodide, copper (I) thiocyanate.

p-n mixed materials, d. H. Donor and acceptor in one material, polymer, block polymer, polymers with C60s, C60 azo dyes, triads carotenoid porphyrin quinode LC donor / acceptor systems as described by Kelly in S. Adv. Mater. 2006, 18, 1754.

All of the aforementioned semiconductor materials may also be doped. Examples of dopants for p-type semiconductor: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F ₄ -TCNQ), etc.

The (novel) compounds (I) according to the invention are also particularly advantageously suitable as organic semiconductors. They usually act as n-semiconductors. If the compounds of the formula (I) used in accordance with the invention are combined with other semiconductor conductors and if the position of the energy levels results in the other semiconductors functioning as n-type semiconductors, the compounds (I) can also function as p-type semiconductors by way of exception. This is z. As in the combination with cyano-substituted perylenetetracarboximides the case. The compounds of the formula (I) are distinguished by their air stability. Furthermore, they have a high charge transport mobility and have a high on / off ratio. They are particularly suitable for organic field effect transistors. The compounds according to the invention are advantageously suitable for the production of integrated circuits (ICs), for hitherto common n-channel MOSFETs (MOSFETs) are used, which are CMOS analog semiconductor devices, eg for microprocessors, microcontrollers, static RAM, and other digital logic devices. For the production of semiconductor materials, the processes according to the invention can be further processed by one of the following processes: printing (offset, flexo, gravure, screen, inkjet, electrophotography), evaporation, laser transfer, photolithography, dropcasting, etc. They are particularly suitable for use in displays (especially large and / or flexible displays) and RFI D tags.

The compounds according to the invention are furthermore particularly advantageously suitable for data storage in diodes, especially in OLEDs, in photovoltaics, as UV absorbers, as optical brighteners, as invisible labels and as fluorescent labels for biomolecules, such as proteins, DNA, sugars and combinations thereof.

The compounds according to the invention are furthermore particularly advantageously suitable as fluorescent dye in a display based on fluorescence conversion; in a light-collecting plastic part, which is optionally combined with a solar cell; as a pigment in electrophoretic displays; as a fluorescent dye in a chemiluminescence-based application (eg in glow sticks).

The compounds according to the invention are furthermore particularly advantageously suitable as fluorescent dye in a display based on fluorescence conversion. Such displays generally include a transparent substrate, a fluorescent dye on the substrate, and a radiation source. Common sources of radiation emit blue (color-by-blue) or UV (color-by-UV) light. The dyes absorb either the blue or the UV light and are used as a green emitter. In these displays z. B. the red light is generated by the red emitter is excited by a blue or UV light-absorbing green emitter. Suitable color-by-blue displays are z. As described in WO 98/28946. Suitable color-by-uv displays are z. By W. A. Crossland, I.D. Sprigle and A.B. Davey in Photoluminescent LCDs (PL-LCD) using phosphors at Cambridge University and Screen Technology Ltd., Cambridge, UK.

The compounds according to the invention are furthermore particularly suitable as fluorescence emitters in OLEDs in which they are excited either by electroluminescence or by a corresponding phosphorescence emitter via Förster energy transfer (FRET).

The compounds according to the invention are furthermore particularly suitable in displays which turn colors on and off based on an electrophoretic effect via charged pigment dyes. Such electrophoretic displays are z. As described in US 2004/0130776. The compounds according to the invention are furthermore particularly suitable for use in a light-collecting plastic part which absorbs light over a large area and emits light at its edges after repeated refraction (so-called LISAs). Such LISAs can be used on the edges of solar cells such. As silicon solar cells or organic solar cells, which convert the concentrated light into electrical energy. A combination of light-collecting plastics with solar cells is z. As described in US 4,110,123.

The compounds according to the invention are furthermore particularly suitable in chemoluminescence applications. These include so-called "Glow Sticks". For their preparation, at least one compound of formula (I) z. B. are dissolved in an alkyl phthalate. An excitation of chemiluminescence can be done by mixing an oxalic acid ester with hydrogen peroxide, for. B. after these two initially separate components are mixed by breaking a glass. The resulting reaction energy leads to the excitation and fluorescence of the dyes. Such glow sticks can be used as emergency light, z. B. used in fishing, life-saving vests or other security applications.

