New materials for organic light-emitting devices

Abstract

The present invention relates to OLED materials for use in electronic devices, in particular in organic light-emitting devices, and to electronic devices, in particular organic light-emitting devices, comprising these OLED materials.

Description

[0001] Foreignfiling text P24-180

[0002] -1 -

[0003] New materials for organic light-emitting devices

[0004] The present invention relates to OLED materials for use in electronic devices, in particular in organic light-emitting devices, as well as electronic devices, in particular organic

[0005] 5 light-emitting devices containing these OLED materials.

[0006] Organic electroluminescent devices (OLEDs) typically comprise one or more emission layers as well as other layers, such as one or more hole injection layers, hole transport layers,

[0007] 10 exciton-blocking layers and / or electron-blocking layers arranged between the emitting layer and the anode, and / or one or more hole-blocking layers, electron transport layers and / or electron injection layers arranged between the emitting layer and the cathode, and / or charge-generation layers.

[0008] 15. The properties of organic electroluminescent devices are not solely determined by the emitters and matrix materials used in the emitting layer. The additional layers listed above also have a significant influence on the performance of electroluminescent devices.

[0009] Improvements to the materials used in these layers can lead to significant enhancements in organic electroluminescent devices, for example, in terms of lifetime, efficiency, and operating voltage. In particular, there is a need for charge transport materials, such as electron transport materials, with materials possessing a low refractive index.

[0010] 25 (refractive index RI). A reduced refractive index of the electron transport layer leads to improved light extraction and thus to an improvement in the external quantum efficiency of the OLED.

[0011] The object of the present invention is to provide compounds which

[0012] 30 are suitable for use in an OLED, in particular as an electron transport material and / or hole-blocking material, and result in good properties there. In particular, it is the object of the present invention to provide materials with a low refractive index for use in an electron transport and / or hole-blocking layer, which thereby lead to improved

[0013] 35 Foreignfiling text P24-180

[0014] -2-

[0015] Light extraction is achieved. These compounds should also exhibit high temperature stability and high electron conductivity. High temperature stability is necessary so that the compounds can be evaporated without decomposition in high vacuum, thus ensuring a long lifetime for the organic electroluminescent device. Furthermore, these compounds should...

[0016] 5. Use in an OLED leads to high efficiency and lifespan and to low operating voltage.

[0017] Surprisingly, it was found that the compounds described below are very well suited for use in an electron transport and / or hole

[0018] These materials are suitable for use in blocking layers and result in very good device properties with regard to efficiency, lifespan, and operating voltage. This applies to both phosphorescent and fluorescent OLEDs. In particular, these materials exhibit a low refractive index, which leads to improved light extraction from the OLED and thus to improved efficiency.

[0019] 15

[0020] The subject of the invention is therefore a compound according to the following formula (1),

[0021] Formula 1)

[0022] 30 where the compound may also be partially or completely deuterated and the symbols and indices have the following meanings:

[0023] ETU is, in each occurrence, either the same or different, an electron-deficient hetero¬

[0024] 35 aryl group containing 5 to 18 aromatic ring atoms, which are partially or Foreignfiling text P24-180

[0025] -3- may be completely deuterated and / or may be substituted by one or more Ar residues and / or by one or more R residues;

[0026] L, in each occurrence, is either a single bond or a phenylene group, which may be partially or completely deuterated and / or

[0027] 5 may be substituted by one or more residues R;

[0028] Ar, in each occurrence, is either the same or different, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which may be partially or completely deuterated and / or divided by one or

[0029] 10 several residues R can be substituted;

[0030] R is the same or different in each occurrence F, CI, Br, I, CN, Si(R 2 )s, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 C-

[0031] 15 atoms, an alkenyl or alkynyl group with 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may each be partially or completely deuterated and / or with one or more R groups 2 can be substituted, with one or more non-adjacent CH2-

