WO2009000831A1

WO2009000831A1 - Bromine-substituted rylene tetracarboxylic acid derivatives, and the use thereof

Info

Publication number: WO2009000831A1
Application number: PCT/EP2008/058011
Authority: WO
Inventors: Martin KÖNEMANN; Gabriele Mattern
Original assignee: Basf Se
Priority date: 2007-06-25
Filing date: 2008-06-24
Publication date: 2008-12-31

Abstract

The present invention relates to bromine-substituted rylene tetracarboxylic acid derivatives of the general formula (I), wherein n is 2, 3, or 4; Rn1, Rn2, Rn3, and Rn4 are halogen or cyano, specifically for Br, wherein at least one of the radicals Rn1, Rn2, Rn3 or Rn4 is Br; Y1 and Y2 are O or NRb; wherein Rb is hydrogen or an organyl radical; Z1, Z2, Z3 and Z4 are O, wherein in case that Y1 is NRa, one of the radicals Z1 and Z2 may also be NRC, wherein the radicals Ra and Rc together are a bridging group having 2 to 5 atoms between the flanking bonds, and wherein in case Y2 is NRb, one of the radicals Z3 and Z4 may also be NRd, wherein the radicals Rb und Rd together are a bridging group having 2 to 5 atoms between the flanking bonds; to the production of compounds of the general formula I by means of reaction of a corresponding compound, wherein at least one of the radicals Rn1, Rn2, Rn3 and/or Rn4 is hydrogen, having N,N'-dibromisocyanuric acid, and to the use of compounds of the general formula I as emitter materials, charge transport materials, or exciton transport materials.

Description

Bromine-substituted rylenetetracarboxylic acid derivatives and their use

description

The present invention relates to bromine substituted, especially perbrominated, rylenetetracarboxylic acid derivatives and their use as emitter materials, charge transport materials or exciton transport materials.

It is expected that in the future, in many areas of the electronics industry, organic semiconductors based on low-molecular or polymeric materials will increasingly be used in addition to the classical inorganic semiconductors. These have many advantages over the classical inorganic semiconductors, for example a better substrate compatibility and a better processability of the semiconductor components based on them. They allow processing on flexible substrates and make it possible to precisely adapt their frontier orbital energies to the respective field of application using the methods of modular modeling. The significantly reduced cost of such components has brought a renaissance to the field of organic electronics research. Organic Electronics "focuses on the development of new materials and manufacturing processes for the fabrication of electronic devices based on organic semiconductor layers, including organic field-effect transistors (OFETs) and organic light-emitting diodes (organic light-emitting diodes). organic light-emitting diodes (OLEDs) and photovoltaics Organic field-effect transistors are attributed a great development potential, for example in memory elements and integrated optoelectronic devices In organic light-emitting diodes (OLEDs), the property of materials is used to emit light as they pass through OLEDs are of particular interest as an alternative to cathode ray tubes and liquid crystal displays for the production of flat screens, because of their very compact design and intrinsic never Drigeren power consumption are suitable devices that contain OLEDs, especially for mobile applications, for example for applications in mobile phones, laptops, etc. A great development potential is also attributed to materials that have the largest possible transport distances and high mobilities for light-induced excited states (high exciton diffusion lengths) and which are thus advantageous for use as an active material in so-called excitonic solar cells. With solar cells based on such materials, very good quantum yields can generally be achieved. There is therefore a great need for organic compounds which are useful as emitter materials, charge transport materials or exciton transport materials.

PCT / EP 2006/070143 (= WO 2007/074137), unpublished on the priority date of the present application, describes compounds of the general formula (A)

in which

at least one of R ¹ , R ² , R ³ or 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 independently of one another are 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 compounds of the formula (A) in which R ¹ , R ² , R ³ or R ^{4 are} bromine are described herein inter alia by reacting corresponding compounds in which the corresponding corresponding radicals R ¹ , R ² , R ³ or R ^{4 are} hydrogen, obtained with N, N'-Dibromisocya- nucleic acid in the presence of oleum.

PCT / EP 2007/051532 (= WO2007 / 093643) unpublished on the priority date of the present application describes the use of compounds of the general formula (B)

in which

n is 2, 3 or 4,

at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or 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. Surprisingly, it has now been found that perbrominated rylenetetracarboxylic acid derivatives of formula I described below are particularly advantageously suitable as emitter materials, charge transport materials or exciton transport materials. They are characterized in particular as air-stable n-type semiconductors with extraordinarily high charge mobilities.

A first subject of the present invention therefore relates to compounds of general formula I,

in which

n is 2, 3 or 4,

R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and especially bromine, where at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} bromine,

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,

in the case where Y ^{1 is} NR ^a , one of the radicals Z ¹ or 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 or 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 flanking bonds stand. Another object of the invention relates to the use of the compounds of formula I as emitter materials, charge transport materials or Excitetonransport- materials.

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 general formula I may be perylenes, terrylenes or quaterrylenes of the following formulas:

(n = 4)

The higher homologues (n = 5, 6, 7, 8) are formed analogously.

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, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. The term alkyl also includes alkyl radicals whose carbon chains are replaced by one or more nonadjacent groups selected from -O-, -S-, -NR ^e -, -C (= O) -, -S (= O) - and / or -S (= O) 2- can be interrupted. R ^e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The term alkyl also includes substituted alkyl radicals. Substituted alkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the length of the alkyl chain. These are preferably selected independently from among cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , nitro and cyano, wherein E ¹ and E ² independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Halogen substituents are preferably fluorine, chlorine or bromine.

Alkylene is divalent straight or branched hydrocarbon radicals having usually 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms and especially 1 to 12 carbon atoms.

Carboxylate and sulfonate represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.

The above statements on alkyl also apply to the alkyl moieties in alkoxy, alkylamino, alkylthio, alkylsulfinyl, alkylsulfonyl, etc.

Aryl substituted alkyl ("arylalkyl") groups have at least one unsubstituted or substituted aryl group as defined below. In this case, the alkyl group in "arylalkyl" may carry at least one further substituent and / or may be substituted by one or more nonadjacent groups which are selected from -O-, -S-, -NR ^e -, -CO- and / or - SO2 be interrupted. Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C4-alkyl, for. For benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1- (phenmeth) eth-1-yl,

