DE102012022880B4 - Electronic devices containing organic layers - Google Patents

Abstract

wobei für die auftretenden Symbole gilt:
E ist eine divalente Gruppe gewählt aus S=O und S(=O)₂;
W, X sind bei jedem Auftreten gleich oder verschieden N, P oder CR¹;
Y ist bei jedem Auftreten gleich oder verschieden NR¹, PR¹, O oder S;
Z ist gleich C, wenn ein Substituent gebunden ist, und ist anderenfalls bei jedem Auftreten gleich oder verschieden CR¹ oder N;
R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, C(=O)R², CN, Si(R²)₃, N(R²)₂, NO₂, P(=O)(R²)₂, S(=O)R², S(=O)₂R², eine geradkettige Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen, wobei die oben genannten Gruppen jeweils mit einem oder mehreren Resten R² substituiert sein können und wobei eine oder mehrere CH₂-Gruppen in den oben genannten Gruppen durch -R²C=CR²-, -C=C-, Si(R²)₂, C=O, C=S, C=NR², -C(=O)O-, -C(=O)NR²-, NR², P(=O)(R²), -O-, -S-, SO oder SO₂ ersetzt sein können und wobei ein oder mehrere H-Atome in den oben genannten Gruppen durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 30 aromatischen Ring-atomen, die durch einen oder mehrere Reste R² substituiert sein kann, wobei zwei oder mehr Reste R¹ miteinander verknüpft sein können und einen Ring bilden können; wobei die Gruppe R¹, die an die Gruppe E gebunden ist, gewählt ist aus aromatischen oder heteroaromatischen Ringsystemen mit 5 bis 30 aromatischen Ringatomen, welche jeweils mit einem oder mehreren Resten R² substituiert sein können;
R² ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, C(=O)R³, CN, Si(R³)₃, N(R³)₂ ^, NO₂, P(=O)(R³)₂, S(=O)R³, S(=O)₂R³, eine geradkettige Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen, wobei die oben genannten Gruppen jeweils mit einem oder mehreren Resten R³ substituiert sein können und wobei eine oder mehrere CH₂-Gruppen in den oben genannten Gruppen durch -R³C=CR³-, -C≡C-, Si(R³)₂, C=O, C=S, C=NR³, -C(=O)O-, -C(=O)NR³-, NR³, P(=O)(R³), -O-, -S-, SO oder SO₂ ersetzt sein können und wobei ein oder mehrere H-Atome in den oben genannten Gruppen durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R³ substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 30 aromatischen Ring-atomen, die durch einen oder mehrere Reste R³ substituiert sein kann, wobei zwei oder mehr Reste R² miteinander verknüpft sein können und einen Ring bilden können;
R³ ist bei jedem Auftreten gleich oder verschieden H, D, F oder ein aliphatischer, aromatischer oder heteroaromatischer organischer Rest mit 1 bis 20 C-Atomen, in dem auch ein oder mehrere H-Atome durch D oder F ersetzt sein können; dabei können zwei oder mehr Substituenten R³ miteinander verknüpft sein und einen Ring bilden.Electronic device containing at least one organic layer, wherein the organic layer comprises one or more compounds of formula (I) or (II)

where the symbols appearing are:
E is a divalent group chosen from S=O and S(=O) ₂ ;
W, X are the same or different at each occurrence as N, P or CR ¹ ;
Y is the same or different at each occurrence: NR ¹ , PR ¹ , O or S;
Z is equal to C when a substituent is attached and is otherwise the same or different at each occurrence and is CR ¹ or N;
R ¹ is, identically or differently at each occurrence, H, D, F, Cl, Br, I, C(=O)R ² , CN, Si(R ² ) ₃ , N(R ² ) ₂ , NO ₂ , P(=O)(R ² ) ₂ , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups can each be substituted by one or more radicals R ² and where one or more CH ₂ groups in the abovementioned groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² ) ₂ , C=O, C=S, C=NR ² , -C(=O)O-, -C(=O)NR ² -, NR ² , P(=O)(R ² ), -O-, -S-, SO or SO ₂ and wherein one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , wherein two or more radicals R ¹ can be linked to one another and can form a ring; wherein the group R ¹ which is bonded to the group E is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² ;
R ² is, identically or differently on each occurrence, H, D, F, Cl, Br, I, C(=O)R ³ , CN, Si(R ³ ) ₃ , N(R ³ ) ₂ ^, NO ₂ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ³ and where one or more CH ₂ groups in the abovementioned groups are replaced by -R ³ C=CR ³ -, -C≡C-, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , -C(=O)O-, -C(=O)NR ³ -, NR ³ , P(=O)(R ³ ), -O-, -S-, SO or SO ₂ and where one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ³ , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ³ , where two or more radicals R ² can be linked to one another and can form a ring;
R ³ is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more R ³ substituents may be linked to one another to form a ring.

Description

The present invention relates to an electronic device containing one or more compounds of formula (I) or (II). The invention further relates to the use of a compound of formula (I) or (II) in an electronic device, preferably in an organic electroluminescent device, particularly preferably as matrix material in an emitting layer. The invention further relates to certain compounds of formula (I) or (II) which are suitable for use in the device according to the invention.

The development of functional compounds for use in electronic devices is currently the subject of intensive research. One of the aims is to develop compounds that enable an improved property profile of the devices. Also of interest is the provision of alternative compounds for use in electronic devices.

According to the present invention, the term electronic device includes, inter alia, organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), organic plasmon-emitting diodes and organic electroluminescent devices (OLEDs).

The structure of the above-mentioned organic electroluminescent devices (OLEDs) is known to the person skilled in the art and is described, among other things, in US 4539507 , US 5151629 , EP 0676461 and WO 1998/27136 described.

With regard to the performance data of the organic electroluminescent devices, further improvements are required, particularly with regard to broad commercial use. Of particular importance in this context are the service life, efficiency and operating voltage of the organic electroluminescent devices as well as the color values achieved. There is potential for improvement in the service life of blue-emitting electroluminescent devices in particular. It is also desirable that the compounds for use as functional materials in electronic devices have high thermal stability and a high glass transition temperature and can be sublimated without decomposition.

There is also a need for matrix materials, particularly matrix materials for phosphorescent emitters, which simultaneously lead to good efficiency, a long service life and a low operating voltage of the electronic devices. There is also particular interest in the provision of matrix materials for green-emitting phosphorescent dopants. The properties of the matrix materials in particular are often limiting for the service life and efficiency of the organic electroluminescent device. In the case of matrix materials for phosphorescent emitters, it is desirable that they have a high T ₁ level (triplet level). This is particularly relevant for matrix materials for blue-emitting phosphorescent emitters.

Furthermore, the provision of new electron transport materials is desirable, since the properties of the electron transport material have a significant influence on the above-mentioned properties of the organic electroluminescent device. In particular, there is a need for electron transport materials that simultaneously lead to good efficiency, a long service life and a low operating voltage.

According to the state of the art, carbazole derivatives, e.g. bis(carbazolyl)biphenyl, are often used as matrix materials for phosphorescent emitters. Ketones ( WO 2004/093207 ), phosphine oxides, sulfones ( WO 2005/003253 ) and triazine compounds such as triazinylspirobifluorene (cf. WO 2010/015306 ) used.

Known in the art is the use of benzimidazole compounds substituted with aryl groups in OLEDs ( WO 2004/080975 ). Also known for this use are benzoxazole and benzothiazole compounds ( WO 2010/027181 ).

In US 2009/184633 , JP 2008/130754 and JP 2006/156847 Benzimidazole compounds substituted with an electron-deficient heteroaryl group are disclosed for use in OLEDs.

• - Korshak et al. : Synthesis and investigation of poly(benzimidazole imides) based on new di-imidodicarboxylic acids, Polymer Science U.S.S.R. 1980, Vol. 22, No 6, S. 1325-1333
• - Jouanneau et al. : Synthesis and characterization of ionic conducting sulfonated polybenzimidazoles, J. Polym. Sci. Part A, 2010, Vol. 48, No. 8, S. 1732-1742
• - Korshak et al. : Two-stage synthesis of poly(N-phenylbenzimidazoles, Macromolecules 1972, Vol. 5, No. 6, S. 807-812 , and
• - WO 2011/076323 A1 .