[0032] 20 groups through C(R 2 )=C(R 2 ), Si(R2 )2, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 which may be replaced by an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40

[0033] 25 aromatic ring atoms, which may be partially or completely deuterated and / or have one or more R groups 2 may be substituted; optionally, two or more adjacent residues R can form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0034] 30

[0035] R 1is the same or different H, D, F, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl group may be partially or completely deuterated and / or have one or more R groups. 2 substitutes Foreignfiling text P24-180

[0036] -4- can be, or a phenyl group which can be partially or completely deuterated; optionally, two R groups can be present in each case. 1 , which bind to the same carbon atom, forming a mono- or polycyclic, aliphatic or aromatic ring system;

[0037] 5 R 2is the same or different in each occurrence H, D, F, CN, an aliphatic hydrocarbon residue with 1 to 20 C atoms, which may be partially or completely deuterated, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which one or more Fl atoms may be replaced by D, F, CI, Br, I or CN and which is connected by a

[0038] 10 or more alkyl groups, each with 1 to 4 carbon atoms, which may be partially or completely deuterated, can be substituted; optionally, two or more, preferably adjacent, R groups can be substituted. 2 form a mono- or polycyclic, aliphatic ring system;

[0039] 15 n, m, o, p are equal or different at each occurrence 0 or 1 with the proviso that n + m + o + p = 1 or 2; q is 0 to (4 - o);

[0040] 20 r is 0 to (4 - p); s is 0 to (4 - m);

[0041] 25 t is 0 to (4 - n).

[0042] An aryl group according to this invention contains 6 to 40 carbon atoms; a heteroaryl group according to this invention contains 2 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms

[0043] 30 yields at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl or heteroaryl group is either a simple aromatic cycle, i.e., 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. Foreignfiling text P24-180

[0044] -5-

[0045] Quinoline, isoquinoline, etc., are understood. Aromatics linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0046] An aromatic ring system according to this invention contains 6 to 60 carbon atoms,

[0047] 5 preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system according to this invention contains 2 to 60 C atoms, preferably 2 to 40 C atoms and at least one heteroatom in the ring system, provided that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic

[0048] 10. A cyclic ring system within the meaning of this invention shall be understood to be a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups may also be connected by a non-aromatic unit, such as a C, N, or O atom. Likewise, systems in which two or more aryl or heteroaryl groups are connected by a non-aromatic unit, such as a C, N, or O atom, shall be understood to be included.

[0049] 15 aryl groups are directly linked to one another, such as biphenyl, terphenyl, bipyridine, or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc., are also to be understood as aromatic ring systems within the meaning of this invention, and

[0050] 20. Systems in which two or more aryl groups are linked, for example, by a short alkyl group are also accepted. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups, as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example, biphenyl or bipyridine, and fluorene or spirobifluorene.

[0051] 25

[0052] An electron-deficient heteroaryl group, as defined as group ETU (= electron transporting unit), is, in the sense of the present invention, a heteroaryl group with 6 aromatic ring atoms containing at least one nitrogen atom, for example pyridine, pyrimidine or triazine, or a heteroaryl group with

[0053] 30 5 aromatic ring atoms containing at least one nitrogen atom and at least one further heteroatom selected from N, O and / or S, for example imidazole, oxazole, thiazole, oxadiazole or triazole, wherein further aryl and / or heteroaryl groups may be fused to the above-mentioned groups, for example benzimidazole, quinazoline or quinoxaline. These groups are Foreignfiling text P24-180

[0054] -6- common features are that, due to the at least one nitrogen atom in the ring, it is an electron-deficient group that can be easily reduced and is therefore suitable for use in an electron-transporting material.