The invention furthermore relates to organic field-effect transistors, comprising a substrate having at least one gate structure, a source electrode and a drain electrode and at least one compound of the formula I, as defined above, as n-type semiconductor. The invention further substrates with a plurality of organic field effect transistors, wherein at least a portion of the field effect transistors contains at least one compound of formula I, as defined above, as n-type semiconductor. The invention also relates to semiconductor devices which comprise at least such a substrate.

A particular embodiment is a substrate having a pattern (topography) of organic field effect transistors, each transistor

an organic semiconductor on the substrate; a gate structure for controlling the conductivity of the conductive channel; and conductive source and drain electrodes at both ends of the channel

wherein the organic semiconductor consists of at least one compound of the formula (I) or comprises a compound of the formula (I). Furthermore, the organic field effect transistor usually comprises a dielectric.

Another specific embodiment is a substrate having a pattern of organic field effect transistors, each transistor forming an integrated circuit. or part of an integrated circuit and wherein at least part of the transistors comprises at least one compound of formula (I).

Suitable substrates are in principle the known materials. Suitable substrates include, for. Metals (preferably metals of Groups 8, 9, 10 or 11 of the Periodic Table such as Au, Ag, Cu), oxidic materials (such as glass, quartz, ceramics, SiO 2), semiconductors (eg doped Si, doped Ge), metal alloys (eg based on Au, Ag, Cu, etc.), semiconductor alloys, polymers (eg polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyimides , Polyurethanes, polyalkyl (meth) acrylates, polystyrene, and mixtures and composites thereof), inorganic solids (eg, ammonium chloride), paper, and combinations thereof. The substrates can be flexible or inflexible solid, with curved or planar geometry, depending on the desired application.

A typical substrate for semiconductor devices comprises a matrix (eg, a quartz or polymer matrix) and, optionally, a dielectric capping layer.

Suitable dielectrics are SiO 2, polystyrene, poly-α-methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene) polyvinylcarbazole, fluorinated polymers (eg Cytop, CYMM) cyanopullanes, polyvinylphenol, poly-p-xylene, polyvinylchloride or thermally or by Humidity crosslinkable polymers. Special dielectrics are "seif assembled nanodielectrics", ie polymers derived from SiCI functionalities containing monomers such. B. CI ₃ SiOSiCI ₃ , CI ₃ Si (CH ₂ ^ -SiCI ₃ , CI ₃ Si (CH ₂ ) ^ - SiCl ₃ and / or which are crosslinked by atmospheric moisture or by the addition of water in dilution with solvents ( See, for example, Faccietti Adv. Mat., 2005, 17, 1705-1725.) Instead of water, it is also possible to use hydroxyl-containing polymers such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene as crosslinking components Crosslinking process, such as polystyrene, which is then crosslinked (see Facietti, US patent application 2006/0202195).

The substrate may additionally include electrodes, such as gate, drain, and source electrodes of OFETs, which are normally located on the substrate (eg, deposited on or embedded in a nonconductive layer on the dielectric). The substrate may additionally include conductive gate electrodes of the OFETs, which are typically disposed below the dielectric capping layer (i.e., the gate dielectric).

According to a special embodiment, an insulator layer (gate insulating layer) is located on at least one part of the substrate surface. The insulator layer comprises at least one insulator which is preferably selected from inorganic insulators such as SiO ₂ , SiN, etc., ferroelectric insulators such as Al ₂ O ₃ , Ta ₂ Os, La ₂ Os, TiO ₂ , Y2O3, etc., organic insulators such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.

Suitable materials for source and drain electrodes are in principle electrically conductive materials. These include metals, preferably metals of groups 8, 9, 10 or 11 of the Periodic Table, such as Pd, Au, Ag, Cu, Al, Ni, Cr, etc. Also suitable are conductive polymers, such as PEDOT (= poly (3,4 PSS (= poly (styrenesulfonate), polyaniline, surface-modified gold, etc. Preferred electrically conductive materials have a resistivity of less than 10 " ³ , preferably less than 10 ^{" 4} , especially less than 10 ^"6 or 10 ^{" 7} ohms x meters.

According to a specific embodiment, drain and source electrodes are at least partially on the organic semiconductor material. Of course, the substrate may include other components, such as are commonly used in semiconductor materials or ICs, such as insulators, resistors, capacitors, interconnects, etc.