Benzimidazole compounds substituted with a sulfoxide or sulfone are also disclosed in the following prior art:

• - Korshak et al. : Synthesis and investigation of poly(benzimidazole imides) based on new di-imidodicarboxylic acids, Polymer Science USSR 1980, Vol. 22, No 6, pp. 1325-1333
• - Jouanneau et al. : Synthesis and characterization of ionic conducting sulfonated polybenzimidazoles, J. Polym. Sci. Part A, 2010, Vol. 48, No. 8, pp. 1732-1742
• - Korshak et al. : Two-stage synthesis of poly(N-phenylbenzimidazoles, Macromolecules 1972, Vol. 5, No. 6, pp. 807-812 , and
• - WO 2011/076323 A1 .

The present invention is therefore based on the technical object of providing alternative compounds which are suitable for use in electronic devices such as OLEDs and which can be used in particular as matrix materials for phosphorescent emitters and/or as electron transport materials.

Within the scope of the present invention, it has now been found that compounds of the formula (I) or (II) given below are excellently suitable for use in electronic devices, in particular as matrix materials for phosphorescent emitters and/or as electron transport materials.

wobei für die auftretenden Symbole gilt:

E

ist eine divalente Gruppe gewählt aus S=O und S(=O)₂;

W, X

sind bei jedem Auftreten gleich oder verschieden N, P oder CR¹;

Y

ist bei jedem Auftreten gleich oder verschieden NR¹, PR¹, O oder S;

Z

ist gleich C, wenn ein Substituent gebunden ist, und ist anderenfalls bei jedem Auftreten gleich oder verschieden CR¹ oder N;

R1

ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, C(=O)R², CN, Si(R²)₃, N(R²)₂, NO₂, P(=O)(R²)₂, S(=O)R², S(=O)₂R², eine geradkettige Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen, wobei die obengenannten Gruppen jeweils mit einem oder mehreren Resten R² substituiert sein können und wobei eine oder mehrere CH₂-Gruppen in den oben genannten Gruppen durch -R²C=CR²-, -C≡C- , Si(R²)₂, C=O, C=S, C=NR², -C(=O)O-, -C(=O)NR²-, NR², P(=O)(R²), -O-, -S-, SO oder SO₂ ersetzt sein können und wobei ein oder mehrere H-Atome in den oben genannten Gruppen durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 30 aromatischen Ringatomen, die durch einen oder mehrere Reste R² substituiert sein kann, wobei zwei oder mehr Reste R¹ miteinander verknüpft sein können und einen Ring bilden können; wobei die Gruppe R¹, die an die Gruppe E gebunden ist, gewählt ist aus aromatischen oder heteroaromatischen Ringsystemen mit 5 bis 30 aromatischen Ringatomen, welche jeweils mit einem oder mehreren Resten R² substituiert sein können;

R2

ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, C(=O)R³, CN, Si(R³)₃, N(R³)₂, NO₂, P(=O)(R³)2, S(=O)R³, S(=O)₂R³, eine geradkettige Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen, wobei die oben genannten Gruppen jeweils mit einem oder mehreren Resten R³ substituiert sein können und wobei eine oder mehrere CH₂-Gruppen in den oben genannten Gruppen durch -R³C=CR³-, -C≡C- , Si(R³)₂, C=O, C=S, C=NR³, -C(=O)O-, -C(=O)NR³-, NR³, P(=O)(R³), -O-, -S-, SO oder SO₂ ersetzt sein können und wobei ein oder mehrere H-Atome in den oben genannten Gruppen durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R³ substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 30 aromatischen Ringatomen, diedurch einen oder mehrere Reste R³ substituiert sein kann, wobei zwei oder mehr Reste R² miteinander verknüpft sein können und einen Ring bilden können;

R3

ist bei jedem Auftreten gleich oder verschieden H, D, F oder ein aliphatischer, aromatischer oder heteroaromatischer organischer Rest mit 1 bis 20 C-Atomen, in dem auch ein oder mehrere H-Atome durch D oder F ersetzt sein können; dabei können zwei oder mehr Substituenten R³ miteinander verknüpft sein und einen Ring bilden.

The invention thus relates to an electronic device comprising at least one organic layer, wherein the organic layer comprises one or more compounds of formula (I) or (II)

where the symbols appearing are:

E

is a divalent group chosen from S=O and S(=O) ₂ ;

W, X

are the same or different at each occurrence: N, P or CR ¹ ;

Y

is the same or different at each occurrence: NR ¹ , PR ¹ , O or S;

Z

is equal to C when a substituent is attached and is otherwise the same or different at each occurrence and is CR ¹ or N;

R1

is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R ² , CN, Si(R ² ) ₃ , N(R ² ) ₂ , NO ₂ , P(=O)(R ² ) ₂ , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ² and where one or more CH ₂ groups in the abovementioned groups are substituted by -R ² C=CR ² -, -C≡C- , Si(R ² ) ₂ , C=O, C=S, C=NR ² , -C(=O)O-, -C(=O)NR ² -, NR ² , P(=O)(R ² ), -O-, -S-, SO or SO ₂ and where one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can be linked to one another and can form a ring; wherein the group R ¹ which is bonded to the group E is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ² ;

R2

is, identically or differently on each occurrence, H, D, F, Cl, Br, I, C(=O)R ³ , CN, Si(R ³ ) ₃ , N(R ³ ) ₂ , NO ₂ , P(=O)(R ³ )2, S(=O)R ³ , S(=O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ³ and where one or more CH ₂ groups in the abovementioned groups are -R ³ C=CR ³ -, -C≡C-, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , -C(=O)O-, -C(=O)NR ³ -, NR ³ , P(=O)(R ³ ), -O-, -S-, SO or SO ₂ and where one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ³ , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ³ , where two or more radicals R ² can be linked to one another and can form a ring;

R3

is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R ³ may be linked to one another to form a ring.

• Eine Arylgruppe im Sinne dieser Erfindung enthält 6 bis 60 aromatische Ringatome; eine Heteroarylgruppe im Sinne dieser Erfindung enthält 5 bis 60 aromatische Ringatome, von denen mindestens eines ein Heteroatom darstellt. Die Heteroatome sind bevorzugt ausgewählt aus N, O und S. Dies stellt die grundlegende Definition dar. Werden in der Beschreibung der vorliegenden Erfindung andere Bevorzugungen angegeben, beispielsweise bezüglich der Zahl der aromatischen Ringatome oder der enthaltenen Heteroatome, so gelten diese.

The following general definitions apply in this application:

• An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms; a heteroaryl group in the sense of this invention contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. The heteroatoms are preferably selected from N, O and S. This represents the basic definition. If other preferences are given in the description of the present invention, for example with regard to the number of aromatic ring atoms or the heteroatoms contained, these apply.

An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a condensed (fused) aromatic or heteroaromatic polycycle, for example naphthalene, phenanthrene, quinoline or carbazole. A condensed (fused) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic cycles condensed together. Such a group is also referred to as a condensed aryl group or heteroaryl group in the context of the present invention.

An aryl or heteroaryl group, which can be substituted by the above-mentioned radicals and which can be linked to the aromatic or heteroaromatic via any position, is understood to mean in particular groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, Naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimi dazol, oxazole, benzopyridazine, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

An aryloxy group according to the definition of the present invention is understood to mean an aryl group as defined above which is bonded via an oxygen atom. An analogous definition applies to heteroaryloxy groups.

An aromatic ring system in the sense of this invention contains 6 to 60 C atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of this invention is to be understood as a system which does not necessarily only contain aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as an sp ³ -hybridized C, Si, N or O atom, an sp ² -hybridized C or N atom or an sp-hybridized C atom. For example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, for example systems such as biphenyl, terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, which can be substituted with residues as defined above and which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean in particular groups which are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzphenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, Isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, Phenanthrimidazole, Pyridimidazole, Pyrazinimidazole, Quinoxalinimidazole, Oxazole, Benzoxazole, Naphthoxazole, Anthroxazole, Phenanthroxazole, Isoxazole, 1,2-thiazole, 1,3-thiazole, Benzothiazole, Pyridazine, Benzopyridazine, Pyrimidine, Benzpyrimidine, Quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or combinations of these groups.