[0055] Within the scope of the present invention, the term alkyl group includes both

[0056] 5 linear, as well as branched and / or cyclic alkyl groups, wherein cyclic alkyl groups can be monocyclic, bicyclic, tricyclic or oligocyclic. The same applies to alkenyl and alkynyl groups. Within the scope of the present invention, an aliphatic hydrocarbon residue or an alkyl group or an alkenyl or alkynyl group, which can contain 1 to 40 carbon atoms, are defined as follows:

[0057] 10 and in which individual H atoms or CH2 groups may also be substituted by the groups mentioned above, preferably the residues methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,

[0058] 15 Propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl are understood. Under an alkoxy group OR 1 with 1 to 40 carbon atoms, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy are preferred.

[0059] 20 n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n- Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2- Ethylhexyloxy, Pentafluorethoxy und 2, 2, 2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe SR 1 mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethyl- thio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio,

[0060] 25 n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclo- pentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio,

[0061] 30 Hexinylthio, heptinylthio or octinylthio. In general, alkyl, alkenyl, alkynyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the groups mentioned above; Foreignfiling text P24-180

[0062] -7- Furthermore, one or more H atoms can also be replaced by D, F, CI, Br, I, CN or NO2, preferably by D, F or CN.

[0063] An aromatic or heteroaromatic ring system with 5–60 aromatic ring atoms, each further compounded with the aforementioned R groups. 1 sub¬

[0064] 5 can be situated, in particular groups are understood to be those derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis-

[0065] 10 or trans-lndolocarbazole, truxene, 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, Benzo-7,8-quinoline, Phenothiazine, Phenoxazine, Pyrazole, Indazole, Imidazole, Benzimidazole,

[0066] 15 Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinazolin, Chinoxalin, 1,5-Diaza-

[0067] 20 anthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1,8-Diazapyren, 4,5- Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Pheno- thiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3- Triazol, 1,2,4-Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1,2,5-Oxa- diazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-

[0068] 25 Thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combinations of these systems.

[0069] The formulation that two or more adjacent residues combine to form a

[0070] The phrase "30 rings can form" in the context of this description means, among other things, that the two residues are linked to each other by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0071] 35 Foreignfiling text P24-180

[0072] -8-

[0073] 5

[0074] Similarly, the formation of a condensed aromatic ring is possible when two substituents R, each representing an alkenyl group, are linked together by a chemical bond with the formal elimination of two hydrogen atoms. Furthermore, the above formulation should also be understood to mean that if one of the two substituents represents hydrogen, the

[0075] 10. The second residue binds to the position to which the hydrogen atom was bound, forming a ring.

[0076] Ring formation occurs through adjacent residues, with adjacent residues in

[0077] 15 In the sense of the present invention, either residues are bonded to carbon atoms directly bonded to one another, or by residues bonded to the same carbon atom.

[0078] The compounds according to the invention can also be used partially or fully.

[0079] 20 can be constantly deuterated, i.e. that both the basic structure and all groups or substituents contained in the compound can be partially or completely deuterated and / or that a deuterium atom (D) can also be bonded at positions that are shown unsubstituted.

[0080] 25

[0081] The compounds of formula (1) and their preferred embodiments are described below. The preferred embodiments also apply to the electronic device or organic electroluminescence device according to the invention.

[0082] 30

[0083] In a preferred embodiment of the invention, the sum of the indices m + n + o + p = 1, such that the compound according to formula (1) contains exactly one group -L-ETU.

[0084] 35 Foreignfiling text P24-180

[0085] -9-

[0086] In one embodiment of the invention, n = 1, and it is a compound according to one of the following formulas (2a) to (2d),

[0087] 5

[0088] 10

[0089] 15

[0090] 20 where the compounds can also be partially or completely deuterated, t = 0,

[0091] 25 1 , 2 or 3 is and the other symbols and indices used have the meanings mentioned above.

[0092] In a further embodiment of the invention, m = 1 or p = 1, wherein, depending on whether m = 1 or p = 1, the corresponding enantiomers are

[0093] 30, and it is a compound according to one of the following formulas (3a) to (3d),

[0094] 35 Foreignfiling text P24-180

[0095] 5

[0096] 10

[0097] 15

[0098] 20 where the compounds may also be partially or completely deuterated, s = 0, 1, 2 or 3 and the other symbols and indices used have the meanings mentioned above.