The electrodes can be applied by conventional methods such as evaporation, lithographic methods or another patterning process.

The semiconductor materials can also be processed with suitable auxiliaries (polymers, surfactants) in disperse phase by printing.

In a first preferred embodiment, the deposition of at least one compound of general formula I (and optionally other semiconductor materials) by a vapor deposition method (Physical Vapor Deposition PVD). PVD processes are performed under high vacuum conditions and include the following steps: evaporation, transport, deposition. Surprisingly, it has been found that the compounds of the general formula I are particularly advantageous for use in a PVD process, since they do not substantially decompose and / or form undesired by-products. The deposited material is obtained in high purity. In a specific embodiment, the deposited material is obtained in the form of crystals or contains a high crystalline content. Generally, at least one compound of general formula I is heated to a temperature above its vaporization temperature for PVD and deposited on a substrate by cooling below the crystallization temperature. The temperature of the substrate in the deposition is preferably in a range of about 20 to 250 ⁰ C, more preferably 50 to 200 ⁰ C. Surprisingly, it was found that increased substrate temperatures in the deposition of the compounds of the formula I advantageous effects on the properties the achieved semiconductor elements can have. The resulting semiconductor layers generally have a thickness sufficient for an ohmic contact between the source and drain electrodes. The deposition may be carried out under an inert atmosphere, e.g. B. under nitrogen, argon or helium.

The deposition is usually carried out at ambient pressure or under reduced pressure. A suitable pressure range is about 10 " ⁷ to 1, 5 bar.

Preferably, the compound of formula (I) is deposited on the substrate in a thickness of 10 to 1000 nm, more preferably 15 to 250 nm. In a special embodiment, the compound of the formula I is deposited at least partially in crystalline form. For this purpose, especially the PVD method described above is suitable. Furthermore, it is possible to use previously prepared organic semiconductor crystals. Suitable methods for obtaining such crystals are described by R. A. Laudise et al. in Physical Vapor Growth of Organic Semi- Conductors, Journal of Crystal Growth 187 (1998), pages 449-454, and in Physical Vapor Growth of Centimeter-sized Crystals of α-Hexathiophene, Journal of Cystal Growth 1982 (1997), pages 416-427, which is incorporated herein by reference.

Compounds of the general formula (I) wherein at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 has} a group of the formulas 11.1 to 11.12 can also be processed particularly advantageously from solution. In a second preferred embodiment, the deposition of at least one such compound of general formula (I) (and optionally further semiconductor materials) is therefore carried out by spin coating. These compounds of the formula (I) should also be suitable for the production of semiconductor elements, especially OFETs or based on OFETs, by a printing process. It can be used for customary printing processes (inkjet, flexo, offset, gravure, gravure, nano print). Preferred solvents for the use of the compounds of the formula (I) in a printing process are aromatic solvents, such as toluene, xylene, etc. It is possible to add thickening substances, such as polymers, to these "semicontrinates", eg. As polystyrene, etc. It uses as a dielectric, the aforementioned compounds.

In a preferred embodiment, the field effect transistor according to the invention is a thin film transistor (TFT). According to a conventional structure, a thin film transistor has a gate electrode disposed on the substrate, a gate insulating layer disposed thereon and the substrate, a semiconductor layer disposed on the gate insulating layer, an ohmic contact layer on the semiconductor layer, and a source electrode and a drain electrode on the ohmic contact layer.

In a preferred embodiment, the surface of the substrate is deposited prior to the deposition of at least one compound of general formula (I) (and given if at least one further semiconductor material) undergoes a modification. This modification serves to form regions that bond the semiconductor materials and / or regions where no semiconductor materials can be deposited. Preferably, the surface of the substrate is modified with at least one compound (C1) which is suitable for bonding to the surface of the substrate as well as the compounds of the formula (I). In a suitable embodiment, a part of the surface or the complete surface of the substrate is coated with at least one compound (C1) in order to allow an improved deposition of at least one compound of the general formula (I) (and optionally other semiconducting compounds). Another embodiment comprises depositing a pattern of compounds of the general formula (C1) on the substrate according to a corresponding production method. These include the well-known mask processes as well as so-called "patterning" method, as z. As described in US 1 1/353934, which is incorporated herein by reference in its entirety.