In the context of the present invention, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which individual H atoms or CH ₂ groups can also be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neo-hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, Trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl or octynyl. Among an alkoxy or thioalkyl group with 1 to 40 carbon atoms, preference is given to methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy, 2,2,2-Trifluorethoxy, Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-Heptylthio, Cyclo heptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, Cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentinylthio, hexynylthio, heptynylthio or octynylthio are understood.

The phrase that two or more residues can form a ring with each other is to be understood in the context of the present application to mean, among other things, that the two residues are linked to each other by a chemical bond. This is illustrated by the following scheme:

Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bound, forming a ring. This is illustrated by the following scheme:

The following preferred embodiments apply to the compounds of formula (I) and (II).

Preferably, E is S(=O) ₂ .

The group E can be bonded to any position on the six-membered ring and is preferably bonded in meta- or para-position to the group Y.

Preferably, W is the same or different at each occurrence from N or CR ¹ . Particularly preferably, W is N.

Preferably, X is the same or different on each occurrence and is N or CR ¹ . Particularly preferably, X is CR ¹ .

Preferably, Y is the same or different on each occurrence and is NR ¹ , O or S, particularly preferably NR ¹ .

Very particularly preferred is an embodiment in which W is N, X is CR ¹ and Y is NR ¹ .

The compound of formula (I) or (II) preferably does not have a condensed aryl group with more than 13 aromatic ring atoms. It has been found that without the presence of a condensed aryl group with more than 13 aromatic ring atoms in the compound, OLEDs with significantly improved properties in terms of efficiency and lifetime can be obtained. This applies in particular to OLEDs containing the compound in a layer which contains one or more phosphorescent emitters. The compound of formula (I) or (II) particularly preferably does not have a condensed aryl group with more than 10 aromatic ring atoms.

In the case where no substituent is bonded to a group Z, this group Z is preferably CR ¹ . It is furthermore preferred that 0, 1 or 2 groups Z per aromatic six-membered ring are N and the remaining groups Z to which no substituent is bonded are CR ¹ . It is furthermore preferred that no more than two adjacent groups Z are N.

Preferably, R ¹ is, identically or differently on each occurrence, H, D, F, CN, Si(R ² ) ₃ , N(R ² ) ₂ , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ² and where in the abovementioned groups one or more CH ₂ groups may be replaced by -C=C-, -R ² C=CR ² -, Si(R ² ) ₂ , C=O, C=NR ² , -NR ² -, -O-, -S-, -C(=O)O- or -C(=O)NR ² -, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, where two or more R ¹ radicals can be linked to one another and can form a ring; where the group R ¹ which is bonded to the group E is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, which can each be substituted by one or more R ² radicals. Preferably, the group R ¹ which is bonded to the group E is selected from aromatic ring systems having 6 to 18 aromatic ring atoms, which can be substituted by one or more R ² radicals.

Preferably, R ² is, identically or differently on each occurrence, H, D, F, CN, Si(R ³ ) ₃ , N(R ³ ) ₂ , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ³ and where in the abovementioned groups one or more CH ₂ groups may be replaced by -C≡C-, -R ³ C=CR ³ -, Si(R ³ ) ₂ , C=O, C=NR ³ , -NR ³ -, -O-, -S-, -C(=O)O- or -C(=O)NR ³ -, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each substituted by one or more several radicals R ³ , where two or more radicals R ² can be linked together to form a ring.

Preferably, at least one group selected from aromatic ring systems having 6 to 18 aromatic ring atoms, preferably 12 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R ² , is bonded to the base body of the compound of formula (I) or (II).

• - Heteroarylgruppen mit 5 bis 20 aromatischen Ringatomen, die mit einem oder mehreren Resten R² substituiert sein können und die mindestens einen heteroaromatischen Fünfring mit zwei oder mehr Heteroatomen gewählt aus N, O und S enthalten;
• - Heteroarylgruppen mit 5 bis 20 aromatischen Ringatomen, die mit einem oder mehreren Resten R² substituiert sein können und die mindestens einen heteroaromatischen Sechsring mit einem oder mehreren Heteroatomen gewählt aus N, O und S enthalten; und
• - Carbazolderivaten, die mit einem oder mehreren Resten R² substituiert sein können.

Particularly preferably, the compound of formula (I) or (II) contains at least one group R ¹ which is selected from

• - heteroaryl groups having 5 to 20 aromatic ring atoms which may be substituted by one or more radicals R ² and which contain at least one heteroaromatic five-membered ring with two or more heteroatoms selected from N, O and S;
• - heteroaryl groups having 5 to 20 aromatic ring atoms, which may be substituted by one or more radicals R ² and which contain at least one heteroaromatic six-membered ring with one or more heteroatoms selected from N, O and S; and
• - Carbazole derivatives which may be substituted by one or more radicals R ² .

For the purposes of the present invention, carbazole derivatives also include carbazole derivatives with fused groups, such as indenocarbazoles or indolocarbazoles, as well as carbazole derivatives in which one or more carbon atoms in the aromatic six-membered rings are replaced by nitrogen.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten und m bei jedem Auftreten gleich 0 oder 1 ist, wobei die Summe der Indices m gleich 1 ist. Bevorzugt sind die oben angegebenen bevorzugten Ausführungsformen der auftretenden Gruppen. Insbesondere bevorzugt ist Z gleich CR¹ oder C. Weiterhin ist bevorzugt E gleich S(=O)₂.Preferred embodiments of the compound according to formula (I) correspond to the following formula

where the definitions given above apply to the groups occurring and m is equal to 0 or 1 at each occurrence, where the sum of the indices m is equal to 1. The preferred embodiments of the groups occurring given above are preferred. Z is particularly preferably CR ¹ or C. Furthermore, E is preferably equal to S(=O) ₂ .

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten. Bevorzugt sind die oben angegebenen bevorzugten Ausführungsformen der auftretenden Gruppen. Insbesondere bevorzugt ist Z gleich CR¹. Weiterhin ist bevorzugt E gleich S(=O)₂.Preferred embodiments of the compound according to formula (II) correspond to the following formulas

where the definitions given above apply to the groups that occur. The preferred embodiments of the groups that occur given above are preferred. Z is particularly preferably CR ¹ . Furthermore, E is preferably S(=O) ₂ .

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten und
m bei jedem Auftreten gleich 0 oder 1 ist, wobei die Summe der Indices m gleich 1 ist, und
p gleich 0, 1 oder 2 ist; und
Ar² eine Aryl- oder Heteroarylgruppe mit 5 bis 10 aromatischen Ringatomen darstellt, welche mit einem oder mehreren Resten R² substituiert sein kann, und
Het eine Gruppe der Formel (Het-a) darstellt

wobei T gleich N oder CR² ist, wobei mindestens eine Gruppe T gleich N ist, und die gestrichelte Linie die Bindung an den Rest der Verbindung bezeichnet,
oder Het eine Gruppe der Formel (Het-b) oder (Het-c) darstellt

wobei die auftretenden Symbole wie oben definiert sind und die gestrichelte Linie die Bindung an den Rest der Verbindung bezeichnet,
oder Het eine Gruppe der Formel (Het-d) oder (Het-e) darstellt

wobei T gleich N oder CR² ist und mindestens eine Gruppe T gleich N ist, und die gestrichelte Linie die Bindung an den Rest der Verbindung bezeichnet.A particularly preferred embodiment of the compound according to formula (I) corresponds to the following formula:

where the definitions given above apply to the groups occurring and
m is equal to 0 or 1 at each occurrence, where the sum of the indices m is equal to 1, and
p is 0, 1 or 2; and
Ar ² represents an aryl or heteroaryl group having 5 to 10 aromatic ring atoms, which may be substituted by one or more radicals R ² , and
Het represents a group of the formula (Het-a)

where T is N or CR ² , where at least one group T is N, and the dashed line indicates the bond to the rest of the compound,
or Het represents a group of the formula (Het-b) or (Het-c)

where the symbols appearing are as defined above and the dashed line indicates the bond to the rest of the compound,
or Het represents a group of the formula (Het-d) or (Het-e)

where T is N or CR ² and at least one T group is N, and the dashed line indicates the bond to the rest of the compound.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.Another particularly preferred embodiment of the compound according to formula (I) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

wobei für die auftretenden Gruppen die oben angegebenen Definitionen gelten.A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:

where the definitions given above apply to the groups that occur.