[0099] In another embodiment of the invention, o = 1, and it is a

[0100] 25 a compound according to one of the following formulas (4a) to (4d),

[0101] 30

[0102] 35 Foreignfiling text P24-180

[0103] 5

[0104] 10 where the compounds may also be partially or completely deuterated, q = 0, 1, 2 or 3 and the other symbols and indices used have the meanings mentioned above.

[0105] 15

[0106] In a preferred embodiment of the compounds of formula (1) or (2a) to (2d), (3a) to (3d) and (4a) to (4d), the indices q, r, s and t are the same or different in each occurrence 0, 1 or 2, particularly preferably 0 or 1 and most preferably 0. Furthermore, it is preferred if the sum of the indices q +

[0107] 20 r + s + t = O, 1 , 2, 3 or 4 is, particularly preferably 0, 1 or 2 and most particularly preferably 0.

[0108] Preferred electron-transporting heteroaryl groups (ETUs) are described below. In a preferred embodiment of the invention, ETU is a

[0109] 25 electron-deficient heteroaryl groups with 5 to 14 aromatic ring atoms, particularly preferably with 6 to 13 aromatic ring atoms and most preferably with 6 to 12 aromatic ring atoms, wherein the electron-deficient heteroaryl group may be partially or completely deuterated and / or substituted by one or more Ar and / or R groups. ETU preferably

[0110] 30. The heteroaryl group contains no more than four heteroatoms, and particularly preferably no more than three heteroatoms. ETU more preferably has at least two heteroatoms in the heteroaryl group, preferably two nitrogen atoms. If the ETU group is substituted, it is preferably substituted by one or more Ar groups and not by further R groups.

[0111] 35 Foreignfiling text P24-180

[0112] -12-

[0113] Preferred ETU groups are selected from the group consisting of pyridine,

[0114] Pyrimidine, Pyridazine, Pyrazine, Triazine, Quinazoline, Quinoxline, Benzimidol,

[0115] Phenanthroline, triazoloquinazoline, diazadibenzofuran and diazadibenzothiophene, in particular from the following structures (ET11-1) to (ET11-33),

[0116] 5

[0117] 10 Foreignfiling text P24-180

[0118] -13-

[0119] 10

[0120] 15 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), and where the structures may also be substituted by one or more Ar and / or R groups

[0121] 20 may be and / or partially or completely deuterated.

[0122] If the above-mentioned structures have one or more substituents, these are preferably substituents Ar and not substituents R, preferably with no, one or two substituents Ar in the group ETU.

[0123] 25 hands are.

[0124] The preferred structures are (ETU-4), (ETU-5), (ETU-6), (ETU-10), (ETU-14), (ETU-11-15), (ETU-11-21), (ETU-22) and (ETU-24), whereby these structures may also be partially or completely deuterated and augmented by one or more residues Ar

[0125] 30 and / or R may be substituted, in particular by no, one or two substituents Ar. The structures (ETU-4), (ETU-6), (ETU-10), (ETU-14) and (ETU-15) are particularly preferred, and the structure (ETU-10), i.e. a triazine group, is especially preferred.

[0126] 35 Foreignfiling text P24-180

[0127] -14-

[0128] Preferred embodiments of groups (ETU-11-4), (ETU-11-5), (ETU-11-6), (ETU-11-10), (ETU-14), (ETU-15), (ETU-21), (ETU-22) and (ETU-24) are the structures of the following formulas (ETU-4a) to (ETU-24a),

[0129] 10

[0130] 15 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), Ar the above

[0131] 25 mentioned meanings and the structures may also be partially or completely deuterated.

[0132] Structures (ETU-4a), (ETU-5a), (ETU-10a), (ETU-14a) and (ETU-15a) are particularly preferred, and structure (ETU-10a) is especially preferred.