1- (phen-methyl) -1- (methyl) -eth-1-yl or - (phen-methyl) -1- (methyl) -prop-1-yl; preferably for benzyl and 2-phenethyl. The term "alkenyl" in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, may carry one or more double bonds (eg 1, 2, 3, 4 or more than 4). Preference is given to C 2 -C 18, particularly preferably C 2 -C 12 -alkenyl groups. In the context of the present invention alkenyl, which carries two double bonds in arbitrary positions, is also referred to as alkadienyl. The term "alkenyl" also includes substituted alkenyl groups which may carry one or more (eg, 1, 2, 3, 4, 5 or more than 5) substituents. Suitable substituents are, for. B. selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO3H, sulfonate, NE ³ E ⁴ , nitro and cyano, wherein E ³ and E ^{4 are} independently Hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Alkenyl is then, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl , 3-hexenyl, 4-hexenyl, 5-hexenyl, penta-1,3-dien-1-yl, hexa-1, 4-dien-1-yl, hexa-1, 4-dien-3-yl, hexa -1, 4-dien-6-yl, hexa-1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, hexa-1, 5-dien-4-yl, hepta-1 , 4-dien-1-yl, hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-yl, hepta-1, 4-dien-7-yl, hepta-1, 5 -dien-1-yl, hepta-1, 5-dien-3-yl, hepta-1, 5-dien-4-yl, hepta-1, 5-dien-7-yl, hepta-1, 6-diene 1-yl, hepta-1, 6-dien-3-yl, hepta-1, 6-dien-4-yl, hepta-1, 6-dien-5-yl, hepta-1, 6-diene-2 -yl, octa-1, 4-dien-1-yl, octa-1, 4-dien-2-yl, octa-1, 4-dien-3-yl, octa-1, 4-dien-6-yl , Octa-1, 4-dien-7-yl, octa-1, 5-dien-1-yl, octa-1, 5-dien-3-yl, octa-1, 5-dien-4-yl, octa -1, 5-dien-7-yl, octa-1, 6-dien-1-yl, octa-1, 6-dien-3-yl, octa-1, 6-dien-4-yl, octa-1 , 6-dien-5-yl, octa-1, 6-dien-2-yl, deca-1, 4-dienyl, deca-1, 5-dienyl, deca-1, 6-dienyl, deca-1, 7 -dienyl, deca-1, 8-dienyl, deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl and the like. The comments on alkenyl also apply to the alkenyl groups in alkenyloxy, alkenylthio, etc.

The term "alkynyl" includes unsubstituted or substituted alkynyl groups having one or more non-adjacent triple bonds, such as ethynyl,

1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4- Hexynyl, 5-hexynyl, and the like. The remarks on alkynyl also apply to the alkynyl groups in alkynyloxy, alkynylthio, etc. Substituted alkynyls preferably carry one or more (eg 1, 2, 3, 4, 5 or more than 5) of the substituents previously mentioned for alkyl.

The term "cycloalkyl" in the context of the present invention comprises unsubstituted as well as substituted cycloalkyl groups, preferably Cs-Cs-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particular particular Cs-Cs-cycloalkyl. Substituted cycloalkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably selected independently of one another from alkyl and the substituents mentioned above for the alkyl groups. In the case of a substitution, the cycloalkyl groups preferably carry one or more, for example one, two, three, four or five

Examples of preferred cycloalkyl groups are 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 cycloalkenyl includes unsubstituted and substituted monounsaturated hydrocarbon groups having 3 to 8, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexene 4-yl and the like. Suitable substituents are those previously mentioned for cycloalkyl.

The term bicycloalkyl preferably includes bicyclic hydrocarbon radicals having 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl , Bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like.

The term "aryl" in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. Aryl is preferably unsubstituted. Or substituted phenyl,

Naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and more preferably phenyl or naphthyl. Substituted aryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems. These are preferably selected independently from among alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO ₃ H, sulfonate, NE ⁵ E ⁶ , nitro and Cyano, wherein E ⁵ and E ^{6 are} independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Halogen substituents are preferably fluorine, chlorine or bromine. Aryl is particularly preferably Phenyl, which in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.

Aryl which carries one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl , 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3 , 5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl , 2,4,6-Tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and

2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl , 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert .-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl , 2,4-, 2,5-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5 -, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-cyanophenyl.

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 are substituted by heteroatoms selected from oxygen, Nitrogen, sulfur and a group -NR ^e - are replaced and which is unsubstituted or substituted by 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, tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl.

The term "heteroaryl" in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mono- or polynuclear groups, 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 preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, carboxy, halogen and cyano. Nitrogen-containing 5- to 7-membered heterocycloalkyl or heteroaryl radicals which optionally contain further heteroatoms selected from oxygen and sulfur include, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, 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 R ^a and R ^b mentioned in the following formulas are in detail:

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 3-methoxypropyl, 3 Ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7- Dioxanonyl, 4,7-dioxaoctyl, 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-butylthio-ethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl, 3-butylthiopropyl,

4-methylthiobutyl, 4-ethylthiobutyl, 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 -Tetrathiatetradecyl;

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-triazodecyl, 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-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-propylsulfinylethyl, 2-isopropylsulfinylethyl, 2-butylsulfinylethyl, 2- and 3-methylsulfinylpropyl, 2- and 3-ethylsulfinylpropyl, 2- and 3-propylsulfinylpropyl, 2- and 3-butylsulfinylpropyl, 2- and 4-methylsulfinylbutyl, 2- and 4-ethylsulfinylbutyl, 2- and 4-propylsulfinylbutyl and 4-butylsulfinylbutyl;

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, 3- and 4-hydroxybutyl and 8-hydroxy-4-oxo-octyl;

2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl;

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, butoxy, pentoxy and hexoxy;

Methylthio, ethylthio, propylthio, butylthio, 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 1-1 -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 11 dodecenyl and 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14-, 15-, 16- and 17-octadecenyl;

Methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, 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-dodecylaminosulfonyl, N, N-diphenylaminosulfonyl, and N, N-bis (4-chlorophenyl) aminosulfonyl;

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy) carbonyl and (4-chlorophenoxy) carbonyl;

Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 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-methyl-cycloheptyl, 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-methyliso -indolyl), 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-tetrahydroisoquinolinyl), 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-ethyl-quinolinyl);

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-butyl-phenyl; 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-butoxy-phenyl; 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-phenylamino-phenyl, 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-naphthyl-azo) -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-pyrimidyloxy and 2-, 4- and 5- Pyτimidylthio.

Preferred fluorine-containing radicals R ^a and R ^b are the following:

2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluoroethyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3, 3,3-pentafluoropropyl, 1H, 1H-pentadecafluorooctyl, 3-bromo-3,3-difluoropropyl, 3,3,3-trifluoropropyl, 3,3,3-trifluoropropyl, 1H, 1H, 2H, 2H-perfluorodecyl, 3- (perfluorooctyl) propyl, 4,4-difluorobutyl, 4,4,4-trifluorobutyl, 5,5,6,6,6-pentafluorohexyl, 2,2-difluoropropyl, 2,2,2- Trifluoro-1-phenylethylamino, 1-benzyl-2,2,2-trifluoroethyl, 2-bromo-2,2-difluoroethyl, 2,2,2-trifluoro-1-pyridin-2-yl-ethyl, 2,2-difluoropropyl,