Suitable compounds of the formula (C1) are capable of a binding interaction both with the substrate and with at least one semiconductor compound of the general formula I. The term "binding interaction" includes the formation of a chemical bond (covalent bond), ionic bond, coordinate interaction, Van der Waals interactions, e.g. Dipole-dipole interactions) etc. and combinations thereof. Suitable compounds of the general formula (C1) are:

Silanes, phosphonic acids, carboxylic acids, hydroxamic acids, such as Alkyltrichlorsila- ne, z. B. n- (octadecyl) trichlorosilane; Compounds with trialkoxysilane groups, e.g. B. alkyltrialkoxysilanes, such as n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltri- (n-propyl) oxysilane, n-octadecyltri- (isopropyl) oxysilane; Tri- alkoxyaminoalkylsilanes such as triethoxyaminopropylsilane and N [(3-triethoxysilyl) -propyl] -ethylenediamine; Trialkoxyalkyl 3-glycidyl ether silanes such as triethoxypropyl 3-glycidyl ether silane; Trialkoxyallylsilanes such as allyltrimethoxysilane; trialkoxy

(Isocyanatoalkyl) silane; Trialkoxysilyl (meth) acryloxyalkanes and trialkoxysilyl (meth) acrylamidoalkanes such as 1-triethoxysilyl-3-acryloxypropane.

Amines, phosphines and sulfur-containing compounds, especially thiols.

Preferably, the compound (C1) is selected from alkyltrialkoxysilanes, especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; Hexaalkyldisilazanes, and especially hexamethyldisilazanes (HMDS); Cs-Cso-alkylthiols, especially hexadecanethiol; Mercaptocarboxylic acids and mercaptosulfonic acids especially mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, 3-mercapto-1-propanesulfonic acid and the alkali metal and ammonium salts thereof. There are also various semiconductor architectures with the semiconductor according to the invention conceivable such. B. Top Contact, Top Gate, Bottom Contact, Bottom Gate, or a vertical structure such. B. a VOFET (Vertical organic field effect transistor) such. As described in US 2004/0046182.

The layer thicknesses are in semiconductors z. B. 10 nm to 5 microns, the dielectric 50 nm to 10 microns, the electrodes may, for. B. 20 nm to 1 micron thick. The OFETs can also be combined to other components such as ring oscillators or inverters.

Another aspect of the invention is the provision of electronic components comprising a plurality of semiconductor components, which may be n- and / or p-type semiconductors. Examples of such devices are field effect transistors (FETs), bipolar junction transistors (BJTs), tunnel diodes, inverters, light emitting devices, biological and chemical detectors or sensors, temperature dependent detectors, photodetectors such as polarization sensitive photodetectors, gates, AND, NAND , NOT, OR, TOR, and NOR gates, registers, switches, time blocks, static or dynamic memories, and other dynamic or sequential logical or other digital components, including programmable circuits.

A special semiconductor element is an inverter. In digital logic, the inverter is a gate that inverts an input signal. The inverter is also called NOT-gate. Real inverter circuits have an output current that is the opposite of the input current. Usual values are z. (0, + 5V) for TTL circuits. The performance of a digital inverter reflects the Voltage Transfer Curve (VTC); H. the order of input current versus output current. Ideally, it is a step function, and the closer the real measured curve approaches to such a step, the better the inverter. In a specific embodiment of the invention, the compounds of the formula (I) are used as organic n-semiconductors in an inverter.

The invention will be further illustrated by the following non-limiting examples.

Examples

example 1

Preparation of 1,6,7,12-tetrakis (4- [3,4,5-tridodecyloxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide La) N, N'-bis (α-methylbenzyl) -1, 6,7,12-tetrachloroperylene-3,4: 9,10-tetracarboxylic diimide

A suspension of 2.00 g (3.77 mmol) of 1,6,6,7-tetrachloroperylene-3,4: 9,10-tetracarboxylic bisanhydride and 2.30 g (18.9 mmol) of D, L-α Methylbenzylamine in propionic acid was refluxed for 21 hours. Upon cooling the reaction mixture to room temperature, a precipitate formed, which was separated by filtration, then washed three times with 15 ml of saturated NaHCO3 solution and three times with 15 ml of water and then under vacuum (10 " ³ mbar) at 100 ⁰ C dried The crude product was purified by column chromatography on silica gel with ChbCb / n-hexane (80:20) to give the perylenediimide as a pale red solid (1.20 g, 1.63 mmol = 43% yield) 359 ⁰ C