[0133] 30

[0134] In a further preferred embodiment of the invention, Ar is, whether identical or different in each occurrence, an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, particularly preferably with 6 to 18 aromatic ring atoms, and most preferably with 6 to 13 aromatic

[0135] 35 ring atoms, each of which may be partially or completely deuterated and / or Foreignfiling text P24-180

[0136] -15- may be substituted by one or more residues R, but is preferably unsubstituted.

[0137] Suitable groups Ar are selected from the following structures (Ar-1) to (Ar-141), either identical or different at each occurrence, where these structures are also partially

[0138] 5. may be either completely or sparingly deuterated and / or substituted by one or more substituents R, but are preferably unsubstituted.

[0139] 10

[0140] 15

[0141] 20

[0142] 25

[0143] 30

[0144] 35 Foreignfiling text P24-180

[0145] 5

[0146] 10

[0147] 15

[0148] 20

[0149] 25

[0150] 30

[0151] 35 Foreignfiling text P24-180

[0152] 5

[0153] 10

[0154] 15

[0155] 20

[0156] 25

[0157] 30

[0158] 35 Foreignfiling text P24-180

[0159] 5

[0160] 10

[0161] 15

[0162] 20

[0163] 25

[0164] 30

[0165] 35 Foreignfiling text P24-180

[0166] 5

[0167] 10

[0168] 15

[0169] 20

[0170] 25

[0171] 30

[0172] 35 Foreignfiling text P24-180

[0173] 5

[0174] 10

[0175] 15

[0176] 20

[0177] 25

[0178] 30

[0179] 35 Foreignfiling text P24-180

[0180] -21-

[0181] 5

[0182] 10

[0183] 15

[0184] 20

[0185] 25

[0186] 30

[0187] 35 Foreignfiling text P24-180

[0188] 5

[0189] 10

[0190] 15

[0191] 20

[0192] Ar is particularly preferred, whether the same or different, and is selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran or dibenzothiophene, each of which may also be partially or completely deuterated.

[0193] 25 may be and / or substituted by one or more R groups, in particular phenyl, meta- or para-biphenyl, terphenyl, dibenzofuran, fluorene or spirobifluorene, each of which may also be partially or completely deuterated and / or substituted by one or more R groups.

[0194] 30 In a further preferred embodiment of the invention, L represents, in each instance, a single bond or a meta- or para-phenylene group, which may be partially or completely deuterated and / or substituted by one or more residues R, but preferably is unsubstituted. Particularly preferably, L represents a single bond or a meta-

[0195] 35 Foreignfiling text P24-180

[0196] -23-

[0197] phenylene group, which may be partially or completely deuterated, and is especially preferred for a single bond.

[0198] According to a further preferred embodiment of the invention, R 1 same or different, selected from the group consisting of H for each occurrence

[0199] 5D, a straight-chain alkyl group with 1 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, wherein the alkyl group may also be partially or completely deuterated; in each case, two R groups may be 1 , which bond to the same carbon atom also form a ring together. R is particularly favored. 1 same or different selected for each occurrence

[0200] 10 of the group consisting of H, D, a straight-chain alkyl group with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein one or more H atoms in the alkyl group may also be replaced by D. R is particularly preferred. 1 same or different for each occurrence, selected from the group

[0201] 15 consisting of H, D or an optionally deuterated methyl group, in particular H.

[0202] In a further preferred embodiment of the invention, R is selected from the group consisting of F, CN, or is the same or different at each occurrence.

[0203] 20 Si(R 2 )a, a straight-chain alkyl group with 1 to 10 carbon atoms, a branched or cyclic alkyl group with 3 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms, wherein the alkyl or alkenyl group may be partially or completely deuterated and / or have one or more R groups 2 may be substituted, or an aromatic or heteroaromatic ring system with

[0204] 25 6 to 24 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2can be substituted; optionally, two adjacent residues R can form a mono- or polycyclic, aliphatic, or aromatic ring system. Particularly preferably, R is selected from the group consisting of F, CN, or a different residue in each occurrence.