2,2,2-trifluoro-1 - (4-methoxyphenyl) ethylamino, 2,2,2-trifluoro-1-phenylethyl, 2,2-difluoro-1-phenylethyl, 1 - (4-bromo-phenyl) -2 , 2,2-trifluoroethyl, 3-bromo-3,3-difluoropropyl, 3,3,3-trifluoropropylamine, 3,3,3-trifluoro-n-propyl, 1H, 1H, 2H, 2H-perfluorodecyl, 3 (Perfluorooctyl) propyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-cyano (2,3,5,6) tetrafluorophenyl, 4-carboxy-2,3,5,6-tetrafluorophenyl,

2,4-difluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 2,5-difluorophenyl, 2-fluoro-5-nitrophenyl, 2-fluoro-5-trifluoromethylphenyl, 2-fluoro-5- methylphenyl, 2,6-difluorophenyl, 4-carboxamido-2,3,5,6-tetrafluorophenyl, 2-bromo-4,6-difluorophenyl, 4-bromo-2-fluorophenyl, 2,3-difluorophenyl, 4-chloro 2-fluorophenyl, 2,3,4-trifluorophenyl, 2-fluoro-4-iodophenyl, 4-bromo-2,3,5,6-tetrafluorophenyl, 2,3,6-trifluorophenyl,

2-bromo-3,4,6-trifluorophenyl, 2-bromo-4,5,6-trifluorophenyl, 4-bromo-2,6-difluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,4-difluoro- 6-nitrophenyl, 2-fluoro-4-nitrophenyl, 2-chloro-6-fluorophenyl, 2-fluoro-4-methylphenyl, 3-chloro-2,4-difluorophenyl, 2,4-dibromo-6-fluorophenyl, 3, 5-dichloro-2,4-difluorophenyl, 4-cyano-2-fluorophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-3-trifluoromethylphenyl, 2-trifluoromethyl-6-fluorophenyl, 2,3,4,6-tetrafluorophenyl, 3-chloro-2-fluorophenyl, 5-chloro-2-fluorophenyl, 2-bromo-4-chloro-6-fluorophenyl, 2,3-dicyano-4,5,6-trifluorophenyl, 2,4,5-trifluoro-3-carboxyphenyl, 2,3,4-trifluoro-6-carboxyphenyl, 2,3,5-trifluorophenyl, 4-trifluoromethyl2,3,5,6-tetrafluorophenyl, 2-fluoro-5-carboxyphenyl,

2-chloro-4,6-difluorophenyl, 6-bromo-3-chloro-2,4-difluorophenyl, 2,3,4-trifluoro-6-nitrophenyl, 2,5-difluoro-4-cyanophenyl, 2,5- Difluoro-4-trifluoromethylphenyl, 2,3-difluoro-6-nitrophenyl, 4-trifluoromethyl-2,3-difluorophenyl, 2-bromo-4,6-difluorophenyl, 4-bromo-2-fluorophenyl, 2-nitrotetrafluorophenyl, 2, 2 ', 3,3', 4 ', 5,5', 6,6'-nonafluorobiphenyl, 2-nitro-3,5,6-trifluorophenyl, 2-bromo-6-fluorophenyl, 4-chloro-2-fluoro 6-iodophenyl, 2-fluoro-6-carboxyphenyl, 2,4-difluoro-3-trifluorophenyl, 2-fluoro-4-trifluorophenyl, 2-fluoro-4-carboxyphenyl, 4-bromo-2,5-difluorophenyl, 2 , 5-Dibromo-3,4,6-trifluorophenyl, 2-fluoro-5-methylsulphonylpenyl, 5-bromo-2-fluorophenyl, 2-fluoro-4-hydroxymethylphenyl, 3-fluoro-4-bromomethylphenyl, 2-nitro-4 trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-bromo-4-trifluoromethylphenyl, 2-bromo-6-chloro-4- (trifluoromethyl) phenyl, 2-chloro-4-trifluoromethylphenyl, 3-nitro-4- (trifluoromethyl) phenyl, 2 , 6-dichloro-4- (trifluoromethyl) phenyl, 4-trifluorophenyl,

2,6-Dibromo-4- (trifluoromethyl) phenyl, 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,5-difluoro-4-trifluoromethylphenyl, 3,5-difluoro 4-trifluoromethylphenyl, 2,3-difluoro-4-trifluoromethylphenyl, 2,4-bis (trifluoromethyl) phenyl, 3-chloro-4-trifluoromethylphenyl, 2-bromo-4,5-di (trifluoromethyl) phenyl, 5-chloro 2-nitro-4- (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 3,4-bis (trifluoromethyl) phenyl, 2-fluoro-3-trifluoromethylphenyl, 2-iodo-4-trifluoromethylphenyl, 2-nitro-4,5-bis (trifluoromethyl) phenyl, 2-methyl-4- (trifluoromethyl) phenyl,

3,5-dichloro-4- (trifluoromethyl) phenyl, 2,3,6-trichloro-4- (trifluoromethyl) phenyl, 4- (trifluoromethyl) benzyl, 2-fluoro-4- (trifluoromethyl) benzyl,

3-Fluoro-4- (trifluoromethyl) benzyl, 3-chloro-4- (trifluoromethyl) benzyl, 4-fluorophenethyl, 3- (trifluoromethyl) phenethyl, 2-chloro-6-fluorophenethyl, 2,6-dichlorophenethyl, 3-fluorophenethyl , 2-fluorophenethyl, (2-trifluoromethyl) phenethyl, 4-fluorophenethyl,

3-fluorophenethyl, 4-trifluoromethylphenethyl, 2,3-difluorophenethyl, 3,4-difluorophenethyl, 2,4-difluorophenethyl, 2,5-difluorophenethyl, 3,5-difluorophenethyl, 2,6-difluorophenethyl, 4- (4-fluorophenyl ) phenethyl, 3,5-di (trifluoromethyl) phenethyl, pentafluorophenethyl, 2,4-di (trifluoromethyl) phenethyl, 2-nitro-4- (trifluoromethyl) phenethyl, (2-fluoro-3-trifluoromethyl) phenethyl, (2- Fluoro-5-trifluoromethyl) phenethyl, (3-fluoro-5-trifluoromethyl) phenethyl, (4-fluoro-2-trifluoromethyl) phenethyl, (4-fluoro-3-trifluoromethyl) phenethyl, (2-fluoro-6-trifluoromethyl) phenethyl, (2,3,6-trifluoro) phenethyl, (2,4,5-trifluoro) phenethyl, (2,4,6-trifluoro) phenethyl, (2,3,4-trifluoro) phenethyl, (3,4 , 5-trifluoro) phenethyl, (2,3,5-trifluoro) phenethyl, (2-chloro-5-fluoro) phenethyl, (3-fluoro-4-trifluoromethyl) phenethyl, (2-chloro-5-trifluoromethyl) phenethyl, (2-fluoro-3-chloro-5-trifluoromethyl) phenethyl, (2 Fluoro-3-chloro) phenethyl, (4-fluoro-3-chloro) phenethyl, (2-fluoro-4-chloro) phenethyl, (2,3-difluoro-4-methyl) phenethyl, 2,6-difluoro 3-chlorophenethyl, (2,6-difluoro-3-methyl) phenethyl, (2-trifluoromethyl-5-chloro) phenethyl, (6-chloro-2-fluoro-5-methyl) phenethyl, (2,4-dichloro 5-fluoro) phenethyl, 5-chloro-2-fluorophenethyl, (2,5-difluoro-6-chloro) phenethyl, (2,3,4,5-tetrafluoro) phenethyl, (2-fluoro-4-trifluoromethyl) phenethyl, 2,3- (difluoro-4-trifluoromethyl) phenethyl, (2,5-di (trifluoromethyl)) phenethyl, 2-fluoro-3,5-dibromophenethyl, (3-fluoro-4-nitro) phenethyl, (2 Bromo-4-trifluoromethyl) phenethyl, 2- (bromo-5-fluoro) phenethyl, (2,6-difluoro-4-bromo) phenethyl, (2,6-difluoro-4-chloro) phenethyl, (3-chloro 5-fluoro) phenethyl, (2-bromo-5-trifluoromethyl) phenethyl and the like.