1.b) N, N'-bis (α-methylbenzyl) -1, 6,7,12-tetrakis (4-methoxyphenoxy) perylene-3,4: 9,10-tetracarboxylic diimide

1.00 g (1.36 mmol) of perylenediimide from Example 1.a), 0.84 g (6.79 mmol) of 4-methoxy-phenol and 0.47 g (3.40 mmol) of dry K 2 CO 3 were dissolved in 20 ml freshly distilled N-methylpyrrolidone (NMP) and stirred under argon atmosphere at 120 ⁰ C 69 h. The mixture changed color from pale red to dark red. After cooling to room temperature, the reaction mixture was added slowly with stirring to 70 ml of a 1 NHCl solution. After another hour of stirring at room temperature, the solid formed was separated by filtration, washed three times with 10 ml of water and three times with 10 ml of methanol and dried in vacuo (silica gel, room temperature, 13 mbar). The crude product was purified by twice acid chromatography (silica gel, ChbCb / n-hexane (80:20)) and the product was obtained in 49% yield (0.73 g, 0.67 mmol).

1.c) 1, 6,7,12-tetrakis (4-hydroxyphenoxy) perylene-3,4: 9,10-tetracarboxylic diimide

0.33 g (0.30 mmol) of perylene diimide of Example 1.b) was dissolved under argon in 30 ml CH2Cl2, cooled to 0 ⁰ C and a solution of BBr3 (5.7 mL, 6.00 mmol, 20 equivalents) in 16 ml of CH 2 Cl 2 added dropwise over 15 minutes, the reaction mixture changing color from red to blue. The mixture was stirred for another hour at 0 ^° C. and for a further 3.5 h at room temperature. The solvent and excess BBr3 were removed by distillation and the residue at 0 ⁰ C and 25 ml of a water / methanol mixture (4: 1) treated. After 30 minutes in the ultrasonic bath, the product was separated by filtration and dried under vacuum (SiO 2, 100 ⁰ C, 10 ^"3 mbar, several days) to give a dark magenta solid with a melting point of> 450 ⁰ C. 1.d) 1,6,7,12-Tetrakis (4- [3,4,5-tridodecyloxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide (1)

To a 100 ml round bottom flask of the 50 ml (0.061 mmol, 1 equivalent) perylenetetracarboxylic diimide from Example 1.c), 2.07 g (3.04 mmol, 50 equivalents) of 3,4,5-tridodecylbenzoic acid, 144 mg (0.70 mmol) N, N'-dicyclohexylcarbodiimide (DCC), 41.4 mg (0.34 mmol) 4-dimethylaminopyridine (DMAP), 93.7 mg (0.32 mmol) 4- (dimethylamino) pyridinium 4-tosylate (DPTS) and 1, 2 g of molecular sieve (4 Å) was 3.1 ml freshly distilled dimethylformamide (DMF) at 0 ⁰ C under argon and added 9.3 ml of CH2Cl2. The suspension was stirred under argon atmosphere at room temperature for 70 h and at 50 ^° C. for 21 h. After cooling to room temperature, 20 ml of water and 40 ml of CH 2 Cl 2 were added to the reaction mixture. The molecular sieve was then filtered off, the organic phase separated and the aqueous phase extracted three times with 30 ml CH 2 Cl 2. From the combined organic phases, the solvent was removed under reduced pressure and the residue was purified twice by column chromatography (silica gel, ChbCb / methanol (gradient 100: 0 to 99.5: 0.5 and then 99: 1)). The product was then precipitated again from ChbCb solution by addition of methanol and dried under vacuum (silica gel, room temperature, 10 ^-3 mbar) to give the title compound as a deep blue solid in 63% yield (132 mg, 0.038 mmol) : 246 to 247 ⁰ C

