DE102009022858A1 - Organic electroluminescent devices - Google Patents

Abstract

The present invention relates to electronic devices, in particular organic electroluminescent devices, which contain compounds according to the formula (1), as well as the corresponding compounds and their use in organic electroluminescent devices.

Description

The present invention relates to organic electroluminescent devices and materials for use in organic electroluminescent devices.

The construction of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US Pat US 4539507 . US 5151629 . EP 0676461 and WO 98/27136 described. In this case, increasingly, organometallic complexes which exhibit phosphorescence instead of fluorescence are used as emitting materials ( MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6 ). For quantum mechanical reasons, up to four times energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, there is still room for improvement in OLEDs, especially in OLEDs, which show triplet emission, especially in terms of efficiency, operating voltage and lifetime. This applies in particular to OLEDs which emit in the shorter-wave range, that is to say green and in particular blue. So far, no devices are known with blue emitting triplet emitters, which meet the technical requirements for industrial application.

The properties of phosphorescent OLEDs are not only determined by the triplet emitters used. Here, in particular, the other materials used, such as matrix materials, hole blocking materials, electron transport materials, hole transport materials and electron or exciton blocking materials are of particular importance. Improvements to these materials can thus also lead to significant improvements in the OLED properties. Even for fluorescent OLEDs there is still room for improvement with these materials.

According to the prior art, ketones (for example according to US Pat WO 04/093207 or according to the application not disclosed DE 102008033943.1 ) or phosphine oxides (eg according to WO 05/003253 ) are used as matrix materials for phosphorescent emitters.

However, with the use of these matrix materials, as with other matrix materials, there is still room for improvement, particularly with regard to the efficiency and the life of the device.

The object of the present invention is to provide compounds which are suitable for use in a fluorescent or phosphorescent OLED, in particular a phosphorescent OLED, for example as matrix material or as hole transport / electron blocking material or exciton blocking material or as electron transport or hole blocking material. In particular, it is the object of the present invention to provide matrix materials which are also suitable for blue and green phosphorescent OLEDs.

Surprisingly, it has been found that certain compounds described in more detail below achieve this object and lead to significant improvements in the organic electroluminescent device, in particular with regard to the service life, the efficiency and the operating voltage. This is especially true for blue and green phosphorescent electroluminescent devices, especially when using the compounds of the invention as a matrix material. Organic electroluminescent devices containing such compounds as well as the corresponding compounds are therefore the subject of the present invention.

wobei für die verwendeten Symbole und Indizes gilt:
A-B und D-E ist jeweils gleich oder verschieden bei jedem Auftreten eine Einheit der folgenden Formel (2), (3), (4), (5) oder (6),

wobei die gestrichelte Bindung jeweils die Verknüpfung mit Z darstellt;
und
Z ist gleich oder verschieden bei jedem Auftreten N-R², O oder S;
oder
A-Z und B-Z ist jeweils gleich oder verschieden bei jedem Auftreten eine Einheit der folgenden Formel (7) und q = 0,

dabei stellt die gestrichelte Bindung in Formel (7) jeweils die Verknüpfung dieser Einheit in der Verbindung der Formel (1) dar, wobei der Stickstoff mit der Gruppe Y verknüpft ist;
Y ist bei jedem Auftreten gleich oder verschieden P(=O), P(=S), P, As(=O), As(=S), As, Sb(=O), Sb(=S), Sb, Bi(=O), Bi(=S) oder Bi;
Ar ist bei jedem Auftreten gleich oder verschieden ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, welches durch einen oder mehrere Reste R¹ substituiert sein kann;
Ar¹ ist bei jedem Auftreten gleich oder verschieden eine Aryl- oder Heteroarylgruppe mit 5 bis 18 aromatischen Ringatomen, welche durch einen oder mehrere Reste R¹ substituiert sein kann;
X ist bei jedem Auftreten gleich oder verschieden CR¹ oder N;
L ist eine Einfachbindung oder eine bivalente, trivalente oder tetravalente Gruppe;
R¹ ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus H, D, F, Cl, Br, I, CN, NO₂, N(R³)₂, C(=O)R³, einer geradkettigen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 40 C-Atomen oder einer Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R³ substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R³C=CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C=O, C=S, C=Se, C=NR³, P(=O)(R³), SO, SO₂, NR³, O, S oder CONR³ ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R³ substituiert sein kann, einer Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die mit einem oder mehreren Resten R³ substituiert sein kann, oder einer Kombination dieser Systeme, wobei optional zwei oder mehr benachbarte Substituenten R¹ ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können, das mit einem oder mehreren Resten R³ substituiert sein kann;
R² ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus einer geradkettigen Alkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkylgruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R³ substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R³C=CR³, C≡C oder C=O ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R³ substituiert sein kann, oder einer Kombination dieser Systeme; dabei können optional solche R¹ und R², die in 1,2-Position zueinander benachbart stehen, ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden, das mit einem oder mehreren Resten R³ substituiert sein;
R³ ist ausgewählt aus der Gruppe bestehend aus H, D, F, CN, aliphatischem Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, aromatischem oder heteroaromatischem Ringsystem mit 5 bis 30 aromatischen Ringatomen, in dem ein oder mehrere H-Atome durch D, F, Cl, Br, I oder CN ersetzt sein können, wobei zwei oder mehr benachbarte Substituenten R³ miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können;
n ist 1 bis 10, bevorzugt 1, 2, 3, 4, 5 oder 6;
m ist 1, wenn L eine Einfachbindung oder eine bivalente Gruppe ist, oder ist 2, wenn L eine trivalente Gruppe ist, oder ist 3, wenn L eine tetravalente Gruppe ist;
q ist bei jedem Auftreten gleich oder verschieden 0 oder 1.The present invention is an electronic device containing at least one compound according to the following formula (1),

where the symbols and indices used are:
Each of AB and DE is the same or different each occurrence of a unit represented by the following formula (2), (3), (4), (5) or (6),

wherein the dashed bond represents the linkage with Z;
and
Z is the same or different at each occurrence, NR ² , O or S;
or
AZ and BZ are each the same or different at each occurrence, a unit of the following formula (7) and q = 0,

the dashed bond in formula (7) represents in each case the linking of this unit in the compound of formula (1), wherein the nitrogen is linked to the group Y;
Y is the same or different at every occurrence P (= O), P (= S), P, As (= O), As (= S), As, Sb (= O), Sb (= S), Sb, Bi (= O), Bi (= S) or Bi;
Ar is identical or different at each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ;
Ar ¹ is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ;
X is the same or different CR ¹ or N at each occurrence;
L is a single bond or a bivalent, trivalent or tetravalent group;
R ¹ is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (R ³ ) ₂ , C (= O) R ³ , a straight-chain alkyl -, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each with a R or more radicals may be substituted ^3, wherein one or more non-adjacent CH ₂ groups represented by R ³ C = CR ^3, C≡C, Si (R ³⁾ _2, Ge (R ³⁾ _2, Sn (R ³ ) ₂ , C = O, C = S, C = Se, C = NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ may be replaced and wherein a or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals Aryloxy or heteroaryloxy group with 5 to 60 aromatic ringate omen, which may be substituted by one or more radicals R ³ , or a combination of these systems, where optionally two or more adjacent substituents R ^{1 is} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals;
R ² is the same or different each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each substituted with one or more R ³ radicals wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ , C≡C or C = O, and wherein one or more H atoms are represented by D, F, Cl, Br, I, CN or NO ₂ may be replaced, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals;
R ³ is selected from the group consisting of H, D, F, CN, aliphatic hydrocarbon radical having 1 to 20 C atoms, aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms by D, F , Cl, Br, I or CN may be replaced, wherein two or more adjacent substituents R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
n is 1 to 10, preferably 1, 2, 3, 4, 5 or 6;
m is 1 if L is a single bond or a divalent group, or 2 if L is a trivalent group, or 3 if L is a tetravalent group;
q is the same or different 0 or 1 for each occurrence.

An aryl group in the sense of this invention contains 6 to 60 C atoms; For the purposes of this invention, a heteroaryl group contains 2 to 60 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms gives at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, under an aryl group or heteroaryl either a simple aromatic cycle, ie benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., understood. By contrast, aromatics linked to one another by single bond, such as, for example, biphenyl, are not designated as aryl or heteroaryl group but as aromatic ring system.