[0205] 30 Si(R 2 )a, a straight-chain alkyl group with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein the alkyl group may be partially or completely deuterated, or an aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms,

[0206] 35 Foreignfiling text P24-180

[0207] -24- which may be partially or completely deuterated and / or containing one or more preferably non-aromatic residues R 2It can be substituted. R is particularly preferred as being the same or different in each occurrence, either methyl or phenyl.

[0208] 5. It is preferred if the above-mentioned preferences occur simultaneously. Therefore, compounds of formula (1) or of formulas (2a) to (2d), (3a) to (3d) or (4a) to (4d) are preferred, for which the following holds:

[0209] ETU is, in each occurrence, either the same or different, an electron-deficient hetero¬

[0210] 10 aryl group with 5 to 14 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms and particularly preferably with 6 to 12 aromatic ring atoms, wherein the electron-deficient heteroaryl group may be partially or completely deuterated and / or substituted by one or more Ar and / or R groups; wherein ETU has no more than four

[0211] 15 heteroatoms in the heteroaryl group, preferably at least two and not more than three heteroatoms;

[0212] L is the same or different in each occurrence, a simple bond or a

[0213] 20 meta- or para-phenylene group, which may be partially or completely deuterated and / or substituted by one or more R residues, but is preferably unsubstituted;

[0214] Ar is, in each occurrence, either the same or different, an aromatic or hetero¬

[0215] 25 Aromatic ring system with 6 to 24 aromatic ring atoms, each of which may be partially or completely deuterated and / or substituted by one or more R groups;

[0216] R is selected from the group in each instance, either the same or different.

[0217] 30 consisting of F, CN, Si(R 2)s, a straight-chain alkyl group with 1 to 10 carbon atoms, a branched or cyclic alkyl group with 3 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms, wherein the alkyl or alkenyl group may be partially or completely deuterated and / or with

[0218] 35 Foreignfiling text P24-180

[0219] -25- one or more residues R 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2 can be substituted; optionally, two adjacent residues R can be a mono- or polycyclic, aliphatic or

[0220] 5 aromatic ring systems are formed;

[0221] R 1is selected from the group consisting of H, D, a straight-chain alkyl group with 1 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, in each occurrence, either the same or different.

[0222] 10 where the alkyl group may also be partially or completely deuterated; two R groups may be involved 1 , which bond to the same carbon atom, each also form a ring with each other; q, r, s, t are the same or different at each occurrence 0, 1 or 2, where the

[0223] 15 The sum of the indices q + r + s + t is at most 4.

[0224] Compounds of formula (1) or of formula (2a) to (2d), (3a) to (3d) or (4a) to (4d) are particularly preferred, for which the following applies:

[0225] 20

[0226] ETU is the same or different at each occurrence selected from the following structures (ETU-1) to (ETU-33),

[0227] 25

[0228] 30

[0229] 35 Foreignfiling text P24-180

[0230] 35 Foreignfiling text P24-180

[0231] -27-

[0232] 10

[0233] 15 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), and where the structures may also be substituted by one or more Ar groups and / or be partially or completely deuterated;

[0234] 20

[0235] L is, in each instance, either a single bond or a meta-phenylene group, which may be partially or completely deuterated;

[0236] Ar is, in each occurrence, either the same or different, an aromatic or hetero¬

[0237] 25 Aromatic ring system with 6 to 18 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms, each of which may be partially or completely deuterated and / or substituted by one or more R groups, but preferably unsubstituted;

[0238] 30

[0239] R is selected from the group consisting of F, CN, Si(R) in each instance, either the same or different. 2 )s, a straight-chain alkyl group with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein the alkyl group