A further embodiment of the invention relates to compounds of the formula (I), where the groups R ^a and R ^{b are} groups of the formula (A) (so-called dovetail radicals). Preferably in the groups of the formula (A) the radicals R ^{e are} selected from C ₄ -Ce-Al kyl, preferably Cs-Cz-alkyl. Preferably, the groups R ^a and R ^b then both represent a group of the formula

(A) wherein

# represents the point of attachment to the imide nitrogen atom, and

the radicals R ^{e are} selected from C ₄ -Ce-Al kyl, preferably Cs-Cz-alkyl. At the leftovers

R ^e are then in particular linear alkyl radicals which are not interrupted by oxygen atoms. A preferred example of a group of formula (A) is

1-Hexylhept-1-yl.

Preference is given to compounds of the formula I in which n is 2 and 5, 6, 7 or 8

R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} bromine.

Preference is furthermore given to compounds of the formula I in which n is 3 and 7, 8, 9, 10, 11 or 12 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} bromine. Preference is furthermore given to compounds of the formula I in which n is 4 and 9, 10, 11, 12, 13, 14, 15 or 16 of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} bromine.

Rylenetetracarboxylic dianhydrides are referred to below as compounds I.A.

Rylenetetracarboxylic diimides are referred to below as compounds I.B, where compounds I. Ba

have no additional bridging group X and compounds I.Bbi and I.Bb2

have such an additional bridging group X. Preferred among the compounds of the formulas IA and I. Ba are the compounds shown below:

in which the radicals R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ^{24 are} halogen or cyano, especially bromine, where at least one of the radicals R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ or R ^{24 is} bromine and R ^a and R ^b independently of one another have one of the abovementioned meanings.

More preferably, at least one of R ^a or R ^{b is} an electron-withdrawing substituted radical.

In a specific embodiment, at least one of the radicals R ^a and R ^{b is} a radical mono- or polysubstituted with fluorine. Particularly preferably, both R ^a and R ^{b are} a radical mono- or polysubstituted with fluorine. Regarding suitable fluorinated radicals Reference will also be made to the statements made at the outset.

In a further specific embodiment, the radicals R ^a and R ^{b are the} same.

A further preferred embodiment is compounds of the general formulas I.Bbi and I.Bb2 where n and R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 have} the meanings given above and X see for a divalent bridging group having 2 to 5 atoms between the flanking bonds stands.

The bridging groups X together with the NC = N group to which they are attached are preferably a 5- to 8-membered heterocycle which is optionally mono-, di- or trisubstituted by cycloalkyl, heterocycloalkyl, aryl and / or hetaryl is fused, with the fused groups independently one, two, three or four substituents selected from alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , nitro and cyano where E ¹ and E ² are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and / or X is one, two or three substituents selected from optionally substituted alkyl, optionally substituted cycloalkyl and optionally substituted aryl , and / or X may be interrupted by 1, 2 or 3 optionally substituted heteroatoms.

Preferably, the bridging groups X are selected from groups of the formulas (III.a) to (III.d)

wherein

R ^ιv , R ^v , R ^vι , R ^v ", R ^vι " and R ^ιx independently of one another are hydrogen, alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl, hetaryloxy, halogen, hydroxyl, mercapto ( -SH), COOH, carboxylate, SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , nitro, alkoxycarbonyl, acyl or cyano, where E ¹ and E ² are each independently hydrogen, alkyl, cycloalkyl, Heterocycloalkyl, aryl or hetaryl are available.

In a specific embodiment, in the groups are (lll.a) to (lll.d), the radicals R ^IV, R ^V, R ^VI, R ^v ", R ^VIII" and R ^ιx hydrogen.

In the following, some particularly preferred compounds according to the invention are reproduced:

The compounds of the general formula I according to the invention can be prepared starting from known compounds having the same skeletal skeleton and ^carrying at least one hydrogen atom as radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ .

Accordingly, another object of the present invention relates to processes for the preparation of compounds of formula I,

where n, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ⁿ⁴ , Y ¹ , Y ² , Z ¹ , Z ² , Z ³ and Z ^{4 have} one of the meanings given above,

in which a compound of the formula II

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and especially bromine and n, Y ¹ , Y ² , Z ¹ , Z ² , Z ³ and Z ^{4 have} one of the previously given meaning of a bromination with N, N'-dibromoisocyanuric acid.

N, N'-dibromoisocyanuric acid is preferably used in an amount of about 0.8: 1 to 4: 1, more preferably about 0.9: 1 to 2: 1, based on one mole of the radicals R ⁿ¹ contained in the compounds of formula II , R ⁿ² , R ⁿ³ and R ⁿ⁴ , which are hydrogen.

The bromination is preferably carried out in the presence of oleum. In particular, oleum will be used as a solvent for the bromination reaction.

The oleum used for the bromination is preferably at least 20%, more preferably at least 25% and most preferably at least 28%, such as. B. 30% oleum.

Alternatively, bromination with N, N'-dibromoisocyanuric acid may also be carried out in the presence of an inorganic or organic acid other than oleum. Especially suitable for this purpose are organic acids, such as acetic acid, propionic acid or butyric acid, in particular acetic acid. Preferably, the organic acid is used as a solvent.

The reaction temperature is usually in the range of -10 to 120 ^° C. The upper limit of the reaction temperature is usually determined by the boiling point of the solvent or the organic or inorganic acid used.

For use of the products as semiconductors, it may be advantageous to subject the products to further purification. These include, for example, column chromatographic methods, wherein the products z. B. dissolved in a halogenated carbon hydrogen such as methylene chloride or a toluene / or petroleum ether / ethyl acetate mixture, a separation or filtration are subjected to silica gel. Furthermore, a purification by sublimation or crystallization is possible.