An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 2 to 60 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms gives at least 5. 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 meaning a system which does not necessarily contain only aryl or heteroaryl groups but in which also several aryl or heteroaryl groups a non-aromatic moiety (preferably less than 10% of the atoms other than H), such as e.g. As an sp ³ -hybridized C, N or O atom, may be interrupted. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are to be understood as aromatic ring systems in the context of this invention, and also systems in which two or more aryl groups, for example are interrupted by a short alkyl group.

In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may typically contain 1 to 40 or also 1 to 20 C atoms, and in which also individual H atoms or CH ₂ - Groups may be substituted by the above groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s Pentyl, cyclopentyl, n-hexyl, cyclohexyl, 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, pentynyl, hexynyl, heptynyl or octynyl. Among an alkoxy group having 1 to 40 carbon atoms, 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, pentafluoroethoxy and 2,2,2-trifluoroethoxy understood. In particular, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-butylthio, n-butylthio, n-butylthio, n-butylthio Hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, 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, pentynylthio, hexynylthio, heptynylthio or octynylthio understood. In general, alkyl, alkoxy or thioalkyl groups according to the present invention straight chain, branched or cyclic, wherein one or more non-adjacent CH ₂ groups by R ³ C = CR ³ , C≡C, Si (R ³ ) ₂ , Ge (R ³ ) ₂ , Sn (R ³ ) ₂ , C = O, C = S, C = Se, C = NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ can; Furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO ₂ , preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

Under an aromatic or heteroaromatic ring system with 5-60 aromatic ring atoms, which may be substituted in each case with the above-mentioned radicals R ³ or a hydrocarbon radical and which may be linked via any position on the aromatic or heteroaromatic, are understood in particular groups derived are benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzpyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene , cis or trans indenocarbazole, cis or trans indolocarbazole, Truxen, isotruxene, spirotruxene, spiroisotruxene, 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, Be nzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, 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.

When the compound of the formula (1) contains a unit represented by one or more of the formulas (2) to (5), Ar ^{1 is} preferably the same or different each occurrence of an aryl or heteroaryl group having 5 to 14 aromatic ring atoms, especially preferably with 5 to 10 aromatic ring atoms, very particularly preferably with 6 aromatic ring atoms. Particularly suitable aryl and heteroaryl groups Ar ¹ are identical or different at each occurrence selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, furan, thiophene, pyrrole, naphthalene, phenanthrene, quinoline, isoquinoline, quinoxaline, indole , Benzofuran, benzothiophene and carbazole.

wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen.Preferred embodiments of the compounds of formula (1) above are the compounds of formulas (8) to (18),

wherein the symbols and indices used have the meanings given above.

In a preferred embodiment of the compounds according to formula (1) or formula (8) to (18), the symbol Y at each occurrence identically or differently represents P (= O), P (= S) or P. This is particularly preferred Symbol Y for P (= O) or P (= S), very particularly preferably for P (= O).

In a further preferred embodiment of the compounds according to formula (1) or formula (8) to (18), the symbol Z, if it does not form a ring according to formula (7) with A or B, is the same or different at each occurrence for NR ² .

In a particularly preferred embodiment of the compounds according to formula (1) or formula (8) to (18) the symbol Y stands for P (= O), and the symbol Z is the same or different NR ² for each occurrence.

In a further preferred embodiment of the compounds according to formula (1) or formula (18), the symbol L stands for a single bond, O, S, NR ² , an alkylene group having 1 to 10 C atoms, which with one or more radicals R ³ may be substituted, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ³ .

In a further preferred embodiment of the invention, a maximum of two symbols X in each cycle stand for N and the other symbols X stand the same or different for each occurrence for CR ¹ . More preferably, at most one symbol X in each cycle is N and the other symbols X are the same or different at each occurrence for CR ¹ . Most preferably, all symbols X are the same or different at each occurrence for CR ¹ .

In a further preferred embodiment of the invention, the group Ar represents an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, particularly preferably having 5 to 24 aromatic ring atoms. In this case, preferably none of the aryl or heteroaryl groups of the aromatic or heteroaromatic ring system contains more than 10 aromatic ring atoms. Preferred groups Ar are therefore each composed of one or more of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, pyrrole, thiophene, furan, naphthalene, quinoline, isoquinoline, quinoxaline, indole, benzothiophene or benzofuran. Particularly preferred groups Ar are each composed of one or more groups benzene, pyridine, pyrimidine, pyridazine, pyrazine or triazine, in particular benzene. Another preferred group Ar is triphenylene.

In a particularly preferred embodiment of the invention, Ar is selected from the group consisting of the units of the following formulas (19) to (36), the dashed bond in each case indicating a link to the group Y:

In a further preferred embodiment of the invention, the index q = 0.

In a further preferred embodiment of the invention, the index n = 1, 2, 3 or 4, particularly preferably 1, 2 or 3, very particularly preferably 1 or 2.

In a further preferred embodiment of the invention, the radical R ^{1 is} identical or different at each occurrence selected from the group consisting of H, D, F, CN, 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 or an alkenyl group having 2 to 20 C atoms, each of which may be substituted by one or more R ³ radicals, one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ or O and wherein one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each with one or more radicals R ³ may be substituted, an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms which may be substituted by one or more R ³ , or a combination of these systems, optionally two o the more adjacent substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more R ³ radicals. Particularly preferably, the radical R ^{1 is the} same or different at each occurrence selected from the group consisting of H, D, CN, F, a straight-chain alkyl group having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, more preferably having 3 to 5 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, more preferably having 2 to 4 carbon atoms, each having one or more radicals R ³ may be substituted, wherein one or more H atoms may be replaced by D, an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, each of which may be substituted by one or more R ³ , or a combination of these systems, optionally two or more adjacent substituents R ^{1 can form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system substituted with one or more R ³ substituie rt can be.

In a further preferred embodiment of the invention, R ^{2 is the} same or different selected on each occurrence from the group consisting of a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each with a or a plurality of R ³ may be substituted, wherein one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R ³ , or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals. In a particularly preferred embodiment of the invention, R ^{2 is the} same or different selected on each occurrence from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted in each case with one or more radicals R ³ . In a very particularly preferred embodiment of the invention, R ^{2 is} phenyl, naphthyl, biphenyl or terphenyl, which may be substituted in each case by one or more radicals R ³ , in particular phenyl or biphenyl, which are each substituted by one or more radicals R ³ may, but is preferably unsubstituted.

Particular preference is given to compounds of the abovementioned formulas (1) or (8) to (18) in which the abovementioned preferences apply at the same time. Particular preference is therefore given to compounds in which:
Ar ¹ is the same or different at each occurrence for an aryl or heteroaryl group having 5 to 14 aromatic ring atoms, more preferably having 5 to 10 aromatic ring atoms, most preferably having 6 aromatic ring atoms;
Y is the same or different P (= O) or P (= S) at each occurrence;
Z is the same or different at each occurrence of NR ² if it does not form with A or B a ring according to formula (7);
X stands for CR ¹ or N, with a maximum of two symbols X representing N, preferably a maximum of one symbol X;
Ar is the same or different and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, particularly preferably having 5 to 24 aromatic ring atoms; preferably none of the aryl or heteroaryl groups of the aromatic or heteroaromatic ring system contains more than 10 aromatic ring atoms;
q is 0;
n is 1, 2, 3 or 4, preferably 1, 2 or 3.

R ¹ is identical or different at each occurrence selected from the group consisting of H, D, F, CN, 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 from 3 to 20 carbon atoms or an alkenyl group having from 2 to 20 carbon atoms, each of which may be substituted with one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups are represented by R ³ C = CR ³ or O may be replaced and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms which may be substituted with one or more R ³ radicals, or a combination of these systems, optionally two or more adjacent substituents R ^{1 being} a monocyclic or polycyc form aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals;
R ² in each occurrence is identically or differently selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is substituted by one or more R ³ radicals wherein one or more H atoms may be replaced by F or D, an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals.

Very particular preference is given to compounds of the formula (1) or of the formula (8) to (18) in which:
Ar ¹ is the same or different at each occurrence selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, furan, thiophene, pyrrole, naphthalene, quinoline, isoquinoline, quinoxaline, indole, benzofuran, benzothiophene and carbazole;
Y is P (= O);
Z is the same or different at each occurrence of NR ² if it does not form with A or B a ring according to formula (7);
X is the same or different every occurrence CR ¹ ;
Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is composed of one or more of the groups benzene, pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, thiophene, furan, naphthalene, triphenylene, quinoline, isoquinoline, quinoxaline, Idol, benzothiophene or benzofuran, preferably from in each case one or more groups benzene, pyridine, pyrimidine, pyridazine, pyrazine or triazine, in particular benzene;
q is 0;
n is 1 or 2;
R ¹ is the same or different at each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms, or a branched or cyclic alkyl group with 3 to 10 C atoms, particularly preferably having 3 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms, which may each be substituted by one or more radicals R ³ , wherein one or more H atoms may be replaced by D, an aromatic or heteroaromatic ring system having from 5 to 12 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals, and a combination of these systems optionally having two or more adjacent ones Substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals;
R ² is the same or different at each occurrence selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals.