[0240] 35 Foreignfiling text P24-180

[0241] -28- may each be partially or completely deuterated, or an aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more preferably non-aromatic residues R 2 may be substituted;

[0242] 5

[0243] R 1 is selected in each occurrence, either the same or different, from the group consisting of H, D, a straight-chain alkyl group with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein in the alkyl group each

[0244] 10. One or more H atoms can also be replaced by D; in this case, two R groups can be involved. 1, which bond to the same carbon atom, each also form a ring with each other; q, r, s, t is the same or different 0 or 1 in each occurrence , where the

[0245] 15 The sum of the indices q + r + s + t is at most 2.

[0246] Compounds of formula (1) or of formula (2a) to (2d), (3a) to (3d) or (4a) to (4d) are particularly preferred, for which the following applies:

[0247] 20

[0248] ETU is the same or different at each occurrence selected from the following structures (ETU-4a) to (ETU-24a), with structure (ETU-10a) being particularly preferred.

[0249] 25

[0250] 30

[0251] 35 Foreignfiling text P24-180

[0252] -29-

[0253] 5 where the dashed bond represents the bond to the corresponding carbon atom

[0254] 20 atoms in formula (1) and the structures may also be partially or completely deuterated;

[0255] L is a single bond;

[0256] 25. Ar is chosen in each occurrence, either the same or different from the structures listed above (Ar-1) to (Ar-141), wherein these structures may also be partially or completely deuterated and / or substituted by one or more substituents R, but are preferably unsubstituted; in this respect, Ar is particularly preferably chosen in each occurrence, either the same or different from the

[0257] 30 Group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran, dibenzothiophene or carbazole, each of which may also be partially or completely deuterated and / or substituted by one or more R groups, but preferably unsubstituted;

[0258] 35 Foreignfiling text P24-180

[0259] R 1 is selected from the group consisting of H, D or an optionally deuterated methyl group, preferably H, in each occurrence, either the same or different; q, r, s, t is 0 in each case.

[0260] 5

[0261] Examples of suitable compounds according to the invention according to formula (1) or the preferred embodiments are listed in Table 1 below.