In the preparation of the compounds of the formula I according to the invention, it is ^{customary to start} from the corresponding compounds of the formula II, in which all the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} hydrogen. However, it may also be advantageous to start from halogen- or cyano-substituted, especially partially brominated, compounds of the formula II. A special subject of the present invention relates to processes for the preparation of rylenetetracarboxylic dianhydrides of the formula I.

in which R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano, especially bromine, in which a rylenetetracarboxylic dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano, especially bromine, and n is 2, 3 or 4, subjected to bromination with N, N'-dibromoisocyanuric acid.

Suitable process conditions for the bromination of the rylene dianhydride are those described above, to which reference is hereby made.

The rylenetetracarboximides of the formulas I.Ba, I.Bbi and I.Bb2 are likewise known from the bromination of the corresponding rylenetetracarboximides, in which at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen

N, N'-dibromoisocyanuric acid can be produced. Usually, however, they will be based on the known rylenetetracarboxylic dianhydrides of the formula ILA for their preparation.

Accordingly, a further subject of the present invention relates to processes for the preparation of compounds of the formula I. Ba,

wherein R ⁿ¹ , R ⁿ² , R ⁿ³ , R ⁿ⁴ , R ^a and R ^{b have} one of the meanings given ^above , ^wherein

a1) a rylene dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano, especially bromine, and n is 2, 3 or 4 is subjected to bromination with N, N'-dibromoisocyanuric acid, and

b1) the compound obtained in step a1) of a reaction with an amine of

Formula R ^a -NH ₂ and optionally a different amine of the formula R ^b -NH ₂ subjects.

Alternatively, the compounds of formula I.Ba can be prepared by a process wherein

a2) a rylene dianhydride of the formula ILA, first subjected to a reaction with an amine of the formula R ^a -NH 2 and optionally a different amine of the formula R ^b -NH 2, and

b2) subjecting the compound obtained in step a2) to bromination with N, N'-dibromoisocyanuric acid. getting produced.

A further subject of the present invention relates to a process for the preparation of compounds of the formulas I.Bbi and / or I.Bb2,

where n, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ⁿ⁴ and X have one of the meanings given ^above , in which one

a3) a rylene dianhydride of the formula ILA,

b3) subjecting the compound obtained in step a3) to a reaction with an amine of the formula H ₂ NX-NH ₂ .

Alternatively, the compounds of formulas I.Bbi and / or I.Bb2 can be prepared by a process in which

a4) subjecting a rylene dianhydride of the formula ILA to a reaction with an amine of the formula H ₂ NX-NH ₂ , and b4) subjecting the compound obtained in step a4) to bromination with N, N'-dibromocyanuric acid.

Steps a1), b2), a3) and b4):

Suitable process conditions for the bromination of the rylene skeleton in steps a1), b2), a3) and b4) are those described above, to which reference is hereby made.

Steps b1), a2), b3) and a4):

The imidation of the carboxylic anhydride groups in the reaction steps b1), a2), b3) and a4) is known in principle and z. B. in DE 10 2004 007 382 A1. Preferably, the reaction of the dianhydride with the primary amine is carried out in the presence of an aromatic solvent such as toluene, xylene, mesitylene, phenol or a polar aprotic solvent. Suitable polar aprotic solvents are nitrogen heterocycles, such as pyridine, pyrimidine, quinoline, isoquinoline, quinaldine, N-methylpiperidine, N-methylpiperidone and N-methylpyrrolidone. For the reaction with an aromatic diamine of the formula H 2 N-X-NH 2, preference is given to using a nitrogen heterocycle or phenol as solvent. Suitable catalysts are those mentioned below. When phenol is used as solvent, preference is given to using piperazine as the catalyst.

The reaction can be carried out in the presence of an imidation catalyst. Suitable imidation catalysts are organic and inorganic acids, eg. For example, formic acid, acetic acid, propionic acid and phosphoric acid. Suitable imidation catalysts are also organic and inorganic salts of transition metals, such as zinc, iron, copper and magnesium. These include z. As zinc acetate, zinc propionate, zinc oxide, iron (II) acetate, iron (III) chloride, iron (II) sulfate, copper (II) acetate, copper (II) oxide and magnesium acetate. The use of an imidation catalyst is preferably carried out in the reaction of aromatic amines and is generally also advantageous for the reaction of cycloaliphatic amines. When reacting aliphatic amines, in particular short-chain aliphatic amines, the use of an imidation catalyst can generally be dispensed with. The amount used of the imidation catalyst is preferably 5 to 80 wt .-%, particularly preferably 10 to 75 wt .-%, based on the total weight of the compound to be amidated. Preferably, the molar ratio of amine to dianhydride is about 2: 1 to 10: 1, more preferably 2: 1 to 4: 1, e.g. From 2.2: 1 to 3: 1.

The organic acids previously mentioned as imidation catalysts are also suitable as solvents.

The reaction temperature is in the steps b1), a2), b3) or a4) is generally ambient temperature to 200 ⁰ C, preferably 40 to 160 ⁰ C. The reaction of aliphatic and cycloaliphatic amines is preferably carried out in a temperature range of about 60 ⁰ C to 100 ⁰ C. The reaction of aromatic amines is preferably carried out in a temperature range of about 120 to 160 ⁰ C.

Preferably, the reaction in the reaction steps b1), a2), b3) or a4) under a protective gas atmosphere, such. Nitrogen.

The reaction steps b1), a2), b3) or a4) can be carried out under atmospheric pressure or, if desired, under elevated pressure. A suitable pressure range is in the range of about 0.8 to 10 bar. Preferably, when using volatile amines (boiling point about ≤ 180 ⁰ C), the use is under increased pressure.

The water formed in the reaction in steps b1), a2), b3) or a4) can be separated by distillation by methods known to the person skilled in the art.

In general, the diimides obtained in reaction step b1), a2), b3) or a4) can be used without further purification. For use of the products as semiconductors, however, it may be advantageous to subject the products to further purification. These include, for example, column chromatographic methods, wherein the products are preferably dissolved in a halogenated hydrocarbon, such as methylene chloride, subjected to separation or filtration on silica gel.

The compounds of the formula I are particularly advantageous as organic semiconductors. They usually act as n-semiconductors. If the compounds of the formula I used according to the invention are combined with other semiconductors and if it results from the position of the energy levels that the other semiconductors function as n-semiconductors, the compounds I can also function as p-type semiconductors by way of exception.

The compounds of the formula I are distinguished by their air stability. Furthermore, they have a high charge transport mobility, which clearly knew about organic semiconductor materials. They also have a high on / off ratio.

The compounds of the formula I are suitable in a particularly advantageous manner for organic field effect transistors. They can be used, for example, for the production of integrated circuits (ICs), for which hitherto usual n-channel MOSFET (metal oxide semiconductor field-effect transistor) are used. These are then CMOS analog semiconductor devices, eg. For microprocessors, microcontrollers, static RAM, and other digital logic cireuits. For the preparation of semiconductor materials, the compounds of the formula I can be further processed by one of the following methods: printing (offset, flexo, gravure, screen, inkjet, electrophotography), evaporation, laser transfer, photolithography, drop casting. They are particularly suitable for use in displays (especially large and / or flexible displays) and RFI D tags.