For compounds which are processed from solution, suitable substituents are in particular also long alkyl groups, for example having 5 to 10 C atoms, or substituted or unsubstituted oligoarylene groups, such as, for example, terphenyl.

Preference is also given to compounds in which all radicals R ^{2 are the} same.

Examples of preferred compounds according to the above-mentioned embodiments or compounds, as they can be preferably used in organic electronic devices, are the compounds of the following structures (1) to (202).

As mentioned above, the compounds according to formula (1) are used in an electronic device. In this case, an electronic device is understood to mean a device which contains at least one layer which contains at least one organic compound. However, the component may also contain inorganic materials or even layers which are completely composed of inorganic materials.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), 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), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon emitting devices "( Koller et al., Nature Photonics 2008, 1-4 ), but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

The organic electroluminescent device includes cathode, anode and at least one emitting layer. In addition to these layers, they may also contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers and / or charge generation layers (charge generation layers). Likewise, interlayer may be introduced between two emitting layers which, for example, have an exciton-blocking function. It should be noted, however, that not necessarily each of these layers must be present. In this case, the organic electroluminescent device may contain an emitting layer, or it may contain a plurality of emitting layers. If several emission layers are present, they preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results, ie in the emitting layers different emitting compounds are used, which can fluoresce or phosphoresce. Particular preference is given to three-layer systems, the three layers showing blue, green and orange or red emission (for the basic structure see, for example, US Pat. WO 05/011013 ).

The compound according to the embodiments listed above can be used in different layers, depending on the exact structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (1) or formula (8) to (18) as matrix material for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters, and / or in a hole blocking layer and / or in an electron transport layer and or in an electron-blocking or exciton-blocking layer and / or in a hole-transport layer. The above-mentioned preferred embodiments also apply to the use of the materials in organic electronic devices.

In a preferred embodiment of the invention, the compound according to formula (1) or formula (8) to (18) is used as matrix material for a fluorescent or phosphorescent compound in an emitting layer. In this case, the organic electroluminescent device may contain an emitting layer, or it may contain a plurality of emitting layers, wherein at least one emitting layer contains at least one compound according to the invention as matrix material.

When the compound according to formula (1) or formula (8) to (18) is used as the matrix material for an emitting compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). In the context of this invention, phosphorescence is understood as meaning the luminescence from an excited state with a higher spin multiplicity, ie a spin state> 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with metals of the second and third transition metal series, in particular all iridium and platinum complexes, are to be regarded as phosphorescent compounds.

The mixture of the compound according to formula (1) or (8) to (18) and the emitting compound contains between 99 and 1% by volume, preferably between 98 and 10% by volume, more preferably between 97 and 60% by volume .-%, in particular between 95 and 80 vol .-% of the compound according to formula (1) or (8) to (18) based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99% by volume, preferably between 2 and 90% by volume, more preferably between 3 and 40% by volume, in particular between 5 and 20% by volume of the emitter, based on the total mixture Emitter and matrix material.

A further preferred embodiment of the present invention is the use of the compound according to formula (1) or formula (8) to (18) as matrix material for a phosphorescent emitter in combination with another matrix material. Particularly suitable matrix materials which can be used in combination with the compounds according to formula (1) or formula (8) to (18) are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, eg. B. according to WO 04/013080 . WO 04/093207 . WO 06/005627 or the undisclosed application DE 102008033943.1 , Triarylamines, carbazole derivatives, e.g. B. CBP (N, N-Biscarbazolylbiphenyl) or in WO 05/039246 . US 2005/0069729 . JP 2004/288381 . EP 1205527 or WO 08/086851 disclosed carbazole derivatives, indolocarbazole derivatives, e.g. B. according to WO 07/063754 or WO 08/056746 , Azacarbazolderivate, z. B. according to EP 1617710 . EP 1617711 . EP 1731584 . JP 2005/347160 , bipolar matrix materials, e.g. B. according to WO 07/137725 , Silane, z. B. according to WO 05/111172 , Azaborole or Boronester, z. B. according to WO 06/117052 , Triazine derivatives, e.g. B. according to the application not disclosed DE 102008036982.9 . WO 07/063754 or WO 08/056746 , Zinc complexes, e.g. B. according to EP 652273 or WO 09/062578 , or diazasilol or tetraazasilol derivatives, z. B. according to the application not disclosed DE 102008056688.8 ,

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

Examples of the emitters described above can be found in the applications WO 00/70655 . WO 01/41512 . WO 02/02714 . WO 02/15645 . EP 1191613 . EP 1191612 . EP 1191614 . WO 05/033244 . WO 05/019373 and US 2005/0258742 be removed. In general, all phosphorescent complexes used in the prior art for phosphorescent OLEDs and as known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art may use other phosphorescent complexes without inventive step.

In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, ie the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, such as in WO 05/053051 described. Further, it is possible to cause a metal complex, which is the same as or similar to the metal complex in the emitting layer, to be directly adjacent to the emitting layer as a hole-transporting material, such as a hole-injecting material. In WO 09/030981 described.

In a further preferred embodiment of the invention, the compound according to formula (1) or (8) to (18) is used as an electron transport material in an electron transport or electron injection layer. In this case, the emitting layer may be fluorescent or phosphorescent. When the compound is used as an electron transport material, it may be preferred if it is doped, for example, with alkali metal complexes, such as. B. Liq (Lithiumhydroxychinolinat).

In yet another preferred embodiment of the invention, the compound according to formula (1) or (8) to (18) is used 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.

It is further possible to use the compound according to formula (1) or (8) to (18) both in a hole blocking layer or electron transport layer and as a matrix in an emitting layer.

In yet another embodiment of the invention, the compound according to formula (1) or (8) to (18) is used in a hole transport layer or in an electron blocking layer or exciton blocking layer.

In the other layers of the organic electroluminescent device according to the invention, all materials can be used, as they are commonly used according to the prior art. The person skilled in the art can therefore use, without inventive step, all materials known for organic electroluminescent devices in combination with the compounds according to the invention of the formula (1) or formulas (8) to (18).

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

Further preferred is an organic electroluminescent device, characterized in that one or more layers of solution, such. B. by spin coating, or with any printing process, such. B. screen printing, flexographic printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (ink jet printing) can be produced. For this purpose, soluble compounds are necessary, which are obtained for example by suitable substitution. These methods are particularly suitable for oligomers, dendrimers and polymers.

These methods are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

The compounds of the formula (1) mentioned above as preferred are new and are therefore also an object of the present invention.

wobei für die verwendeten Symbole und Indizes gilt:
A-B und D-E ist jeweils gleich oder verschieden bei jedem Auftreten eine Einheit der folgenden Formel (2), (3), (4), (5) oder (6),

dabei stellt die gestrichelte Bindung jeweils die Bindung zu Z dar;
und
Z ist gleich oder verschieden bei jedem Auftreten N-R², O oder S, mit der Maßgabe, dass nicht beide Gruppen Z, die an dieselbe Gruppe Y binden, für O stehen;
oder
A-Z und B-Z ist jeweils gleich oder verschieden bei jedem Auftreten eine Einheit der folgenden Formel (7) und q = 0,