Preferably, for compounds of the formula (I-1-a), (1-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b), Z is CR ¹ and E is S(=O) ₂ . Preferably, p is 0.

Preferably, in groups of the formula (Het-a), two or three groups T are equal to N. Particularly preferred groups (Het-a) are selected from pyrimidyl, pyridazinyl, pyrazinyl and triazinyl, which can optionally be substituted by radicals R ² .

The compounds of the formula (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b) are as such the subject of the present invention.

1 2 3

4 5 6

7 8 9

10 11 12

13 14 15

16 17 18

19 20 21

22 23 24

25 26 27

28 29 30

31 32 33

34 35 36

37 38 39

40 41 42

43 44 45

46 47 48

49 50 51

52 53 54

55 56 57

58 59 60

61 62 63

64 65 66

67 68 69

70 71 72

73 74 75

76 77 78

79 80 81

82 The following compounds are examples of compounds according to formula (I) or (II).

1 2 3

4 5 6

7 8 9

10 11 12

13 14 15

16 17 18

19 20 21

22 23 24

25 26 27

28 29 30

31 32 33

34 35 36

37 38 39

40 41 42

43 44 45

46 47 48

49 50 51

52 53 54

55 56 57

58 59 60

61 62 63

64 65 66

67 68 69

70 71 72

73 74 75

76 77 78

79 80 81

82

The compounds according to formula (I) and (II) can be prepared by suitable combination of organic reactions known to the person skilled in the art, for example Buchwald coupling and condensation reactions between amines and aldehydes.

• Ar: Aryl- oder Heteroarylgruppe
• R: organischer Rest
• L: Abgangsgruppe, beispielsweise Halogenid, Tosylat oder Mesylat

Exemplary reaction routes for preparing the compounds are shown below. The person skilled in the art can deviate from these reaction routes or modify them within the scope of his general technical knowledge in order to prepare further compounds falling within the scope of formulas (I) and (II).

• Ar: aryl or heteroaryl group
• R: organic residue
• L: leaving group, for example halide, tosylate or mesylate

• Ar: Aryl- oder Heteroarylgruppe
• R: organischer Rest
• L: Abgangsgruppe, beispielsweise Halogenid, Tosylat oder Mesylat

According to the reaction pathway shown in Scheme 1, a thio-substituted benzimidazole group is prepared from a 1,2-diaminobenzene with a thio group via a condensation reaction with an aldehyde. The corresponding sulfoxide derivative is then prepared from this via an oxidation reaction. The free NH group of the benzimidazole is then substituted with an aryl or heteroaryl group, for example via a Buchwald coupling.

• Ar: aryl or heteroaryl group
• R: organic residue
• L: leaving group, for example halide, tosylate or mesylate

Scheme 2 shows an analogous reaction pathway for the preparation of derivatives according to formula (II). The reactions correspond to those discussed in Scheme 1.

The invention thus relates to a process for preparing compounds of (I-1-a), (1-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b), characterized in that at least one condensation reaction between an aldehyde and an aryl compound which contains at least one amino group is involved.

The process preferably further comprises at least one oxidation reaction. The process also preferably further comprises at least one transition metal-catalyzed coupling reaction, preferably a Buchwald coupling reaction.

The compounds according to the invention described above, in particular compounds which are substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters, can be used as monomers for producing corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic acid esters, amines, alkenyl or alkynyl groups with a terminal C-C double bond or C-C triple bond, oxiranes, oxetanes, groups which undergo a cycloaddition, for example a 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

The invention therefore further relates to oligomers, polymers or dendrimers containing one or more compounds according to formula (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b), where the bond(s) to the polymer, oligomer or dendrimer can be located at any position substituted with R ¹ or R ^2. Depending on the linkage of the compound according to the invention, the compound is part of a side chain of the oligomer or polymer or part of the main chain. An oligomer in the sense of this invention is understood to mean a compound which is made up of at least three monomer units. A polymer in the sense of the invention is understood to mean a compound which is made up of at least ten monomer units. The polymers, oligomers or dendrimers according to the invention can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers according to the invention can be linear, branched or dendritic. In the linearly linked structures, the units according to the abovementioned formulas can be linked directly to one another or they can be linked to one another via a bivalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a bivalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units according to the abovementioned formulas can be linked to form a branched or dendritic oligomer or polymer via a trivalent or higher-valent group, for example via a trivalent or higher-valent aromatic or heteroaromatic group.

The same preferences apply to the repeat units in oligomers, dendrimers and polymers as described above for the compounds according to the invention.

To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorenes (e.g. according to EP 842208 or WO 2000/22026 ), spirobifluorenes (e.g. according to EP 707020 , EP 894107 or WO 2006/061181 ), paraphenylenes (e.g. according to WO 1992/18552 ), carbazoles (e.g. according to WO 2004/070772 or WO 2004/113468 ), thiophenes (e.g. according to EP 1028136 ), dihydrophenanthrenes (e.g. according to WO 2005/014689 or WO 2007/006383 ), cis- and trans-indenofluorenes (e.g. according to WO 2004/041901 or WO 2004/113412 ), ketones (e.g. according to WO 2005/040302 ), phenanthrenes (e.g. according to WO 2005/104264 or WO 2007/017066 ) or several of these units. The polymers, oligomers and dendrimers usually contain further units, for example emitting (fluorescent or phosphorescent) units, such as vinyltriarylamines (e.g. according to WO 2007/068325 ) or phosphorescent metal complexes (e.g. according to WO 2006/003000 ), and/or charge transport units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long lifetimes, high efficiencies and good color coordinates.

1. (A) SUZUKI-Polymerisation;
2. (B) YAMAMOTO-Polymerisation;
3. (C) STILLE-Polymerisation; und
4. (D) HARTWIG-BUCHWALD-Polymerisation.

The polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomer, of which at least one monomer in the polymer leads to repeat units of the above-mentioned formulas. Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that lead to CC or CN linkages are the following:

1. (A) SUZUKI polymerization;
2. (B) YAMAMOTO polymerization;
3. (C) STILLE polymerization; and
4. (D) HARTWIG-BUCHWALD polymerization.

How the polymerization can be carried out using these methods and how the polymers can then be separated from the reaction medium and purified is known to the person skilled in the art and is described in the literature, for example in WO 2003/048225 , WO 2004/037887 and WO 2004/037887 , described in detail.

The present invention therefore also relates to a process for preparing the polymers, oligomers and dendrimers according to the invention, which is characterized in that they are prepared by polymerization according to SUZUKI, polymerization according to YAMAMOTO, polymerization according to STILLE or polymerization according to HARTWIG-BUCHWALD. The dendrimers according to the invention can be prepared by processes known to the person skilled in the art or in analogy thereto. Suitable processes are described in the literature, such as in Frechet, Jean MJ; Hawker, Craig J., “Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers,” Reactive & Functional Polymers (1995), 26(1-3), 127-36 ; Janssen, H.M.; Meijer, EW, “The synthesis and characterization of dendritic molecules,” Materials Science and Technology (1999), 20 (Synthesis of Polymers), 403-458 ; Tomalia, Donald A., “Dendrimer molecules,” Scientific American (1995), 272(5), 62-6 ; WO 2002/067343 A1 and WO 2005/026144 A1 .

For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions or miniemulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane or mixtures of these solvents.

The invention therefore further relates to a formulation, in particular a solution, dispersion or miniemulsion, containing at least one compound according to formula (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b) or at least one polymer, oligomer or dendrimer containing at least one unit according to these formulas and at least one solvent, preferably an organic solvent. How such solutions can be prepared is known to the person skilled in the art and is described, for example, in WO 2002/072714 , WO 2003/019694 and the literature cited therein.

The compounds according to formula (I) or (II) are suitable for use in electronic devices, in particular in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and in different layers of the organic electroluminescent device.

In general, the use of the compounds in an electron-transporting layer or in an emitting layer is preferred.