The compounds of the formula I are particularly advantageous as electron conductors in organic field effect transistors, organic solar cells and in organic light emitting diodes. They are furthermore particularly advantageous as exciton-transport material in excitonic solar cells.

The compounds of the formula I 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. From W.A. Crossland, I.D. Sprigle and A.B. Davey described in Photoluminescent LCDs (PL-LCD) using phosphors at Cambridge University and Screen Technology Ltd., Cambridge, UK. The compounds of the formula I are furthermore particularly suitable in displays which switch 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 of formula I are also particularly suitable for laser welding or thermal management. 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 a semiconductor, especially as an n-type semiconductor.

The invention further substrates with a plurality of organic field effect transistors, wherein at least a portion of the Feldeffektransistoren at least one compound of formula I, as defined above, contains 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 forming part of an integrated circuit, and wherein at least a portion of the transistors comprise 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, ceramics, SiO 2, especially quartz), 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 may be flexible or inflexible, 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), cyanopulluans (eg CYMM), polyvinylphenol, poly-p xylene, polyvinyl chloride, or thermally or moisture crosslinkable polymers. Special dielectrics are "seif assembled nanodielectrics", ie polymers derived from SiCI functionalities containing monomers such. B. CI ₃ SiOSiCl ₃ , CI ₃ Si (CH ₂ ) 6-SiCl ₃ , CI ₃ Si (CH ₂ ) ^ - SiCl ₃ and / or which by atmospheric moisture or by the addition of water in

Dilution can be crosslinked with solvents (see, for example, Faccietti Adv. Mat. 2005, 17, 1705-1725). Instead of water, hydroxyl-containing polymers such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene can serve as crosslinking components. There may also be at least one further polymer present during the crosslinking process, such as e.g. 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 , Si ₃ N ₄ , etc., ferroelectric insulators such as AbO ₃ , Ta ₂ Os, La ₂ Os, TiO ₂ , Y ₂ O ₃ , 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 6, 7, 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-ethylene): 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 commonly used in semiconductor materials or ICs, such as insulators, resistors, capacitors, printed conductors, 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 the general formula I (and, if appropriate, further semiconductor materials) is carried out 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 general formula I are particularly advantageous for use in a PVD process, since they do not decompose substantially 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. In general, 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 during the deposition is preferably in a range from about 20 to 250 ^° C., particularly preferably 50 to 200 ^° C. Surprisingly, it has been found that increased substrate temperatures during the deposition of the compounds of the formula I have advantageous effects on the properties of the compounds obtained May have semiconductor elements.

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 the formula I is deposited on the substrate in a thickness of 10 to 1000 nm, more preferably 15 to 250 nm. In a specific 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 RA Laudise et al. in "Physical Vapor Growth of Organic Semi- Conductors", Journal of Crystal Growth 187 (1998), pages 449-454, and "Physical Vapor Growth of Centimeter-sized Crystals of α-Hexathiophene", Journal of Cystal Growth 1982 (1997 ), Pages 416-427, to which reference is hereby made.

In a second preferred embodiment, the deposition of at least one compound of general formula I (and optionally other semiconductor materials) by a spin coating. Surprisingly, the compounds of the formula I used according to the invention can therefore also be used in a wet processing method (wet processing) for the production of semiconductor substrates. The compounds of the formula I should therefore also be suitable for the production of semiconductor elements, especially OFETs or based on OFETs, by a printing process. Standard printing processes (inkjet, flexo, offset, engraving, rotogravure, nano print) can be used. 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 to these "semiconductor inks" thickening substances, such as polymers, for. 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 located on the substrate, a gate insulating layer located thereon and the substrate, a semiconductor layer located 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 prior to the separation of at least one compound of general formula I (and optionally at least one further semiconductor material) is subjected to a modification. This modification serves to form regions that bond the semiconductor materials and / or regions where no semiconductor materials can be deposited. The surface of the substrate is preferred with at least one compound (C1) which is suitable for binding to the surface of the substrate and to 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 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. In US Pat. No. 11 / 353,934, which is hereby incorporated 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 bonding, coordinative interaction, van der Waals interactions, eg. 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; Trialkoxyaminoalkylsilanes such as triethoxyaminopropylsilane and N [(3-triethoxysilyl) -propyl] -ethylenediamine; Trialkoxyalkyl-3-glycidyl ether silanes, such as triethoxypropyl

3-glycidylethersilan; Trialkoxyallylsilanes such as allyltrimethoxysilane; Trialkoxy (isocyanatoalkyl) silanes; 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 hexamethyldisilazane (HMDS); Cs-Cso-alkylthiols, especially hexadecanethiol; Mercaptocarboxylic acids and mercaptosulphonic 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 semiconductors according to the invention conceivable such. Top Contact, Top Gate, Bottom Contact, Bottom Gate, or else 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 components are field effect transistors (FETs), bipolar junction transistors (BJTs), tunnel diodes, inverters, light-emitting components, 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. B. (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 compounds of the formula I are furthermore 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. 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 are capable of conducting the excited states along the polymer layer. allow chain. Such solar cells are referred to as excitonic solar cells within the meaning of the invention. The direct conversion of solar energy into electrical energy in solar cells is based on the internal photoelectric effect of a semiconductor material, ie the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a pn 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 pn 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. Solar cells usually consist of two absorbing materials with different band gaps 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. As described in US 2005/0098726 A1 and US 2005/0224905 A1, which is incorporated herein by reference in its entirety.

Suitable substrates are for. As oxidic materials (such as glass, ceramic, SiÜ2, especially quartz, etc.), polymers (eg., Polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) - acrylates, polystyrene and mixtures and composites thereof) and combinations thereof.

In principle, metals (preferably groups 2, 8, 9, 10, 11 or 13 of the Periodic Table, eg Pt, Au, Ag, Cu, Al, In, Mg, Ca) are suitable as electrodes (cathode, anode). , 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, an essentially transparent material is used as the anode with respect 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 at least one layer containing as organic semiconductor material at least one compound selected from compounds of the formula I 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, exciton blocking layers, EBL) that are not supposed to absorb multiplication layers. Suitable excitons and holes blocking layers are for. As described in US 6,451, 415.