dabei stellt die gestrichelte Bindung in Formel (7) die Verknüpfung dieser Einheit in der Verbindung der Formel (1) dar, wobei der Stickstoff mit der Gruppe Y verknüpft ist;
Y ist bei jedem Auftreten gleich oder verschieden P(=O), As(=O), As(=S), Sb(=O), Sb(=S), Bi(=O) oder Bi(=S);
Ar ist bei jedem Auftreten gleich oder verschieden ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, welches durch einen oder mehrere Reste R¹ substituiert sein kann;
Ar¹ ist bei jedem Auftreten gleich oder verschieden eine Aryl- oder Heteroarylgruppe mit 5 bis 16 aromatischen Ringatomen, welche durch einen oder mehrere Reste R¹ substituiert sein kann;
X ist bei jedem Auftreten gleich oder verschieden CR¹ oder N;
L ist eine Einfachbindung oder eine bivalente, trivalente oder tetravalente Gruppe;
R¹ ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus H, D, F, Cl, Br, I, CN, NO₂, N(R³)₂, C(=O)R³, einer geradkettigen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 40 C-Atomen oder einer Alkenyl oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R³ substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R³C=CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C=O, C=S, C=Se, C=NR³, P(=O)(R³), SO, SO₂, NR³, O, S oder CONR³ ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R³ substituiert sein kann, einer Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die mit einem oder mehreren Resten R³ substituiert sein kann, oder einer Kombination dieser Systeme, wobei optional zwei oder mehr benachbarte Substituenten R¹ ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können, das mit einem oder mehreren Resten R³ substituiert sein kann;
R² ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus einer geradkettigen Alkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkylgruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R³ substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R³C=CR³, C≡C oder C=O ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R³ substituiert sein kann, oder einer Kombination dieser Systeme; dabei können optional solche R¹ und R², die in 1,2-Position zueinander benachbart stehen, ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden, das mit einem oder mehreren Resten R³ substituiert sein;
R³ ist ausgewählt aus der Gruppe bestehend aus H, D, F, CN, aliphatischem Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, aromatischem oder heteroaromatischem Ringsystem mit 5 bis 30 aromatischen Ringatomen, in dem ein oder mehrere H-Atome durch D, F, Cl, Br, I oder CN ersetzt sein können, wobei zwei oder mehr benachbarte Substituenten R³ miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können;
n ist 1 bis 10, bevorzugt 1, 2, 3, 4, 5 oder 6;
m ist 1, wenn L eine Einfachbindung oder eine bivalente Gruppe ist, oder ist 2, wenn L eine trivalente Gruppe ist, oder ist 3, wenn L eine tetravalente Gruppe ist;
q ist bei jedem Auftreten gleich oder verschieden 0 oder 1;
dabei sind die folgenden Verbindungen von der Erfindung ausgeschlossen:

The invention therefore relates to compounds according to formula (1 '),

where the symbols and indices used are:
Each of AB and DE is the same or different each occurrence of a unit represented by the following formula (2), (3), (4), (5) or (6),

the dashed bond represents the bond to Z;
and
Z is the same or different every occurrence of NR ² , O or S, provided that both groups Z, which bind to the same group Y, are not O;
or
AZ and BZ are each the same or different at each occurrence, a unit of the following formula (7) and q = 0,

where the dotted bond in formula (7) represents the linking of this moiety in the compound of formula (1) wherein the nitrogen is linked to the group Y;
Y is the same or different at every occurrence P (= O), As (= O), As (= S), Sb (= O), Sb (= S), Bi (= O) or Bi (= S);
Ar is identical or different at each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ;
Ar ¹ is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 16 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ;
X is the same or different CR ¹ or N at each occurrence;
L is a single bond or a bivalent, trivalent or tetravalent group;
R ¹ is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (R ³ ) ₂ , C (= O) R ³ , a straight-chain alkyl -, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each with one or R more radicals may be substituted ^3, wherein one or more non-adjacent CH ₂ groups represented by R ³ C = CR ^3, C≡C, Si (R ³⁾ _2, Ge (R ³⁾ _2, Sn (R ³⁾ ₂ , C = O, C = S, C = Se, C = NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ may be replaced and wherein one or a plurality of H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ringato which may be substituted by one or more radicals R ³ , or a combination of these systems, wherein optionally two or more adjacent substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system containing one or more radicals R ³ may be substituted;
R ² is the same or different each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each substituted with one or more R ³ radicals wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ , C≡C or C = O, and wherein one or more H atoms are represented by D, F, Cl, Br, I, CN or NO ₂ may be replaced, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals;
R ³ is selected from the group consisting of H, D, F, CN, aliphatic hydrocarbon radical having 1 to 20 C atoms, aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms by D, F , Cl, Br, I or CN may be replaced, wherein two or more adjacent substituents R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
n is 1 to 10, preferably 1, 2, 3, 4, 5 or 6;
m is 1 if L is a single bond or a divalent group, or 2 if L is a trivalent group, or 3 if L is a tetravalent group;
q is the same or different 0 or 1 at each occurrence;
The following compounds are excluded from the invention:

For the compounds according to formula (1 ') according to the invention, the same preferences apply as stated above for the electronic device.

Another object of the invention is therefore the use of the compounds of the invention in an electronic device.

wobei die verwendeten Symbole und Indizes oben für Formel (1) genannten Bedeutungen haben und t eine ganze Zahl von 1 bis 10, bevorzugt 1, 2, 3, 4, 5 oder 6, darstellt. Dabei gelten die oben für Formel (1) aufgeführten bevorzugten Ausführungsformen ebenso für Verbindungen der Formel (39). The invention furthermore relates to compounds of the formula (39) and their use in electronic devices and electronic devices, in particular organic electroluminescent devices comprising these compounds:

wherein the symbols and indices used have the meanings given above for formula (1) and t represents an integer from 1 to 10, preferably 1, 2, 3, 4, 5 or 6. The preferred embodiments given above for formula (1) also apply to compounds of the formula (39).

For the preparation of the compounds according to formula (1) or the compounds according to the invention, the process described below has been found to be particularly suitable. For this purpose, either an ortho-dibromo-substituted aromatic is reacted with a primary amine or an ortho-diamino-substituted aromatic with an aryl bromide in a Hartwig-Buchwald coupling, as listed in Scheme 1 as path A and path B. The resulting diamine is reacted with an aromatic phosphonic acid chloride or an aromatic bis (phosphonic acid chloride) to form the corresponding compound according to formula (1) or (1 '). The synthesis shown by way of example in Scheme 1 can, of course, be carried out quite analogously with other aromatic groups or with differently substituted groups.

Scheme 1:

The synthesis of compounds according to formula (1), which are substituted differently on the two ortho nitrogen atoms, is shown in Scheme 2. These compounds are accessible through the use of an ortho-diamino-substituted aromatic in which one of the two amino groups is substituted. Scheme 2:

A further subject of the present invention is a process for the preparation of the abovementioned compounds according to the invention by reacting an ortho-diamino-substituted aromatic, wherein the amino groups are unsubstituted or preferably monosubstituted, with an aromatic phosphonic acid chloride derivative or an aromatic Oligophosphonsäurechloridderivat.

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, or with reactive, polymerizable groups, such as olefins or oxetanes, can be used as monomers for producing corresponding oligomers, dendrimers or Find polymer use. The oligomerization or polymerization is preferably carried out via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is also possible to crosslink the polymers via such groups. The polymers of the invention can be used as a crosslinked or uncrosslinked layer.

The invention therefore further oligomers, polymers or dendrimers containing one or more of the compounds of the invention listed above, wherein one or more bonds of the inventive compound to the polymer, oligomer or dendrimer are present. Depending on the linkage of the compound according to the invention, this therefore forms a side chain of the oligomer or polymer or is linked in the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. The repeat units of the compounds according to the invention in oligomers, dendrimers and polymers have the same preferences as described above.

To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Preference is given to homopolymers or copolymers in which the units of the formula (1) or (8) to (18) or (39) to 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol% present are. Suitable and preferred comonomers which form the polymer backbone are selected from fluorene (e.g. EP 842208 or WO 00/22026 ), Spirobifluorenes (eg according to EP 707020 . EP 894107 or WO 06/061181 ), Para-phenylenes (e.g. WO 92/18552 ), Carbazoles (eg according to WO 04/070772 or WO 04/113468 ), Thiophenes (eg according to EP 1028136 ), Dihydrophenanthrenes (e.g. WO 05/014689 ), cis and trans indenofluorenes (eg according to WO 04/041901 or WO 04/113412 ), Ketones (eg according to WO 05/040302 ), Phenanthrenes (eg according to WO 05/104264 or WO 07/017066 ) or several of these units. The polymers, oligomers and dendrimers may also contain other units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units. In addition, the polymers may either be copolymerized or mixed in as a blend containing triplet emitters. Especially the combination of units according to the formulas (1) or (8) to (18) with triplet emitters leads to particularly good results.

wobei die verwendeten Symbole die oben genannten Bedeutungen aufweisen und r für eine ganze Zahl zwischen 2 und 1000000 steht. Diese Verbindungen, Oligomere und Polymere sind ebenfalls Gegenstand der vorliegenden Erfindung. Dabei gelten für die in Formel (37) und (38) aufgeführten Symbole die oben genannten Bevorzugungen. Insbesondere bevorzugt ist die Gruppe Ar¹ gleich oder verschieden bei jedem Auftreten gewählt aus 1,2,4,5-verknüpftem Benzol oder 1,2,3,4-verknüpftem Benzol.Another possibility of the polymerization is the reaction of a compound Hal ₂ Y-Ar-YHal ₂ , where Hal is Cl, Br or I, with a corresponding tetramine. This leads to compounds, oligomers and polymers according to the following formula (37). Analogously, the formation of compounds, oligomers and polymers according to the following formula (38) is possible.

where the symbols used have the meanings given above and r stands for an integer between 2 and 1,000,000. These compounds, oligomers and polymers are also the subject of the present invention. The above-mentioned preferences apply to the symbols listed in formulas (37) and (38). Most preferably, the group Ar ^{1 is the} same or different at each occurrence selected from 1,2,4,5-linked benzene or 1,2,3,4-linked benzene.