The invention therefore further relates to the use of the compounds according to formula (I) or (II) in electronic devices. The electronic devices are preferably selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), organic plasmon-emitting diodes and particularly preferably organic electroluminescent devices (OLEDs).

The organic electroluminescent device according to the invention preferably contains an anode, a cathode and one or more organic layers, wherein at least one organic layer contains one or more compounds of the formula (I) or (II). The organic electroluminescent device further preferably contains at least one electroluminescent layer. The electroluminescent layer can contain a compound of the formula (I) or (II), the compound of the formula (I) or (II) can but may also be present exclusively in another layer of the device, for example in an electron transport layer.

These other layers, which can optionally be present in the organic electroluminescent device according to the invention, are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers (charge generation layers, IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer )) and/or organic or inorganic p/n junctions. It should be noted, however, that not all of these layers must necessarily be present and the choice of layers always depends on the compounds used and, in particular, on whether the electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device can also contain several emitting layers. In this case, these emission layers particularly preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, ie different emitting compounds are used in the emitting layers that can fluoresce or phosphoresce and that emit blue and yellow, orange or red light. Systems with three emitting layers are particularly preferred, with the three layers showing blue, green and orange or red emission (for the basic structure, see e.g. WO 2005/011013 ). Emitters that have broadband emission bands and therefore show white emission are also suitable for white emission.

It is preferred that the device according to the invention has one or more phosphorescent dopants. Furthermore, the compound can also have one or more fluorescent dopants. According to one possible embodiment, the device according to the invention has at least one phosphorescent dopant and at least one fluorescent dopant. However, the device according to the invention can also have exclusively one or more fluorescent dopants.

Particularly suitable as phosphorescent dopants (= triplet emitters) are compounds which emit light, preferably in the visible range, when suitably excited and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are used as phosphorescent emitters, in particular compounds containing iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

In a preferred embodiment of the present invention, the compounds according to the invention are used as matrix material in combination with one or more dopants, preferably phosphorescent dopants.

In a system containing a matrix material and a dopant, a dopant is understood to be the component whose proportion in the mixture is the smaller. Accordingly, in a system containing a matrix material and a dopant, a matrix material is understood to be the component whose proportion in the mixture is the larger.

The proportion of the matrix material in the emitting layer is typically between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.% and particularly preferably for fluorescent emitting layers between 92.0 and 99.5 vol.% and for phosphorescent emitting layers between 85.0 and 97.0 vol.%. Accordingly, the proportion of the dopant is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.% and particularly preferably for fluorescent emitting layers between 0.5 and 8.0 vol.% and for phosphorescent emitting layers between 3.0 and 15.0 vol.%.

An emitting layer of an organic electroluminescent device can also contain systems comprising several matrix materials (mixed matrix systems) and/or several dopants. Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. In the case of mixed matrix systems too, the dopants are generally those materials whose proportion in the system is the smaller and the matrix materials are those materials whose proportion in the system is the larger. In individual cases, however, the proportion of an individual matrix material in the system can be smaller than the proportion of an individual dopant.

In a preferred embodiment of the invention, the compounds according to the invention are used as a component of mixed matrix systems. The mixed matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other is a material with electron-transporting properties. Preferably, the compounds according to the invention are the material with electron-transporting properties.

The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 and most preferably 1:4 to 1:1.

The mixed matrix systems can comprise one or more dopants. According to the invention, the dopant compound or the dopant compounds together have a proportion of 0.1 to 50.0 vol.% of the total mixture and preferably a proportion of 0.5 to 20.0 vol.% of the total mixture. Accordingly, the matrix components together have a proportion of 50.0 to 99.9 vol.% of the total mixture and preferably a proportion of 80.0 to 99.5 vol.% of the total mixture.

Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of a mixed matrix system are aromatic amines, in particular triarylamines, e.g. according to US 2005/0069729 , carbazole derivatives (e.g. CBP, N,N-biscarbazolylbiphenyl) or compounds according to WO 2005/039246 , US 2005/0069729 , JP 2004/288381 , EP 1205527 or WO 2008/086851 , bridged carbazole derivatives, e.g. according to WO 2011/088877 and WO 2011/128017 , Indenocarbazole derivatives, e.g. according to WO 2010/136109 and WO 2011/000455 , azacarbazole derivatives, e.g. according to EP 1617710 , EP 1617711 , EP 1731584 , JP 2005/347160 , Indolocarbazole derivatives, e.g. according to WO 2007/063754 or WO 2008/056746 , ketones, e.g. according to WO 2004/093207 or WO 2010/006680 , phosphine oxides, sulfoxides and sulfones, e.g. according to WO 2005/003253 , oligophenylenes, bipolar matrix materials, e.g. according to WO 2007/137725 , silanes, e.g. according to WO 2005/111172 , azaboroles or boronates, e.g. according to WO 2006/117052 , triazine derivatives, e.g. B. according to WO 2010/015306 , WO 2007/063754 or WO 2008/056746 , zinc complexes, e.g. according to EP 652273 or WO 2009/062578 , aluminium complexes, e.g. BAlq, diazasilol and tetraazasilol derivatives, e.g. according to WO 2010/054729 , diazaphosphole derivatives, e.g. according to WO 2010/054730 and aluminum complexes, e.g. BAlQ.

For phosphorescent dopants for use in mixed-matrix systems, the same preferences as stated above apply.

In a further preferred embodiment of the invention, the compounds according to the invention are used as electron transport material in an electron transport or electron injection layer. The emitting layer can contain fluorescent and/or phosphorescent emitters. If the compounds are used as electron transport material, it can be preferred if they are doped, for example with alkali metal complexes, such as Liq (lithium hydroxyquinolinate). The combination of the compound according to the invention in an electron transport layer with an electron injection layer is also suitable. Suitable materials for the electron injection layer are, for example, alkali or alkaline earth fluorides, such as LiF.

In yet another preferred embodiment of the invention, the compounds according to the invention are used as hole-blocking material in a hole-blocking layer. A hole-blocking layer is understood to be a layer which directly adjoins an emitting layer on the cathode side.

The materials preferably used in the electronic devices according to the invention for the respective functions are listed below.

Preferred fluorescent dopants are selected from the class of arylamines. An arylamine or an aromatic amine in the sense of this invention is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, whereby the diarylamino groups on the pyrene are preferably bonded in the 1-position or in the 1,6-position.

Preferred phosphorescent dopants can be found in the applications WO 2000/70655 , WO 2001/41512 , WO 2002/02714 , WO 2002/15645 , EP 1191613 , EP 1191612 , EP 1191614 , WO 2005/033244 , WO 2005/019373 and US 2005/0258742 In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

Preferred matrix materials for fluorescent dopants are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular the oligoarylenes containing condensed aromatic groups, the oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461 ), the polypodal metal complexes (e.g. according to WO 2004/081017 ), the hole-conducting connections (e.g. according to WO 2004/058911 ), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO 2005/084081 and WO 2005/084082 ), the atropisomers (e.g. according to WO 2006/048268 ), the boronic acid derivatives (e.g. according to WO 2006/117052 ) or benzanthracenes (e.g. according to WO 2008/145239 ). Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and/or pyrene or atropisomers of these compounds. An oligoarylene in the sense of this invention is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

Preferred matrix materials for phosphorescent dopants, for use as single matrix or mixed matrix, have been given above.

Suitable charge transport materials, such as can be used in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the organic electroluminescent device according to the invention, are, in addition to the compounds according to the invention, for example those in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 disclosed compounds or other materials as used in these layers according to the prior art.

Examples of preferred hole transport materials that can be used in a hole transport, hole injection or electron blocking layer in the electroluminescent device according to the invention are indenofluorenamines and derivatives (e.g. according to WO 06/122630 or WO 06/100896 ), which in EP 1661888 disclosed amine derivatives, hexaazatriphenylene derivatives (e.g. according to WO 01/049806 ), amine derivatives with condensed aromatics (e.g. according to US 5,061,569 ), which in WO 95/09147 disclosed amine derivatives, monobenzoindenofluorenamines (e.g. according to WO 08/006449 ) or dibenzoindenofluorenamines (e.g. according to WO 07/140847 ). Other suitable hole transport and hole injection materials are derivatives of the compounds shown above, as described in JP 2001/226331 , EP 676461 , EP 650955 , WO 01/049806 , US 4780536 , WO 98/30071 , EP 891121 , EP 1661888 , JP 2006/253445 , EP 650955 , WO 06/073054 and US 5061569 be revealed.