FIG. 2 shows the UV / VIS spectrum (line a) and the fluorescence spectrum (h line b) in CH 2 Cl 2 (10 μM) and the UV / VIS spectrum (line c) and the fluorescence spectrum (line d) in methylcyclohexane (10 μM) ). The UV / VIS absorption spectrum and the fluorescence spectrum in CH2CI2 show the typical features of a perylene bisimide chromophore. The absorption maximum of the strong allowed So-Si transition appears at 570 nm (absorption coefficient ε = 41600 M ^-1 cnτ ¹ ) and the fluorescence emission spectrum with a maximum at λ _ma χ = 602 nm is a mirror image of S0-S1 absorption band with a Stokes Shift of 32 nm. The UV / VIS absorption spectrum and the fluorescence spectrum of the aggregates present in the polar solvent methylcyclohexane differ greatly from the spectra of the monomeric compound. They show a strong bathochromic shift and unusually narrow bands of intense intensity. The absorption maximum of the aggregates shifts to λ _ma χ = 642 nm, the fwhm value is reduced to 885 cm- ¹ and the dipole moment for the So-Si transition increases from 6.7 D (monomer) to 8, 3 D (aggregates). The fluorescence spectrum of the aggregates, which is a mirror image of the absorption spectrum, has its maximum at λ _ma χ = 654 nm with a very small Stokes shift of 12 nm and an equally small fwhm value of 878 cm ^-1 .

Atomic force microscopy AFM (atomic force microscopy) measurements were performed under normal conditions with a Veeco MultiMode ™ Nanoscope IV system in air tapping mode. Silicon cantilevers (Olympus, OMCL-AC160TS) with a resonant frequency of ~ 300 kHz were used. The 512x512 pixel images were recorded at a scan rate of 2 lines per second. Solutions of (1) in methylcyclohexane were spin-coated onto highly oriented pyrolytic graphite (HOPG, NanoTechnology Instruments, Netherlands) (60 μM, 4000 rpm) or silicon wafers (NanoWorld AG, Switzerland) (9 μM, 2000 rpm).

Figure 3 (A, B) shows AFM plots of monolayers of (1) adsorbed at the basal plane of HOPG by spincoating (4000 rpm) from MCH solution (60 μM). A cross-sectional analysis (small window in A) showed an average thickness of 0.3 ± 0.1 nm and a width of 5.7 ± 0.2 nm for the aligned rows. The scaling is 45 nm, z-axis (A): 1, 5 nm, (B): 2.0 nm. AFM studies with solutions of (1) in toluene and CCU gave comparable results. Partial figures (C and D) show tapping-mode AFM representations of the self-assembly of (1) on silicon wafers. The application was carried out by (2000 rpm) a 9 μM solution in MCH. The scaling (white lines in the lower right corner of the image) corresponds to 300 nm, the z-scale is 6 nm. Figure (E) shows an enlarged detail of (D). The scaling (white line in the lower right corner) is 45 nm. Figure (F) shows a model of the aggregate, where p is the helical pitch. The half pitch distance p / 2 was determined to be 6.5 ± 1.7 nm. This is in good agreement with the calculated value of 6 nm.

FIG. 4 shows concentration-dependent UV / Vis spectra of (1) (1.1 μM to 14 mM) in toluene at room temperature. Small picture: change in the extinction coefficient at 639 nm (■) and regression line according to an isodesmic or equal K model. The deviation of the calculated line from the measured ε vs concentration values suggests a strong orientation across hydrogen bonds with π-π stacks.

Scanning tunneling microscopy (FIG. 5)

Scanning Tunneling Microscopy (STM) measurements with a Veeco MultiMode ™ - Nanoscope IV system using Pt / Ir (90:10) tips (MakTecK GmbH, Germany). Solutions of (1) in methylcyclohexane were spin-coated onto highly oriented pyrolytic graphite (HOPG, NanoTechnology Instruments, Netherlands) (60 μM, 4000 rpm). One drop of 1-phenyloctane was added to the films on the substrates. All representations in FIG. 5 were obtained in the current mode.

Figure 5 shows STM plots of (1) adsorbed at the basal plane of HOPG by spincoating (4000 rpm) from MCH solution (60 μM). Tunnel parameters: (A) I = 1, 32 pA, U = -0.87V; (B) I = 1, 0 pA, U = -1, 20 V. The scaling is 20 nm, z-axis: 0.7 nm. Figure (C) is an enlarged and filtered section of (B), the scaling is 20 nm. (D) shows the molecular structure and arrangement of (1) on a unit cell as depicted in the STM plot.