Furthermore, the compounds of the formula (1) or (1 ') can also be further functionalized and thus converted to extended structures. As an example, the reaction with arylboronic acids according to SUZUKI or with primary or secondary amines according to HARTWIG-BUCHWALD should be mentioned here. Thus, the compounds of the formula (1) or (1 ') can also be bonded directly to phosphorescent metal complexes or else to other metal complexes.

• 1. Die erfindungsgemäßen Verbindungen bzw. Verbindungen gemäß Formel (1) bzw. Formel (8) bis (18), eingesetzt als Matrixmaterial für fluoreszierende oder phosphoreszierende Emitter führen zu sehr hohen Effizienzen sowie zu langen Lebensdauern. Dies gilt insbesondere, wenn die Verbindungen als Matrixmaterial für einen phosphoreszierenden Emitter eingesetzt werden. Dabei werden wesentlich bessere Effizienzen, insbesondere Leistungseffizienzen, und Lebensdauern erhalten als bei Einsatz von strukturell ähnlichen Phosphinoxiden als Matrixmaterialien.
• 2. Die erfindungsgemäßen Verbindungen bzw. Verbindungen gemäß Formel (1) bzw. (8) bis (18) eignen sich nicht nur als Matrix für grün und rot phosphoreszierende Verbindungen, sondern insbesondere auch für blau phosphoreszierende Verbindungen.
• 3. Im Gegensatz zu vielen Verbindungen gemäß dem Stand der Technik, die der teilweisen oder vollständigen pyrolytischen Zersetzung bei Sublimation unterliegen, weisen die erfindungsgemäßen Verbindungen eine hohe thermische Stabilität auf.
• 4. Die erfindungsgemäßen Verbindungen, eingesetzt in organischen Elektrolumineszenzvorrichtungen, führen zu hohen Effizienzen und zu steilen Strom-Spannungs-Kurven mit niedrigen Einsatzspannungen.

The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by the following surprising advantages over the prior art:

• 1. The compounds of the invention or compounds of formula (1) or formula (8) to (18), used as a matrix material for fluorescent or phosphorescent emitters lead to very high efficiencies and to long lifetimes. This applies in particular if the compounds are used as matrix material for a phosphorescent emitter. Significantly better efficiencies, in particular power efficiencies, and lifetimes are obtained than with the use of structurally similar phosphine oxides as matrix materials.
• 2. The compounds of the invention or compounds of the formula (1) or (8) to (18) are not only suitable as a matrix for green and red phosphorescent compounds, but in particular also for blue phosphorescent compounds.
• 3. In contrast to many prior art compounds that undergo partial or complete pyrolytic decomposition on sublimation, the compounds of the invention have high thermal stability.
• 4. The compounds of the invention used in organic electroluminescent, lead to high efficiencies and steep current-voltage curves with low threshold voltages.

These advantages mentioned above are not accompanied by a deterioration of the other electronic properties.

The invention is explained in more detail by the following examples without wishing to restrict them thereby. The person skilled in the art can, from the descriptions, carry out the invention in the entire disclosed area and produce other inventive complexes without inventive step and use these in electronic devices or use the method according to the invention.

Examples:

Unless stated otherwise, the following syntheses are carried out under an inert gas atmosphere in dried solvents. As a starting compound z. B. 1,4-bis (phosphonic acid) benzene ( Inorganic Chemistry 1996, 35 (17), 4942-4949 ), N, N'-diphenyl-1,2-benzenediamine ( Organic Letters 2007, 9 (7), 1339-1342 ) or N-phenyl-o-phenylenediamine ( Indian Journal of Pharmaceutical Sciences 2003, 65 (2), 135-138 ) serve. Example 1: Synthesis of 1,4-bis (phosphonic acid chloride) benzene:

55.2 g (232 mmol) of 1,4-bis (phosphonic acid) benzene are initially charged in 1400 ml of methylene chloride and admixed with 10 drops of DMF. At room temperature, 86.3 ml (1020 mmol) of oxalyl chloride are added dropwise in 400 ml of methylene chloride and stirred at 45 ° C for 5 h. The solvent is removed in vacuo and the product recrystallized under inert gas in hexane. Yield: 70 g (227 mmol), 98%.

Example 2: General Synthesis of N, N'-Diaryl-1,2-benzenediamine

In 660 ml of degassed toluene, 1.06 g (4.75 mmol) of Pd (OAc) ₂ and 14.46 ml (14.46 mmol) of tri-tert-butylphosphine (1 M solution in toluene) are added and stirred for 5 min. touched. Then, the solution with 240 mmol of 1,2-dibromobenzene derivative, 505 mmol of arylamine and 67.22 g (700 mmol) of sodium tert-butoxide, post-degassed and stirred for 10 h at 140 ° C under a protective gas atmosphere. After cooling, the solution is treated with 600 ml of NH ₄ Cl solution and 150 ml of ethyl acetate, separated phases, washed with water, dried over MgSO ₄ and concentrated. The solid is dissolved in toluene and filtered through Celite. The crude product is stirred hot with heptane. Example 3: Synthesis of 4,5-dimethyl-N, N'-diphenyl-1,2-benzenediamine

The synthesis is carried out according to the general procedure according to Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 46 ml (505 mmol) of aniline. The precipitated solid is recrystallized from toluene / acetonitrile (5: 1) and the residue is washed with MeOH. This gives 65 g (223 mmol) of a crystalline solid. The total yield is 93%. Example 4: Synthesis of N, N'-ditolyl-1,2-benzenediamine

The synthesis is carried out according to the general procedure according to Example 2 from 56.6 g (240 mmol) of 1,2-dibromobenzene and 54 ml (505 mmol) of p-toluidine. The precipitated solid is recrystallized from toluene / acetonitrile (5: 1) and the residue is washed with MeOH. This gives 75 g (262 mmol) of a crystalline solid. The total yield is 98%. Example 5: Synthesis of N, N'-di-o-tolyl-1,2-benzenamine

The synthesis is carried out according to the general procedure according to Example 2 from 56.6 g (240 mmol) of 1,2-dibromobenzene and 54 ml (505 mmol) of o-toluidine. The precipitated solid is recrystallized from toluene / acetonitrile (5: 1) and the residue is washed with MeOH. This gives 68 g (237 mmol) of a crystalline solid. The total yield is 90%. Example 6: Synthesis of 4,5-dimethyl-N, N'-di-p-tolyl-1,2-benzenediamine

The synthesis is carried out according to the general procedure according to Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 54 ml (505 mmol) of p-toluidine. The precipitated solid is from toluene / acetonitrile Recrystallized (5: 1) and the residue washed with MeOH. This gives 69 g (218 mmol) of a crystalline solid. The total yield is 91%. Example 7: Synthesis of N, N'-bis (biphenyl-4-yl) -1,2-benzenediamine

The synthesis is carried out according to the general procedure according to Example 2 from 56.6 g (240 mmol) of 1,2-dibromobenzene and 85.4 g (505 mmol) of 4-aminobiphenyl. The precipitated solid is recrystallized from toluene / acetonitrile (5: 1) and the residue is washed with MeOH. This gives 78 g (189 mmol) of a crystalline solid. The total yield is 80%. Example 8: Synthesis of 4,5-dimethyl-N, N'-bis (biphenyl-4-yl) -1,2-benzenediamine

The synthesis is carried out according to the general procedure according to Example 2 from 63.3 g (240 mmol) of 1,2-dibromo-4,5-dimethylbenzene and 85.4 g (505 mmol) of 4-aminobiphenyl. The precipitated solid is recrystallized from toluene / acetonitrile (5: 1) and the residue is washed with MeOH. This gives 80.3 g (182 mmol) of a crystalline solid. The total yield is 76%. Example 9: Synthesis of N-biphenyl-4-yl-N'-phenyl-1,2-benzenediamine

In 660 ml of degassed toluene, 0.35 g (1.58 mmol) of Pd (OAc) ₂ and 4.8 ml (4.86 mmol) of tri-tert-butylphosphine (1 M solution in toluene) are added and stirred for 5 min. touched. Then, the solution with 37.2 g (160 mmol) of 4-bromobiphenyl, 29.4 g (160 mmol) of N-phenyl-o-phenylenediamine and 22.4 g (233 mmol) of sodium tert-butoxide, post-degassed and Stirred at 140 ° C under a protective gas atmosphere for 10 h. After cooling, the solution is treated with 200 ml of NH ₄ Cl solution and 50 ml of ethyl acetate, separated phases, washed with water, dried over MgSO ₄ and concentrated. The solid is dissolved in toluene and filtered through Celite. The crude product is stirred hot with heptane and washed with MeOH. This gives 47 g (140 mmol) of a crystalline solid. The total yield is 80%.