Metals with a low work function, metal alloys or multilayer structures made of different metals are preferred as the cathode of the organic electroluminescent device, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver are also suitable, for example an alloy of magnesium and silver. In the case of multilayer structures, other metals that have a relatively high work function can also be used in addition to the metals mentioned, such as. B. Ag or Al, whereby combinations of metals such as Ca/Ag, Mg/Ag or Ba/Ag are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. For example, alkali metal or alkaline earth metal fluorides are suitable for this, but also the corresponding oxides or carbonates (e.g. LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ , etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness is preferably between 0.5 and 5 nm.

Materials with a high work function are preferred as anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. On the one hand, metals with a high redox potential are suitable for this, such as Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (e.g. Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, in particular conductive doped polymers.

The device is structured, contacted and finally sealed accordingly (depending on the application), since the service life of the devices according to the invention is shortened in the presence of water and/or air.

In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that one or more layers are coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 ^-7 mbar.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation. The materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case of this method is the OVJP (Organic Vapour Jet Printing) method, in which the materials are applied directly through a nozzle and thus structured (e.g. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301 ).

Also preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, gravure printing (engraving), slot-die printing, slot-die coating, nozzle printing or offset printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing. Soluble compounds according to formula (I) or formula (II) are required for this. High solubility can be achieved by suitable substitution of the compounds.

It is further preferred that, in order to produce an organic electroluminescent device according to the invention, one or more layers are applied from solution and one or more layers are applied by a sublimation process.

According to the invention, the electronic devices comprising one or more compounds according to formula (I) or (II) can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (e.g. light therapy).

• - bei Verwendung der Verbindungen gemäß Formel (I) oder (II) in den Vorrichtungen, insbesondere als Matrixmaterialien für phosphoreszierende Emitter, können eine hohe Leistungseffizienz und eine niedrige Betriebsspannung der Vorrichtungen erreicht werden
• - bei Verwendung der Verbindungen gemäß Formel (I) oder (II) wird eine lange Lebensdauer der elektronischen Vorrichtung erhalten.
• - die Verbindungen gemäß Formel (I) oder (II) weisen deutlich bessere Löslichkeit und Filmbildungseigenschaften auf im Vergleich zu im Stand der Technik bekannten Materialien, insbesondere im Vergleich zu carbazolbasierten Matrixmaterialien

The devices according to the invention preferably have one or more of the advantages listed below:

• - when using the compounds according to formula (I) or (II) in the devices, in particular as matrix materials for phosphorescent emitters, a high power efficiency and a low operating voltage of the devices can be achieved
• - when using the compounds according to formula (I) or (II), a long lifetime of the electronic device is obtained.
• - the compounds according to formula (I) or (II) have significantly better solubility and film-forming properties compared to materials known in the prior art, in particular compared to carbazole-based matrix materials

The invention is explained in more detail by the following embodiments. The invention is not limited to the scope of the explicitly disclosed examples.

implementation examples

15.7 g (90.8 mmol) 5-Chlor-2-nitroanilin und 10.2 g (90.8 mmol) Natriumtert-butylat werden zu einer Lösung aus 23.8 g (86.5 mmol) 4-(9H-Carbazol-9-yl)-Benzenthiol in 600 ml Propanol gegeben und für 4 h zum Sieden erhitzt. Das Gemisch wird in 1000 mL Wasser gegossen, der beige Niederschlag abgesaugt, mit Wasser gewaschen und getrocknet. Der Gehalt an Produkt beträgt gemäß ¹H-NMR ca. 97 % bei einer Gesamtausbeute von 33.8 g (95 %).

56.4 g (323.2 mmol) Na₂S₂O₄ werden zu einer Lösung aus 33.2 g (80.8 mmol) 5[(4-N-Carbazolphenyl)thio]-2-nitro-benzenamin in 1200 ml Ethanol und 300 ml Wasser portionsweise zugegeben und anschließend für 4 h zum Sieden erhitzt. Das Ethanol wird im Vakuum abdestilliert und die Mischung mit Essigsäureethylester extrahiert. Die organische Phase wird mit 4 x 50 mL H₂O gewaschen, über MgSO₄ getrocknet und die Lösungsmittel im Vakuum entfernt. Das reine Produkt erhält man durch Umkristallisation. Der Gehalt an Produkt beträgt gemäß HPLC 98 % bei einer Gesamtausbeute von 30.2 g (98 %).

5 g (50 mmol) Benzaldehyd wird tropfenweise zu 19 g (50 mmol) 5[(4-N-Carbazolphenyl)thio]-1,2-benzendiamin in 300 ml DMF und 10 ml konz. Schwefelsäure gegeben und für 2 h bei Raumtemperatur gerührt. Die Mischung wird auf 500 g Eis gegeben und und mit Dichloromethan extrahiert. Die organische Phase wird mit 4 x 50 mL H₂O gewaschen, über MgSO₄ getrocknet, und die Lösungsmittel werden im Vakuum entfernt. Das reine Produkt erhält man durch Umkristallisation. Der Gehalt an Produkt beträgt gemäß HPLC 98 % bei einer Gesamtausbeute von 11.4 g (49 %).

15.7 g (90.8 mmol) 5-chloro-2-nitroaniline and 10.2 g (90.8 mmol) sodium tert-butoxide are added to a solution of 23.8 g (86.5 mmol) 4-(9H-carbazol-9-yl)-benzenethiol in 600 ml propanol and heated to boiling for 4 h. The mixture is poured into 1000 mL water, the beige precipitate is filtered off with suction, washed with water and dried. The product content is approximately 97% according to ¹ H-NMR with a total yield of 33.8 g (95%).

56.4 g (323.2 mmol) of Na ₂ S ₂ O ₄ are added in portions to a solution of 33.2 g (80.8 mmol) of 5[(4-N-carbazolphenyl)thio]-2-nitro-benzenamine in 1200 ml of ethanol and 300 ml of water and then heated to boiling for 4 h. The ethanol is distilled off in vacuo and the mixture is extracted with ethyl acetate. The organic phase is washed with 4 x 50 mL H ₂ O, dried over MgSO ₄ and the solvents are removed in vacuo. The pure product is obtained by recrystallization. The product content is 98% according to HPLC with a total yield of 30.2 g (98%).

5 g (50 mmol) of benzaldehyde is added dropwise to 19 g (50 mmol) of 5[(4-N-carbazolphenyl)thio]-1,2-benzenediamine in 300 ml of DMF and 10 ml of concentrated sulfuric acid and stirred for 2 h at room temperature. The mixture is poured onto 500 g of ice and extracted with dichloromethane. The organic phase is washed with 4 x 50 mL H ₂ O, dried over MgSO ₄ and the solvents are removed in vacuo. The Pure product is obtained by recrystallization. The product content according to HPLC is 98% with a total yield of 11.4 g (49%).

14.3 g (28.2 mmol) 5[(2-Phenyl-1 H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazol werden in 225 ml Dimethylformamid unter Schutzgasatmosphäre gelöst und mit 1.5 g NaH, 60%ig in Mineralöl (37.5 mmol) versetzt. Nach 1 h bei Raumtemperatur wird eine Lösung von 2-Chlor-4,6-diphenyl-[1,3,5]-triazin (8.5 g, 31.75 mmol) in 75 mL Dimethylformamid zugetropft. Das Reaktionsgemisch wird dann 12 h bei Raumtemperatur gerührt. Nach dieser Zeit wird das Reaktionsgemisch auf Eis gegossen und dreimal mit Dichlormethan extrahiert. Die vereinigten organischen Phasen werden über Na₂SO₄ getrocknet und eingeengt. Der Rückstand wird mit Toluol heiß extrahiert und im Toluol umkristallisiert, abschließend im Hochvakuum sublimiert, die Reinheit beträgt 99.9%. Die Ausbeute beträgt 17.36 g (23.7 mmol, 83%).Under protective gas, 22.9 g (49 mmol) of 5[(2-phenyl-1 H-benzimidazol-5-yl)thio]-9-phenyl-N-carbazole are placed in 0.3 L of glacial acetic acid. 33 mL (619 mmol) of 30% H ₂ O ₂ solution are added dropwise to this solution and stirred overnight. The mixture is treated with Na ₂ SO ₃ solution, the phases are separated and the solvent is removed in vacuo. The product content is approximately 98% according to ¹ H-NMR, with a total yield of 23.2 g (95%).