Suitable Excitonenblockerschichten are z. B. Bathocuproine (BCP), 4,4 ', 4 "-Tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA) or Polyethylendioxythiophen (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 (hole transport material, hole transport material), the corresponding ETM (exciton transport material, exciton transport material) must be selected such that, after excitation of the compounds, rapid electron transfer to the ETM occurs. Suitable ETMs are z. B. C60 and other fullerenes, perylene-3,4: 9,10-bis (dicarboximide) (PTCDI), etc. If at least one compound of formula I is used as ETM, the complementary HTM must be chosen so that after excitation of the Connecting a fast 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., 252, 243-258 (1994).) Or as a bulk heterojunction or interpenetrated donor-acceptor network, cf., for example, Messner, M. Möbus, F. Stölzle, Mol. BCJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater., 11 (1), 15 (2001).). The photoactive layer based on a heterojunction between at least one compound of the formula I and one HTL (hole transport layer) or ETL (exciton transport layer, exciton transport layer) 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 4,461,922, US 6,198,091 and US 6,198,092). It can also be used in tandem cells 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 vacuum evaporation or in an 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, engraving, 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 and substituted acenes. Substituted acetals include 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, 4,8,1-tetraalkoxypentacenes and rubrene (5,6,11,12-tetraphenylnaphthacene). Suitable substituted pentacenes are described in US 2003/0100779 and US Pat. No. 6,864,396. A preferred acene is rubrene (5,6,1 1, 12-tetraphenylnaphthacene).

Phthalocyanines, such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, containing metal-free and divalent metals, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, in particular copper phthalocyanine, zinc phthalocyanine cyanine and metal-free phthalocyanine, hexadecachloro copper phthalocyanine, hexadecachlorozinc phthalocyanine, metal-free hexadechlorophthacocyanine, hexadecafluoro copper phthalocyanine, hexadecafluorophthalocyanine or metal-free hexafluorophathocyanocyanine.

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

Liquid crystalline (LC) materials, such as. Hexabenzocoronene (HBC-PhCl 2) or other coronene, coronodiimides, or triphenylenes such as 2,3,6,7,10,1-hexahexylthiotriphenylene (HTT6) or 2,3,6,7,10,11-hexakis - (4-n-nonylphenyl) -triphenylene (PTP9), 2,3,6,7,10,11-hexakis- (undecyloxy) -triphenylenes (HAT11). Particularly preferred are LCs 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.

Preferred thiophenes, oligothiophenes and substituted derivatives thereof are poly-3-hexylthiophene (P3HT) or compounds of the type α, α'-bis (2,2-dicyanovinyl) quinethiophene (DCV5T), poly (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), pyridine-containing polymers such as poly (pyridopyrazine vinylene), poly (pyridopyrazine vinylene) modified with alkyl groups, e.g., EHH-PpyPz, copolymers PTPTB , Polybenzimidazobenzophenanthroline (BBL), poly (9,9-dioctylfluorene-co-bis-N, N '- (4-methoxyphenyl) -bis-N, N'-phenyl-1,4-phenylenediamine) (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 (PPV), MEH-PPV (poly (2-methoxy-5- (2'-ethylhexyloxy) -1, 4-phenylenevinylene, MDMO-PPV (poly (2-methoxy-5- (3 ', 7'-dimethyloctyl-oxy) -1, 4-phenylenevinylene), cyano-paraphenylenevinylene (CN-PPV), CN-PPV modified with various alkoxy groups. PPE-PPV hybrid polymers (phenylene-ethynylene / phenylene-vinylene hybrid polymers).

Polyfluorene and alternating polyfluorene copolymers such. With 4,7-dithien-2'-yl-2,1,3-benzothiadiazole, and further poly (9,9'-dioctylfluorene-co-benzothiadiazole) (F ₈ BT), poly (9,9'- dioctylfluorene-co-bis-N, N '- (4-butylphenyl) -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.

Triarylamines, polytriarylamines, polycyclopentadienes, polypyrroles, polyfuran, polysilanes, polyphospholes, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine (TPD), 4,4'-bis ( carbazol-9-yl) biphenyl (CBP), 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) - 9,9'-spirobifluorene (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 would be a hole conductor.

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

p-n mixed materials, d. H. Donor and acceptor in one material, polymer, block polymers, polymers with C60s, C60 azo dyes, trimeric mixed material containing carotenoid type compounds, porphyrin type and quinoidal liquid crystalline compounds as 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: Br 2, tetrafluorotetracyanoquinodimethane (F ₄ -TCNQ), etc.

Another object of the invention is an organic light-emitting diode (OLED), which contains at least one compound of general formula I, as defined above. The compounds of the formula I can serve as charge transport material (electron conductor).

Organic light emitting diodes are basically made up of several layers. These include: 1. anode 2. hole-transporting layer 3. light-emitting layer 4. electron-transporting layer 5. cathode. It is also possible that the organi- see light-emitting diode does not have all of the layers mentioned, for example, an organic light-emitting diode with the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is also suitable, the functions of the layers ( 2) (hole-transporting layer) and (4) (electron-transporting layer) are taken over by the adjacent layers. OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable. The structure of organic light-emitting diodes and methods for their preparation are known in principle to those skilled in the art, for example from WO 2005/019373. Suitable materials for the individual layers of OLEDs are z. As disclosed in WO 00/70655. The disclosure of these documents is hereby incorporated by reference. The production of OLEDs according to the invention can be carried out by methods known to the person skilled in the art. Generally, an OLED is made by sequential vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass or polymer films. For vapor deposition, conventional techniques can be used such as thermal evaporation, chemical vapor deposition and others. In an alternative method, the organic layers may be coated from solutions or dispersions in suitable solvents using coating techniques known to those skilled in the art. Compositions which, in addition to a compound of the general formula I, comprise a polymeric material in one of the layers of the OLEDs, preferably in the light-emitting layer, are generally applied as a layer by processing from solution.

By the use according to the invention of the compounds I, OLEDs can be obtained with high efficiency. The OLEDs according to the invention can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are z. For example, screens of computers, televisions, screens in printers, kitchen appliances, and billboards, lights, and billboards. Mobile screens are z. For example, screens in cell phones, laptops, digital cameras, vehicles, and destination displays on buses and trains. Furthermore, the compounds I can be used in OLEDs with inverse structure. The compounds I are preferably used in these inverse OLEDs again in the light-emitting layer. The construction of inverse OLEDs and the materials usually used therein are known to the person skilled in the art.

Before they can be used as charge transport materials or exciton transport materials, it may be useful to subject the compounds of the formula I to a purification process. Suitable purification methods include transferring the compounds gene of formula I in the gas phase. These include cleaning by sublimation or PVD (physical vapor deposition). Preference is given to a fractional sublimation. For fractional sublimation and / or deposition of the compound, a temperature gradient is used. Preferably, the compound of the formula I is sublimated with heating in a carrier gas stream. The carrier gas then flows through a separation chamber. A suitable separation chamber has at least two different separation zones with different temperatures. Preferably, a so-called "three-zone furnace" is used. A suitable method and apparatus for fractional sublimation is described in US 4,036,594.

Another object of the invention is a method for the deposition or application of at least one compound of formula I on a (em) substrate by a gas phase deposition method or a wet application method.