Example 10 General Synthesis of Diazaphospholes

158 mmol of N, N'-diaryl-1,2-benzenediamine are dissolved in 500 ml of pyridine and cooled to 0 ° C. 74 mmol of 1,4-bis (phosphonic acid chloride) benzene, dissolved in 1000 ml of toluene, are added dropwise dropwise at 0 ° C., with good stirring, to this solution, stirred for 1 h and then heated under reflux for 24 h. The solvent is distilled off in vacuo, the solid is boiled in ethyl acetate, filtered off with suction, washed once with 100 ml of acetic acid ester and then recrystallized from dioxane. Example 11: Synthesis of H3

The synthesis is carried out according to the general procedure according to Example 10 from 42 g (158 mmol) of N, N'-diphenyl-1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis (phosphonic acid) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 34.4 g (50 mmol), 68%, purity 99.9% (HPLC). Example 12: Synthesis of H4

The synthesis is carried out according to the general procedure according to Example 10 from 45.5 g (158 mmol) of 4,5-dimethyl-N, N'-diphenyl-1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis ( phosphonsäurechlorid) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 35.7 g (48 mmol), 65%, purity 99.9% (HPLC). Example 13: Synthesis of H5

The synthesis is carried out according to the general procedure according to Example 10 from 45.5 g (158 mmol) of N, N'-ditolyl-1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis (phosphonic acid chloride) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 37.9 g (51 mmol), 69%, purity 99.9% (HPLC). Example 14: Synthesis of H6

The synthesis is carried out according to the general procedure according to Example 10 from 65 g (158 mmol) of N, N'-bis (biphenyl-4-yl) -1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis (phosphonic acid chloride )benzene. The resulting solid is recrystallized several times from dioxane. Yield: 43.9 g (44.3 mmol), 60%, purity 99.9% (HPLC). Example 15: Synthesis of H7

The synthesis is carried out according to the general procedure of Example 10 from 45.5 g (158 mmol) of N, N'-di-o-tolyl-1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis (phosphonic acid chloride) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 34.6 g (46.5 mmol), 63%, purity 99.9% (HPLC). Example 16: Synthesis of H8

The synthesis is carried out according to the general procedure of Example 10 from 50.6 g (158 mmol) of 4,5-dimethyl-N, N'-di-p-tolyl-1,2-benzenediamine and 23 g (74 mmol) 1, 4-bis benzene (phosphonsäurechlorid). The resulting solid is recrystallized several times from dioxane. Yield: 35.4 g (44.3 mmol), 60%, purity 99.9% (HPLC). Example 17: Synthesis of H9

The synthesis is carried out according to the general procedure according to Example 10 from 69.6 g (158 mmol) of 4,5-dimethyl-N, N'-bis (biphenyl-4-yl) -1,2-benzenediamine and 23 g (74 mmol ) 1,4-bis (phosphonic acid chloride) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 48.8 g (46.6 mmol), 63%, purity 99.9% (HPLC). Example 18: Synthesis of H10

The synthesis is carried out according to the general procedure according to Example 9 from 53.1 g (158 mmol) of N-biphenyl-4-yl-N'-phenyl-1,2-benzenediamine and 23 g (74 mmol) of 1,4-bis ( phosphonsäurechlorid) benzene. The resulting solid is recrystallized several times from dioxane. Yield: 50.2 g (42 mmol), 81%, purity 99.9% (HPLC).

Example 19: Production of the OLEDs

The preparation of inventive OLEDs and OLEDs according to the prior art is carried out according to a general method according to WO 04/058911 , which is adapted to the conditions described here (layer thickness variation, materials used).

In the following Examples 20 to 36 (see Tables 1 and 2) the results of different OLEDs are presented. Glass slides coated with structured ITO (Indium Tin Oxide) 150 nm thick are coated with 20 nm PEDOT for improved processing (poly (3,4-ethylenedioxy-2,5-thiophene) spin-on from water; Starck, Goslar, Germany). These coated glass plates form the substrates to which the OLEDs are applied. In principle, the OLEDs have the following layer structure: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally one Cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs is shown in Table 1. The materials used to make the OLEDs are shown in Table 3.

All materials are thermally evaporated in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter), which is admixed to the matrix material or the matrix materials by co-evaporation in a certain volume fraction. An indication such as H1: CBP: TER1 (55%: 35%: 10%) here means that the material H1 in a volume fraction of 55%, CBP in a volume fraction of 35% and TER1 in a volume fraction of 10% in the layer is present. Analogously, the electron transport layer may consist of a mixture of two materials.

The OLEDs are characterized by default. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminance, calculated from current-voltage-brightness characteristics ( IUL characteristics), as well as the service life. The life is defined as the time after which the luminance has dropped from a certain starting luminous density I ₀ to a certain proportion. The term LD80 means that the said lifetime is the time at which the luminance has fallen to 0.8 · I ₀ (to 80%), ie of z. B. 4000 cd / m ² to 3200 cd / m ² .

The compounds according to the invention can be used inter alia as matrix materials (host materials, host materials) for phosphorescent dopants. Here are the compounds of the invention H3, H4, H5, H6 and H7 are used. As a comparison according to the prior art, the compounds H1 and H2 are used. There will be OLEDs with the green emitting dopant TEG1 as well the red emitting dopant TER1. The results of the OLEDs are summarized in Table 2. Ex. 20-26 show OLEDs with prior art materials and serve as comparative examples. The inventive OLEDs 27-36 show the advantages when using compounds according to formula (1).

The use of compounds according to the invention makes it possible to achieve improvements in all relevant parameters, above all life and power efficiency, as compared with the prior art. Especially the improvement of the power efficiency is of great importance, since the running time of mobile devices depends crucially on the energy consumption. Already increases of 10% can be regarded as significant progress.

Compared with the phosphine oxide-containing matrix material H2, the compounds according to the invention show the greatest progress (comparison of Ex. 24-26 with Ex. 32-36). By using the matrix materials H3, H4, H5, H6 and H7 according to the invention, comparable operating voltages are obtained as with the use of H2 according to the prior art, but the current efficiency can be significantly increased. The improvement is between about 25% (example 33 and example 25) up to about 50% (example 36 and example 26), which gives correspondingly improved performance efficiencies. This is especially evident when H1 is used as the electron transport material, here the improvement in power efficiency compared to the prior art is about 50% (Ex. 36 and Ex. 26). It should be noted that the improvement in power efficiency is accompanied by a significant increase in service life. Compared with the state of the art, the lifetime increases by a factor of 1.8 (example 33 and example 25) up to 2.8 (example 35 and example 25) by using compounds according to the invention.