14.3 g (28.2 mmol) of 5[(2-phenyl-1H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazole are dissolved in 225 ml of dimethylformamide under a protective gas atmosphere and 1.5 g of NaH, 60% in mineral oil (37.5 mmol) are added. After 1 h at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3,5]-triazine (8.5 g, 31.75 mmol) in 75 mL of dimethylformamide is added dropwise. The reaction mixture is then stirred for 12 h at room temperature. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na ₂ SO ₄ and concentrated. The residue is extracted hot with toluene and recrystallized in toluene, finally sublimated under high vacuum, the purity is 99.9%. The yield is 17.36 g (23.7 mmol, 83%).

2) Synthesis of precursors analogous to step 3 in Example 1

46% 3a

46% 4a

53%

15.6 g (50 mmol) 2,2 Dibrom-1,1-biphenyl werden in 500 ml Toluol gelöst. Anschließend werden 2.3 g (2.5 mmol) Tris(dibenzylidenaceton)-dipalladium(0), 10 mL 1M t-Bu₃P in Toluol und 11.5 g (120 mmol) Natrium tert-butoxid zugegeben. Anschließend werden 19.9 g (40 mmol) 4-(2-Phenyl-3H-benzimidazol-5-sulfonyl)-phenylamin zugegeben. Der Ansatz wird 20 h auf 110 °C erhitzt, dann auf Raumtemperatur abgekühlt und es werden 400 ml Wasser zugegeben. Es wird mit Essigester extrahiert, danach werden die vereinigten organischen Phasen über Natriumsulfat getrocknet, und unter vermindertem Druck eingeengt. Der Rückstand wird aus Toluol und aus Dichlormethan/iso-Propanol umkristallisiert. Die Ausbeute beträgt 12.8 g (25.6 mmol), entsprechend 45 % der Theorie.

6.6 g (42.12 mmol ) Brombenzol, 23.4 g (47 mmol) 9-[4-(2-Phenyl-3H-benzimidazol-5-sulfonyl)-phenyl]-9H-carbazol und 29.2 g Rb₂CO₃ werden in 250 mL p-Xylol suspendiert. Zu dieser Suspension werden 0.95 g (4.2 mmol) Pd(OAc)₂ und 12.6 ml einer 1M Tri-tert-butylphosphinlösung gegeben. Die Reaktionsmischung wird 16 h unter Rückfluss erhitzt. Nach Erkalten wird die organische Phase abgetrennt, dreimal mit 200 mL Wasser gewaschen und anschließend zur Trockene eingeengt. Der Rückstand wird mit Toluol heiß extrahiert, aus Toluol umkristallisiert und abschließend im Hochvakuum sublimiert. Die Reinheit beträgt 99.9%. Ausbeute: 19.4 g (33 mmol), 72% der Theorie. reactant reactant product yield 2a

46% 3a

46% 4a

53%

15.6 g (50 mmol) of 2,2-dibromo-1,1-biphenyl are dissolved in 500 ml of toluene. Then 2.3 g (2.5 mmol) of tris(dibenzylideneacetone)-dipalladium(0), 10 mL of 1M t-Bu ₃ P in toluene and 11.5 g (120 mmol) of sodium tert-butoxide are added. Then 19.9 g (40 mmol) of 4-(2-phenyl-3H-benzimidazole-5-sulfonyl)-phenylamine are added. The mixture is heated to 110 °C for 20 h, then cooled to room temperature and 400 ml of water are added. It is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is recrystallized from toluene and from dichloromethane/isopropanol. The yield is 12.8 g (25.6 mmol), corresponding to 45 % of theory.

6.6 g (42.12 mmol) bromobenzene, 23.4 g (47 mmol) 9-[4-(2-phenyl-3H-benzimidazole-5-sulfonyl)-phenyl]-9H-carbazole and 29.2 g Rb ₂ CO ₃ are suspended in 250 mL p-xylene. 0.95 g (4.2 mmol) Pd(OAc) ₂ and 12.6 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 200 mL water and then evaporated to dryness. The residue is extracted hot with toluene, recrystallized from toluene and finally sublimated under high vacuum. The purity is 99.9%. Yield: 19.4 g (33 mmol), 72% of theory.

4) Synthesis of compound 5

57% Analogously to the last step in Example 1, the following compound 5 can be obtained: example reactant reactant product yield 5

57%

5) Synthesis of compound 6

13.5 g (42.12 mmol) 3-Bromo-9-phenyl-9H-carbazol, 23.3 g (47 mmol) 5[(2-Phenyl-1 H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazol und 29.2 g Rb₂CO₃ werden in 250 mL p-Xylol suspendiert. Zu dieser Suspension werden 0.95 g (4.2 mmol) Pd(OAc)₂ und 12.6 ml einer 1M Tri-tert-butylphosphinlösung gegeben. Die Reaktionsmischung wird 16 h unter Rückfluss erhitzt. Nach Erkalten wird die organische Phase abgetrennt, dreimal mit 200 mL Wasser gewaschen und anschließend zur Trockene eingeengt. Der Rückstand wird mit Toluol heiß extrahiert, aus Toluol umkristallisiert und abschließend im Hochvakuum sublimiert, die Reinheit beträgt 99.9%. Ausbeute: 26 g (35 mmol), 75 % der Theorie.

13.5 g (42.12 mmol) 3-bromo-9-phenyl-9H-carbazole, 23.3 g (47 mmol) 5[(2-phenyl-1 H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazole and 29.2 g Rb ₂ CO ₃ are suspended in 250 mL p-xylene. 0.95 g (4.2 mmol) Pd(OAc) ₂ and 12.6 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 200 mL water and then evaporated to dryness. The residue is extracted hot with toluene, recrystallized from toluene and finally sublimated under high vacuum; the purity is 99.9%. Yield: 26 g (35 mmol), 75% of theory.

6) Syntheses of compounds 2, 4, 7, 8 and 9

46% 4

48% 7

72% 8

47% 9

39% Analogous to the step described above, the following compounds can be obtained: example reactant reactant product yield 2

46% 4

48% 7

72% 8

47% 9

39%

7) Synthesis of compound 10

33 g (120 mmol) 5-Phenylsulfonyl-1 H-benzoimidazol-2-ylamin werden in 300 ml MeOH mit 12.1 g (100 mmol) Phenylboronsäure versetzt. Zu dieser Lösung wird 0.78 g (5.5 mmol) Cu₂O zugegeben und bei Raumtemperatur 4h gerührt. Dann wird auf Raumtemperatur abgekühlt und es wird 400 ml Wasser zugegeben. Es wird mit Essigester extrahiert, danach werden die vereinigten organischen Phasen über Natriumsulfat getrocknet und unter vermindertem Druck eingeengt. Der Rückstand wird aus Toluol umkristallisiert. Die Ausbeute beträgt 28 g (80 mmol), entsprechend 67% der Theorie.

33 g (120 mmol) of 5-phenylsulfonyl-1H-benzoimidazol-2-ylamine in 300 ml of MeOH are mixed with 12.1 g (100 mmol) of phenylboronic acid. 0.78 g (5.5 mmol) of Cu ₂ O is added to this solution and the mixture is stirred at room temperature for 4 hours. It is then cooled to room temperature and 400 ml of water is added. It is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is recrystallized from toluene. The yield is 28 g (80 mmol), corresponding to 67% of theory.