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

Examples

Synthesis Examples:

Example 1 :

To a solution of 1, 6,7,12-tetrabromoperylene-3,4: 9,10-tetracarboxylic anhydride (15.0 g, 0.021 mol) in oleum (30%, 250 ml) at a temperature of 40 ⁰ C. over a period of 2 hours a solution of N, N'-dibromoisocyanuric acid (21, 5 g, 0.075 mol) in oleum (30%, 250 ml) was added dropwise. After the addition has ended, the reaction mixture is heated to 50 ^° C. and stirred at this temperature for 16 hours. Additional N, N'-dibromoisocyanuric acid (6.1 g, 0.02 mol) is added and stirred for an additional 16 hours. The reaction mixture is then added to ice-water, the precipitated solid is filtered off, washed neutral and dried in vacuo. Octabromylene-3,4: 9,10-tetracarboxylic anhydride was obtained as a red solid in an amount of 18.2 g (yield 85%). Example 2:

To a solution of N, N'-dimethyl-perylene-3,4: 9,10-tetracarboxylic acid imide (1.76 g, 4.2 mmol) in oleum (30%, 50 ml) is added at a temperature of 50 ⁰ CN, N'-dibromoisocyanuric acid (8.6 g, 30 mmol) and stirred for 16 hours. Subsequently, more N, N'-dibromoisocyanuric acid (1, 23 g) is added and stirred for a further 70 hours. The reaction mixture is then added to ice-water, the precipitated solid is filtered off, washed neutral and dried in vacuo. N, N'-dimethyl-octabromoperylene-3,4: 9,10-tetracarboxylic acid imide was obtained as a red solid in an amount of 3.4 g (yield 77%).

Claims

Patentantsprüche

1. Use of compounds of general formula I,

in which

n is 2, 3 or 4,

R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano, where at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} bromine,

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 ^{2 is} NR ^b , one of the radicals Z ³ or 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 flanking bonds stand,

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

2. Use according to claim 1, wherein n is 2.

3. Use according to claim 1, wherein n is 3.

4. Use according to claim 1, wherein n is 4.

5. Use according to one of the preceding claims of compounds of the formulas I. A

wherein R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} bromine.

6. Use according to one of claims 1 to 4 of compounds of the formula I. Ba

wherein R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} bromo and R ^a and R ^{b are} independently hydrogen or unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or Heteroaryl stand.

Use according to one of Claims 1 to 4 of compounds of the formulas I.Bbi and I.Bb2

in which

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

X represents a divalent bridging group of 2 to 5 atoms between the flanking bonds.

8. Use of compounds of the general formula I as defined in any of claims 1 to 7, as electron conductors in organic field effect transistors, organic solar cells and in organic light emitting diodes.

9. Use according to claim 8 as a semiconductor material in organic field effect transistors.

10. Use of compounds of general formula I, as defined in any one of claims 1 to 7, as an emitter material in organic light-emitting diodes.

1 1. Use of compounds of general formula I, as defined in any one of claims 1 to 7, as an active material in organic photovoltaics, in particular as an exciton transport material in excitonic solar cells.

12. Use of compounds of the general formula I as defined in any one of claims 1 to 7, as a light absorber or light emitter.

13. Use of a compound of the general formula I as defined in any one of claims 1 to 7, for optical labels, for the invisible marking of products, as fluorescent dyes, as a fluorescent label for biomolecules and as pigments.

14. Use of a compound of the general formula I as defined in any one of claims 1 to 7, as a fluorescent dye in a fluorescence on version 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 chemiluminescence-based application.

15. Process for the preparation of compounds of the formula I,

where n, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ⁿ⁴ , Y ¹ , Y ² , Z ¹ , Z ² , Z ³ and Z ^{4 have} one of the meanings given in one of claims 1 to 7,

in which a compound of the formula II

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and n, Y ¹ , Y ² , Z ¹ , Z ² , Z ³ and Z ^{4 have} one of the given in one of claims 1 to 7 given to a bromination with N, N'-dibromoisocyanuric acid in the presence of an inorganic or organic acid.

16. The method according to claim 15, wherein the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ⁿ⁴ in the compound of formula II are hydrogen.

17. Process for the preparation of compounds of the formula I.A,

in which the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano, where at least one of the radicals R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} bromine,

in which a rylenetetracarboxylic acid dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and n is 2, 3 or 4, one Bromination with N, N'-dibromoisocyanuric acid subjects.

18. Process for the preparation of compounds of the formula I. Ba,

wherein n is 2, 3, or 4, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ^{n4 are} halogen or cyano and R ^a and R ^{b are} independently hydrogen or unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, Cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl, in which a1) a rylenetetracarboxylic acid dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and n is 2, 3 or 4, one Bromination with N, N'-dibromo- isocyanuric acid, and

b1) subjecting the compound obtained in step a1) to a reaction with an amine of the formula R ^a -NH 2 and, if appropriate, a different amine of the formula R ^b -NH 2.

19. Process for the preparation of compounds of the formula LBa,

wherein n is 2, 3 or 4, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ^{n4 are} halogen or cyano and R ^a and R ^{b are} independently hydrogen or unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl , Bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl in which

a2) a rylenetetracarboxylic acid dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and n is 2, 3 or 4, one Reaction with an amine of the formula R ^a -NH 2 and optionally a different amine of the formula R ^b -NH2 subjects, and

b2) subjecting the compound obtained in step a2) to bromination with N, N'-dibromoisocyanuric acid.

20. Process for the preparation of compounds of the formulas I.Bbi and / or I.Bb2,

wherein n is 2, 3 or 4, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ^{n4 are} halogen or cyano and X is a divalent bridging group having 2 to 5 atoms between the flanking bonds, ^wherein

a3) a rylenetetracarboxylic dianhydride of the formula ILA,

b3) subjecting the compound obtained in step a3) to a reaction with an amine of the formula H 2 N -X-NH 2.

21. Process for the preparation of compounds of the formulas I.Bbi and / or I.Bb2,

wherein n is 2, 3, or 4, R ⁿ¹ , R ⁿ² , R ⁿ³ , R ^{n4 are} halogen or cyano and X is a divalent bridging group having 2 to 5 atoms between the flanking bonds, ^wherein

a4) a rylenetetracarboxylic dianhydride of the formula ILA,

wherein at least one of R ⁿ¹ , R ⁿ² , R ⁿ³ or R ^{n4 is} hydrogen, the remaining R ⁿ¹ , R ⁿ² , R ⁿ³ and R ^{n4 are} halogen or cyano and n is 2, 3 or 4, one Reaction with an amine of the formula H2N-X-NH2 subjects, and

b4) subjecting the compound obtained in step a4) to bromination with N, N'-dibromocyanuric acid.

22. Compounds of general formula I as defined in any one of claims 1 to 7.

23. 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 formula I as defined in any one of claims 1 to 7, as n-type semiconductor.

24. A substrate having a multiplicity of organic field-effect transistors, wherein at least part of the field-effect transistors contains at least one compound of the formula I as defined in one of claims 1 to 7 as n-type semiconductor.

25. A semiconductor device comprising at least one substrate as defined in claim 24.

26. OLED containing at least one compound of the formula I as defined in one of claims 1 to 7.