Compared to OLEDs containing H1, which already show relatively good performance data, it is also possible to achieve significant improvements by using compounds according to the invention. This applies to red-emitting (examples 20, 21 in comparison to examples 27, 28) as well as for green-emitting OLEDs (examples 22, 23 and examples 29-31). With red-emitting OLEDs, the power efficiency can be significantly increased by a little more than 15%, and above all, the lifetime. The improvement in the lifetime is slightly over 50%. In the case of green-emitting OLEDs, the compounds according to the invention lead only to a slight or no increase in the power efficiency, but the use of H3, H4 and H5 as matrix materials results in a very significant improvement in the service life. The increase is up to 55% (Ex 29 and Ex 22). Table 1: Structure of the OLEDs Ex. HTL thickness IL thickness EBL thickness EML thickness HBL thickness ETL thickness EIL thickness 20 (Cf.) HTM1 20 nm - NPB 20 nm H1: TER1 (85%: 15%) 30 nm - Alq ₃ 20 nm LiF 1 nm 21 (Cf.) HTM1 20 nm - NPB 20 nm H1: CBP: TER1 (45%: 45%: 10%) 30 nm H1 10 nm Alq ₃ 20 nm LiF 1 nm 22 (See) HTM1 160 nm - EBM1 20 nm H1: TEG1 (90%: 10%) 30 nm H1 10 nm ETM1: LiQ (50%: 50%) 40 nm - 23 (Cf.) HTM1 160 nm - EBM1 20 nm H1: TEG1 (90%: 10%) 30 nm - ETM1: LiQ (50%: 50%) 40 nm - 24 (Cf.) HTM1 160 nm - EBM1 20 nm H2: TEG1 (90%: 10%) 30 nm H1 10 nm Alq ₃ 20 nm LiF 1 nm 25 (Cf.) HTM1 140 nm HIL1 5 nm EBM1 130 nm H2: TEG1 (85%: 15%) 30 nm - H1: LiQ (50%: 50%) 40 nm - 26 (Cf.) HTM1 140 nm HIL1 5 nm EBM1 130 nm H2: TEG1 (85%: 15%) - H1 40 nm LiQ 3 nm 27 HTM1 20 nm - NPB 20 nm H4: TER1 (85%: 15%) 30 nm - Alq ₃ 20 nm LiF 1 nm 28 HTM1 20 nm - NPB 20 nm H4: CBP: TER1 (45%: 45%: 10%) 30 nm H1 10 nm Alq ₃ 20 nm LiF 1 nm 29 HTM1 160 nm - EBM1 20 nm H3: TEG1 (90%: 10%) 30 nm H1 10 nm ETM1: LiQ (50%: 50%) 40 nm - 30 HTM1 160 nm - EBM1 20 nm H5: TEG1 (90%: 10%) 30 nm H1 10 nm ETM1: LiQ (50%: 50%) 40 nm - 31 HTM1 160 nm - EBM1 20 nm H4: TEG1 (90%: 10%) 30 nm - ETM1: LiQ (50%: 50%) 40 nm - 32 HTM1 160 nm - EBM1 20 nm H4: TEG1 (90%: 10%) 30 nm H1 10 nm Alq ₃ 20 nm LiF 1 nm 33 HTM1 140 nm HIL1 5 nm EBM1 130 nm H3: TEG1 (85%: 15%) 30 nm - H1: LiQ (50%: 50%) 40 nm - 34 HTM1 140 nm HIL1 5 nm EBM1 130 nm H6: TEG1 (85%: 15%) 30 nm - H1: LiQ (50%: 50%) 40 nm - 35 HTM1 140 nm HIL1 5 nm EBM1 130 nm H5: TEG1 (85%: 15%) - H1 40 nm LiQ 3 nm 36 HTM1 140 nm HIL1 5 nm EBM1 130 nm H7: TEG1 (85%: 15%) - H1 40 nm LiQ 3 nm Table 2: Results for the OLEDs Ex. Voltage for 1000 cd / m2 Efficiency at 1000 cd / m2 Efficiency at 1000 cd / m ² CIE x / y at 1000 cd / m ² LD80 I ₀ = 4000 cd / m ² 20 (Cf.) 5.0V 7.2 cd / A 4.5 lm / W 0.69 / 0.31 230 h 21 (Cf.) 5.2 V. 8.1 cd / A 4.9 lm / W 0.68 / 12:32 250 h 22 (See) 4.7 V 55 cd / A 37 lm / W 0.36 / 0.61 440 h 23 (Cf.) 4.6 V 54 cd / A 37 lm / W 0.37 / 0.60 400 h 24 (Cf.) 4.2 V 42 cd / A 31 lm / W 0.36 / 0.61 230 h 25 (Cf.) 4.0 V 43 cd / A 33 lm / W 0.38 / 12:59 300 h 26 (Cf.) 3.8 V 39 cd / A 32 lm / W 0.38 / 0.60 210 h 27 4.4 V 7.4 cd / A 5.3 lm / W 0.69 / 12:32 350 h 28 4.5 V 8.0 cd / A 5.6 lm / W 0.68 / 12:32 390 h ²⁹ 4.6 V 54 cd / A 37 lm / W 0.35 / 0.61 680 h 30 4.4 V 52 cd / A 37 lm / W 0.36 / 0.61 590 h 31 4.2 V 57 cd / A 43 lm / W 0.36 / 0.60 560 h 32 4.4 V 54 cd / A 39 lm / W 0.36 / 0.60 620 h 33 4.3 V 53 cd / A 38 lm / W 0.36 / 0.60 550 h 34 4.2 V 58 cd / A 43 lm / W 0.35 / 0.61 630 h 35 3.7 V 55 cd / A 47 lm / W 0.36 / 0.60 590 h 36 3.9 V 59 cd / A 48 lm / W 0.35 / 0.61 530 h

Table 3: Structural formulas of the materials used

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4539507 [0002]
• US 5151629 [0002]
• EP 0676461 [0002]
• WO 98/27136 [0002]
• WO 04/093207 [0004, 0039]
• DE 102008033943 [0004, 0039]
• WO 05/003253 [0004]
• WO 05/011013 [0034]
• WO 04/013080 [0039]
• WO 06/005627 [0039]
• WO 05/039246 [0039]
• US 2005/0069729 [0039]
• JP 2004/288381 [0039]
• EP 1205527 [0039]
• WO 08/086851 [0039]
• WO 07/063754 [0039, 0039]
• WO 08/056746 [0039, 0039]
• EP 1617710 [0039]
• EP 1617711 [0039]
• EP 1731584 [0039]
• JP 2005/347160 [0039]
• WO 07/137725 [0039]
• WO 05/111172 [0039]
• WO 06/117052 [0039]
• DE 102008036982 [0039]
• EP 652273 [0039]
• WO 09/062578 [0039]
• DE 102008056688 [0039]
• WO 00/70655 [0041]
• WO 01/41512 [0041]
• WO 02/02714 [0041]
• WO 02/15645 [0041]
• EP 1191613 [0041]
• EP 1191612 [0041]
• EP 1191614 [0041]
• WO 05/033244 [0041]
• WO 05/019373 [0041]
• US 2005/0258742 [0041]
• WO 05/053051 [0042]
• WO 09/030981 [0042]
• EP 842208 [0062]
• WO 00/22026 [0062]
• EP 707020 [0062]
• EP 894107 [0062]
• WO 06/061181 [0062]
• WO 92/18552 [0062]
• WO 04/070772 [0062]
• WO 04/113468 [0062]
• EP 1028136 [0062]
• WO 05/014689 [0062]
• WO 04/041901 [0062]
• WO 04/113412 [0062]
• WO 05/040302 [0062]
• WO 05/104264 [0062]
• WO 07/017066 [0062]
• WO 04/058911 [0087]

Cited non-patent literature

• MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6 [0002]
• Koller et al., Nature Photonics 2008, 1-4 [0033]
• MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301 [0049]
• Inorganic Chemistry 1996, 35 (17), 4942-4949 [0068]
• Organic Letters 2007, 9 (7), 1339-1342 [0068]
• Indian Journal of Pharmaceutical Sciences 2003, 65 (2), 135-138 [0068]

Claims (15)

Electronic device containing at least one compound according to formula (1),

where, for the symbols and indices used, AB and DE are each the same or different and each occurrence is a unit of the following formula (2), (3), (4), (5) or (6),

wherein the dashed bond represents the linkage with Z; and Z is the same or different at each occurrence of NR ² , O or S; or AZ and BZ are each the same or different at each occurrence, a unit of the following formula (7) and q = 0,