54% According to the first step of the synthesis of compound 3, compound 10 is obtained from intermediate 10b: example reactant reactant product yield 10

54%

8) Synthesis of compound 11

46% According to the first step of the synthesis of compound 3, compound 11 can be obtained: example reactant reactant product yield 11

46%

The following reference materials are used:

Example 9: Solutions and compositions containing matrix materials and TEG1 for OLEDs

Solutions Ref and A to K, as summarized in Table 1, are prepared as follows: First, 200 mg of TMM and 50 mg of TEG1 are dissolved in 10 mL of chlorobenzene and stirred until the solution is clear. The solution is filtered using a Millipore Millex LS, Hydrophobic PTFE 5.0 µm filter. Table 1: Composition of the solutions composition ratio (based on weight) concentration Solution-Ref TMM1 + TEG1 75% : 25% 15 mg/ml Solution A 1 + TEG1 75% : 25% 25 mg/ml Solution B 5 + TEG1 75% : 25% 25 mg/ml Solution C 6 + TEG1 75% : 25% 25 mg/ml Solution D 7 + TEG1 75% : 25% 25 mg/ml Solution E 2 + TEG1 75% : 25% 25 mg/ml Solution F 4 + TEG1 75% : 25% 25 mg/ml Solution G 8 + TEG1 75% : 25% 25 mg/ml Solution H 9 + TEG1 75% : 25% 25 mg/ml Solution I 10 + TEG1 75% : 25% 25 mg/ml Solution J 11 + TEG1 75% : 25% 25 mg/ml Solution K 3 + TEG1 75% : 25% 25 mg/ml

The solutions are used to coat the emitting layer of OLEDs. The corresponding solid composition can be obtained by evaporating the solvent of the solutions. This can be used to prepare further formulations.

Example 10: Production of OLEDs

1. 1) Beschichtung von 80 nm PEDOT (Baytron P Al 4083) auf ein ITObeschichtetes Glassubstrat durch Spin-Coating, und 10 Minuten bei 180°C ausheizen.
2. 2) Beschichtung einer 20 nm Interlayer durch Spin-Coating einer Toluollösung von HIL-012 (Merck KGaA) (Konzentration 0.5 Gew.%) in einer Glovebox.
3. 3) Ausheizen der Interlayer bei 180 °C für 1 h in einer Glovebox.
4. 4) Beschichtung einer 80 nm emittierenden Schicht durch Spin-Coating einer entsprechenden Lösung gemäß Tabelle 1.
5. 5) Ausheizen der Vorrichtung bei 180 °C für 10 min.
6. 6) Aufdampfen einer Ba/Al-Kathode (3 nm + 150 nm).
7. 7) Verkapselung der Vorrichtung.

OLED-Ref as well as the inventive OLED-A to OLED-K, which all have the structure IOT/PEDOT/interlayer/EML/cathode, are manufactured using the corresponding solutions as summarized in Table 2 according to the following procedure:

1. 1) Coating of 80 nm PEDOT (Baytron P Al 4083) on an ITO coated glass substrate by spin coating and annealing for 10 minutes at 180°C.
2. 2) Coating of a 20 nm interlayer by spin-coating a toluene solution of HIL-012 (Merck KGaA) (concentration 0.5 wt%) in a glove box.
3. 3) Bake the interlayer at 180 °C for 1 h in a glove box.
4. 4) Coating of an 80 nm emitting layer by spin-coating an appropriate solution according to Table 1.
5. 5) Bake the device at 180 °C for 10 min.
6. 6) Evaporation of a Ba/Al cathode (3 nm + 150 nm).
7. 7) Encapsulation of the device.

Example 11: Measurements and comparison of results

The OLEDs obtained in this way are characterized using standard methods. The following properties are measured: UIL characteristics, electroluminescence spectrum, color coordinates (CIEx and CIEy), efficiency and operating voltage. The results are summarized in Table 3, with OLED-Ref serving as a comparison according to the state of the art. In Table 3, U _on stands for the operating voltage and U(100) for the voltage at 100 cd/m ² . Table 3: Measurement results with OLED-Ref and OLED-A to OLED-K Max. Eff. [cd/A] Uon [V] U(100) [V] CIEx @ 100 cd/m ² CIEy @ 100 cd/m ² OLED-Ref 8.2 3.8 6.5 0.33 0.62 OLED-A 27.0 3.0 4.5 0.33 0.62 OLED-B 24.5 2.5 3.6 0.33 0.62 OLED-C 32.3 2.6 4.0 0.34 0.62 OLED-D 29.2 2.6 3.7 0.33 0.62 OLED-E 16.4 2.9 4.6 0.33 0.62 OLED-F 30.3 2.6 4.0 0.35 0.62 OLED-G 30.4 2.6 4.0 0.34 0.62 OLED-H 27.0 2.7 4.2 0.34 0.61 OLED-I 18.7 3.3 5.6 0.34 0.62 OLED-J 28.8 2.7 3.8 0.33 0.62 OLED-K 32.7 2.7 4.9 0.35 0.61

As can be seen from Table 3, using the matrix materials according to the invention, significantly improved phosphorescent OLEDs are obtained in terms of operating voltage and efficiency. All OLEDs show comparable color coordinates.

It is also possible (not explicitly shown) to use the compounds according to the invention as triplet matrix materials in combination with another matrix material (mixed matrix).

Furthermore, the use with triplet emitters other than TEG1 also produces good results.

Claims (9)

Electronic device containing at least one organic layer, wherein the organic layer comprises one or more compounds of formula (I) or (II)

where the following applies to the symbols occurring: E is a divalent group selected from S=O and S(=O) ₂ ; W, X are the same or different on each occurrence and are N, P or CR ¹ ; Y is the same or different on each occurrence and are NR ¹ , PR ¹ , O or S; Z is C if a substituent is attached and is otherwise the same or different on each occurrence and are CR ¹ or N; R ¹ is, identically or differently on each occurrence, H, D, F, Cl, Br, I, C(=O)R ² , CN, Si(R ² ) ₃ , N(R ² ) ₂ , NO ₂ , P(=O)(R ² ) ₂ , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ² and where one or more CH ₂ groups in the abovementioned groups are replaced by -R ² C=CR ² -, -C=C-, Si(R ² ) ₂ , C=O, C=S, C=NR ² , -C(=O)O-, -C(=O)NR ² -, NR ² , P(=O)(R ² ), -O-, -S-, SO or SO ₂ and where one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group with 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can be linked to one another and can form a ring; wherein the group R ¹ which is bonded to the group E is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ² ; R ² is, identically or differently on each occurrence, H, D, F, Cl, Br, I, C(=O)R ³ , CN, Si(R ³ ) ₃ , N(R ³ ) ₂ ^, NO ₂ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups may each be substituted by one or more radicals R ³ and where one or more CH ₂ groups in the abovementioned groups are replaced by -R ³ C=CR ³ -, -C≡C-, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , -C(=O)O-, -C(=O)NR ³ -, NR ³ , P(=O)(R ³ ), -O-, -S-, SO or SO ₂ and where one or more H atoms in the abovementioned groups can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ³ , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ³ , where two or more radicals R ² can be linked to one another and can form a ring; R ³ is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more R ³ substituents may be linked to one another to form a ring. Electronic device according to claim 1 , characterized in that E is equal to S(=O) ₂ . Electronic device according to claim 1 or 2 , characterized in that the group E is bonded in meta- or para-position to the group Y. Electronic device according to one or more of the Claims 1 until 3 , characterized in that W is equal to N. Electronic device according to one or more of the Claims 1 until 4 , characterized in that X is equal to CR ¹ . Electronic device according to one or more of the Claims 1 until 5 , characterized in that Y is equal to NR ¹ . Electronic device according to one or more of the Claims 1 until 6 , characterized in that the compound of formula (I) or (II) contains at least one group R ¹ which is selected from - heteroaryl groups having 5 to 20 aromatic ring atoms which may be substituted by one or more radicals R ² and which contain at least one heteroaromatic five-membered ring with two or more heteroatoms selected from N, O and S; - heteroaryl groups having 5 to 20 aromatic ring atoms which may be substituted by one or more radicals R ² and which contain at least one heteroaromatic six-membered ring with one or more heteroatoms selected from N, O and S; and - carbazole derivatives which may be substituted by one or more radicals R ² . Electronic device according to one or more of the Claims 1 until 7 , characterized in that the device is selected from organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), organic plasmon-emitting diodes and organic electroluminescent devices (OLEDs). Electronic device according to one or more of the Claims 1 until 8 , characterized in that the compound according to formula (I) or (II) is contained as matrix material in an emitting layer or is contained as electron transport material in an electron transport layer or an electron injection layer.