Claims

claims

1. Use of homo-aggregates of compounds of general formula I.

which are at least partially in the form of J-aggregates, wherein

n is 1, 2, 3 or 4,

as emitter materials, charge transport materials or exciton transport materials.

2. Use according to claim 1, wherein n is 2, 3 or 4.

3. Use according to one of the preceding claims, wherein at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is a radical other than} hydrogen, which is selected from aryloxy radicals.

Use according to one of the preceding claims, where at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} aryloxy, arylthio, hetaryloxy or hetarylthio which bears at least two substituents which are each independently selected from C 4 -C 30 Alkyl, C 4 -C 30 -alkoxy and C 4 -C 30 -alkylthio, where the alkyl radicals of the alkyl, alkoxy and alkylthio substituents can be interrupted by one or more nonadjacent oxygen atoms,

or where at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 represents} aryloxy, arylthio, hetaryloxy or hetarylthio and, as structural element, an additional aryl group group or hetaryl group which carries at least two substituents, each independently selected from C4-C3o-alkyl, C4-C30-alkoxy and C4-C3o-alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents one or more non-adjacent oxygen atom (s) may be interrupted.

5. Use according to one of the preceding claims, where at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 is} a group of the formulas (11.1) to (11.12)

(11.1) (II.2)

(II.5) (II.

6)

(II.7) (II.8)

(II.9) (11.10)

(H-11) (11-12)

stands in which

# represents the point of attachment to the rylene skeleton, x is 2 or 3, in the compounds of the formulas 11.10, 11.11 and 11.12 x being 2,

A is a divalent bridging group which is selected from -O-, -S-, -O-arylene-, -S-arylene-, -O-arylene-C (= O) O-, -S-arylene- C (= O) O-,

-O-arylene-OC (= O) - and -S-arylene-OC (= O) -, and

R ^{1 are} each independently selected from C 4 -C 30 -alkyl,

C4-C3o-alkoxy and C4-C30-alkylthio, wherein the alkyl chains of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s).

Use according to claim 5, wherein A is a bridging group

where # represents the point of attachment to the rylene skeleton.

7. Use according to one of the preceding claims as an active material in organic photovoltaics.

8. Use according to one of the preceding claims in excitonic solar cells.

9. Process for the preparation of compounds of the formula I.

in which n is 1, 2, 3 or 4,

in which a diimide of the formula (IV)

wherein

n is 1, 2, 3 or 4,

R ^a1 and R ^{a2 are} independently aryl, and

wherein, when R ^b1 and R ^b2 are each independently alkyl, subjecting the compound of formula IV to a reaction with a strong Lewis acid and a proton donor, and wherein in the case where R ^b1 and R ^{b2 are} hydrogen the compound of formula IV is subjected to a hydrogenolysis.

10. Homo-aggregates, which are present at least partially in the form of J-aggregates, as defined in any one of claims 1 to 6.

1 1. Compounds of general formula I, as defined in any one of claims 1 to 6 defined.

12. An organic field effect transistor comprising a substrate having at least one gate structure, a source electrode and a drain electrode and at least one compound of the formula I as defined in any one of claims 1 to 6, as n-type semiconductor.

13. A substrate having a plurality of organic field effect transistors, wherein at least a portion of the field effect transistors at least one compound of formula I, as defined in any one of claims 1 to 6, as n-type semiconductor.

14. A semiconductor device comprising at least one substrate as defined in claim 13.

15. Use of at least one compound of general formula I, as defined in any one of claims 1 to 6, in organic electronics, in particular in organic field effect transistors.

16. Use of at least one compound of the general formula I as defined in one of claims 1 to 6 for optical labels, for the invisible marking of products, as fluorescent dyes, as a fluorescent label for biomolecules and as pigments.

17. Use of at least one compound of the general formula I as defined in any one of claims 1 to 6, as a fluorescent dye in a fluorescence conversion-based display; in a light-collecting plastic part, which is optionally combined with a solar cell; as a pigment in electrophoretic displays; as a fluorescent dye in a chemoluminescence-based application.

18. Use of at least one compound of general formula I as defined in any one of claims 1 to 6 as emitter in OLED.