the dashed bond represents the linkage of this moiety in the compound of formula (1) wherein the nitrogen is linked to the group Y; Y is the same or different at every occurrence P (= O), P (= S), P, As (= O), As (= S), As, Sb (= O), Sb (= S), Sb, Bi (= O), Bi (= S) or Bi; Ar is identical or different at each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; Ar ¹ is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; X is the same or different CR ¹ or N at each occurrence; L is a single bond or a bivalent, trivalent or tetravalent group; R ¹ is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (R ³ ) ₂ , C (= O) R ³ , a straight-chain alkyl -, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each with a R or more radicals may be substituted ^3, wherein one or more non-adjacent CH ₂ groups represented by R ³ C = CR ^3, C≡C, Si (R ³⁾ _2, Ge (R ³⁾ _2, Sn (R ³ ) ₂ , C = O, C = S, C = Se, C = NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ may be replaced and wherein a or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals Aryloxy or heteroaryloxy group with 5 to 60 aromatic ringate omen, which may be substituted by one or more radicals R ³ , or a combination of these systems, wherein optionally two or more adjacent substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system containing one or more radicals R ³ may be substituted; R ² is the same or different each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each substituted with one or more R ³ radicals wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ , C≡C or C = O, and wherein one or more H atoms are represented by D, F, Cl, Br, I, CN or NO ₂ may be replaced, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals; R ³ is selected from the group consisting of H, D, F, CN, aliphatic hydrocarbon radical having 1 to 20 C atoms, aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms by D, F , Cl, Br, I or CN may be replaced, wherein two or more adjacent substituents R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; n is 1 to 10, preferably 1, 2, 3, 4, 5 or 6; m is 1 if L is a single bond or a divalent group, or 2 if L is a trivalent group, or 3 if L is a tetravalent group; q is the same or different 0 or 1 for each occurrence. Electronic device according to claim 1, characterized in that Ar ^{1 is} identical or different at each occurrence for an aryl or heteroaryl group having 5 to 14 aromatic ring atoms, preferably having 5 to 10 aromatic ring atoms, particularly preferably benzene, pyridine, pyrimidine, pyridazine, Pyrazine, triazine, furan, thiophene, pyrrole, naphthalene, phenanthrene, quinoline, isoquinoline, quinoxaline, indole, benzofuran, benzothiophene or carbazole. Electronic device according to claim 1 or 2, characterized in that the compound according to formula (1) is selected from compounds of formulas (8) to (18),

wherein the symbols and indices used have the meanings mentioned in claim 1. Electronic device according to one or more of claims 1 to 3, characterized in that the symbol Y for P (= O) and the symbol Z at each occurrence is the same or different for NR ² . Electronic device according to one or more of claims 1 to 4, characterized in that the group Ar is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably selected from the group consisting of the units of the following formulas (19) to ( 36), where the dashed bond indicates a link to the group Y:

Electronic device according to one or more of claims 1 to 5, characterized in that R ^{2 is the} same or different at each occurrence selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each with one or more radicals R ³ may be substituted, preferably phenyl, naphthyl, biphenyl or terphenyl, which may be substituted in each case with one or more radicals R ³ . Electronic device according to one or more of claims 1 to 6, characterized in that for the symbols and indices: Ar ¹ is identical or different at each occurrence for an aryl or heteroaryl group having 5 to 14 aromatic ring atoms, preferably 5 to 10 aromatic ring atoms, more preferably having 6 aromatic ring atoms; Y is the same or different P (= O) or P (= S) at each occurrence; Z is the same or different at each occurrence of NR ² if it does not form with A or B a ring according to formula (7); X stands for CR ¹ or N, with a maximum of two symbols X representing N, preferably a maximum of one symbol X; Ar is the same or different and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms; preferably none of the aryl or heteroaryl groups of the aromatic or heteroaromatic ring system contains more than 10 aromatic ring atoms; q is 0; n is 1, 2, 3 or 4, preferably 1, 2 or 3. R ¹ is the same or different in each occurrence selected from the group consisting of H, D, F, CN, 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 or an alkenyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R ³ , wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ or O and wherein one or more H atoms may be replaced by D or F aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ , an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms which may be substituted by one or more radicals R ³ , or one Combination of these systems wherein optionally two or more adjacent substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more R ³ groups; R ² in each occurrence is identically or differently selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is substituted by one or more R ³ radicals wherein one or more H atoms may be replaced by F or D, an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals; the further symbols and indices have the meanings mentioned in claim 1. Electronic device according to one or more of claims 1 to 7, characterized in that for the symbols and indices used: Ar ¹ is the same or different at each occurrence selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine , Furan, thiophene, pyrrole, naphthalene, quinoline, isoquinoline, quinoxaline, indole, benzofuran, benzothiophene and carbazole; Y is P (= O); Z is the same or different at each occurrence of NR ² if it does not form with A or B a ring according to formula (7); X is the same or different every occurrence CR ¹ ; Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is composed of one or more of the groups benzene, pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, thiophene, furan, naphthalene, triphenylene, quinoline, isoquinoline, quinoxaline, Indole, benzothiophene or benzofuran, preferably from in each case one or more groups benzene, pyridine, pyrimidine, pyridazine, pyrazine or triazine, in particular benzene; q is 0; n is 1 or 2; R ¹ is the same or different at each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms, or a branched or cyclic alkyl group with 3 to 10 C atoms, particularly preferably having 3 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms, which may each be substituted by one or more radicals R ³ , wherein one or more H atoms may be replaced by D, an aromatic or heteroaromatic ring system having from 5 to 12 aromatic ring atoms, each of which may be substituted with one or more R ³ radicals, and a combination of these systems optionally having two or more adjacent ones Substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals; R ² in each occurrence is identically or differently selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals; the other symbols and indices used have the meanings mentioned in claim 1. Electronic device according to one or more of claims 1 to 8, selected from the group consisting of organic electroluminescent devices (OLEDs), 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), light-emitting electrochemical cells (LECs), organic laser diodes ( O-lasers) and "organic plasmon emitting devices". Organic electroluminescent device according to one or more of claims 1 to 9, characterized in that the compound of formula (1) or formula (8) to (18) as a matrix material for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters, and / or as Lochblockiermaterial in a Lochblockierschicht and / or as an electron transport material in an electron transport layer or an electron injection layer and / or electron blocking material or exciton blocking in an electron-blocking or exciton-blocking layer and / or as a hole transport material in a hole transport layer or hole injection layer is used. Organic electroluminescent device according to claim 10, characterized in that the phosphorescent emitter used is a compound which contains copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular iridium or platinum , Compound according to formula (1 '),

where, for the symbols and indices used, AB and DE are each the same or different and each occurrence is a unit of the following formula (2), (3), (4), (5) or (6),

the dashed bond represents the bond to Z; and Z is the same or different at each occurrence of NR ² , O or S, provided that both groups Z, which bind to the same group Y, are not O; or AZ and BZ are each the same or different at each occurrence, a unit of the following formula (7) and q = 0,

where the dotted bond in formula (7) represents the linking of this moiety in the compound of formula (1) wherein the nitrogen is linked to the group Y; Y is the same or different at every occurrence P (= O), As (= O), As (= S), Sb (= O), Sb (= S), Bi (= O) or Bi (= S); Ar is identical or different at each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; Ar ¹ is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 16 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; X is the same or different CR ¹ or N at each occurrence; L is a single bond or a bivalent, trivalent or tetravalent group; R ¹ is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (R ³ ) ₂ , C (= O) R ³ , a straight-chain alkyl -, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each with one or R more radicals may be substituted ^3, wherein one or more non-adjacent CH ₂ groups represented by R ³ C = CR ^3, C≡C, Si (R ³⁾ _2, Ge (R ³⁾ _2, Sn (R ³⁾ ₂ , C = O, C = S, C = Se, C = NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ may be replaced and wherein one or a plurality of H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ringato which may be substituted by one or more radicals R ³ , or a combination of these systems, wherein optionally two or more adjacent substituents R ^{1 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system containing one or more radicals R ³ may be substituted; R ² is the same or different each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each substituted with one or more R ³ radicals wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C = CR ³ , C≡C or C = O, and wherein one or more H atoms are represented by D, F, Cl, Br, I, CN or NO ₂ may be replaced, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or a combination of these systems; Optionally, those R ¹ and R ² adjacent to one another in the 1,2-position may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ³ radicals; R ³ is selected from the group consisting of H, D, F, CN, aliphatic hydrocarbon radical having 1 to 20 C atoms, aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms by D, F , Cl, Br, I or CN may be replaced, wherein two or more adjacent substituents R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; n is 1 to 10, preferably 1, 2, 3, 4, 5 or 6; m is 1 if L is a single bond or a divalent group, or 2 if L is a trivalent group, or 3 if L is a tetravalent group; q is the same or different 0 or 1 at each occurrence; The following compounds are excluded from the invention:

Use of a compound according to claim 12 in an electronic device. A process for the preparation of a compound according to claim 12 by reacting an ortho-diamino-substituted aromatic, wherein the amino groups are unsubstituted or preferably monosubstituted, with an aromatic phosphonic acid chloride derivative and an aromatic oligophosphonic acid chloride derivative, respectively. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 12, wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present, or oligomer or polymer according to formula (37) or formula (38),

wherein the symbols used have the meanings mentioned in claim 11 and r stands for an integer between 2 and 1,000,000.