[0262] 10

[0263] 15

[0264] 20

[0265] 25

[0266] 30

[0267] 35 Foreignfiling text P24-180

[0268] -31-

[0269] 5

[0270] 10

[0271] 15

[0272] 20

[0273] 25

[0274] 35 Foreignfiling text P24-180

[0275] -32-

[0276] 5

[0277] 10

[0278] 15

[0279] 20

[0280] 25

[0281] 30

[0282] 35 Foreignfiling text P24-180

[0283] -33-

[0284] 5

[0285] 10

[0286] 15

[0287] 20

[0288] 25

[0289] 35 Foreignfiling text P24-180

[0290] 5

[0291] 10

[0292] 15

[0293] 20

[0294] 25

[0295] 30

[0296] 35 Foreignfiling text P24-180

[0297] -35-

[0298] 10

[0299] 15

[0300] 20

[0301] 25 Foreignfiling text P24-180

[0302] 5

[0303] 10

[0304] 15

[0305] 20

[0306] 25

[0307] 30 Foreignfiling text P24-180

[0308] -37-

[0309] 35 Foreignfiling text P24-180

[0310] -38-

[0311] 30

[0312] 35 Foreignfiling text P24-180 Foreignfiling text P24-180

[0313] 5

[0314] 10

[0315] 15

[0316] 20

[0317] 25

[0318] 30

[0319] 35 Foreignfiling text P24-180

[0320] 5

[0321] 10

[0322] 15

[0323] 20

[0324] 25

[0325] 30

[0326] 35 Foreignfiling text P24-180

[0327] 5

[0328] 10

[0329] 15

[0330] 20

[0331] 25

[0332] 30

[0333] 35 Foreignfiling text P24-180

[0334] 5

[0335] 10

[0336] 15

[0337] 20

[0338] 25

[0339] 30

[0340] 35 Foreignfiling text P24-180

[0341] 5

[0342] 10

[0343] 15

[0344] 20

[0345] 25

[0346] 30

[0347] 35 Foreignfiling text P24-180

[0348] 5

[0349] 10

[0350] 15

[0351] 20

[0352] 25

[0353] 30

[0354] 35 Foreignfiling text P24-180

[0355] -46-

[0356] 5

[0357] 10

[0358] 15

[0359] 20

[0360] 25

[0361] 30

[0362] 35 Foreignfiling text P24-180

[0363] 5

[0364] 10

[0365] 15

[0366] 20

[0367] 25

[0368] 30

[0369] 35 Foreignfiling text P24-180

[0370] 5

[0371] 10

[0372] 15

[0373] 20

[0374] 25

[0375] 30

[0376] 35 Foreignfiling text P24-180

[0377] -49-

[0378] 5

[0379] 10

[0380] 15

[0381] 20

[0382] 25

[0383] 30

[0384] 35 Foreignfiling text P24-180

[0385] -50-

[0386] 5

[0387] 10

[0388] 15

[0389] 20

[0390] 25

[0391] 30

[0392] 35 Foreignfiling text P24-180 Foreignfiling text P24-180

[0393] -52-

[0394] 5

[0395] 10

[0396] 15

[0397] 20

[0398] 25

[0399] 30

[0400] 35 Foreignfiling text P24-180

[0401] -53-

[0402] 5

[0403] 10

[0404] 15

[0405] 20

[0406] 25

[0407] 30

[0408] 35 Foreignfiling text P24-180

[0409] -54-

[0410] 5

[0411] The compounds according to the invention can be synthesized using synthesis steps generally known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. Thus, the

[0412] 10. The basic framework of the compounds according to the invention, which is substituted with a reactive leaving group X, for example chlorine, is synthesized according to the methods shown in Schemes 1 and 2. For the sake of clarity, only a small number of substituents are shown in the schemes.

[0413] Paragraph 15 does not preclude the presence of further substituents in the processes. The processes shown for the synthesis of the compounds according to the invention are to be understood as examples. The person skilled in the art can develop alternative synthetic routes within the scope of their general technical knowledge.

[0414] 20 Scheme 1

[0415] 30

[0416] Scheme 2

[0417] 35 Foreignfiling text P24-180

[0418] 10. In Schemes 1 and 2, X represents a reactive leaving group, for example, CI. The basic structure shown in Schemes 1 and 2 can be further converted in a coupling reaction. For example, the reactive leaving group X can be converted to a boronic acid or a boronic acid ester, which can then be coupled in a Suzuki reaction with a group ETLI-Y or ETU-LY, respectively.

[0419] 15 is coupled, where Y represents a reactive exit group, for example CI or Br, as shown in Scheme 3.

[0420] Scheme 3

[0421] 1) Butyllithium

[0422] 20 G

[0423] 25

[0424] In Scheme 3, Y represents a reactive leaving group, for example CI or Br. Analogously to Scheme 3, the starting material from Scheme 2 can also be converted to corresponding compounds according to the invention.

[0425] Another object of the present invention is therefore a method for

[0426] 30 Preparation of the compounds according to the invention, comprising the steps:

[0427] (a) Provision of the basic structure of the compound of formula (1), which, instead of the -L-ETU group, has a reactive leaving group, for example boronic acid,

[0428] 35 Boronic acid esters, chlorine or bromine, carries; and Foreignfiling text P24-180

[0429] -56-

[0430] (b) Introduction of the group -L-ETU by a clutch reaction, for example a Suzuki clutch.

[0431] As described above, the compounds according to the invention can also be partially or completely deuterated. This can be achieved in the synthesis by either

[0432] 5 deuterated starting materials are used, or a non-deuterated compound of formula (1) is first synthesized, which is then deuterated in a subsequent step. Deuteration methods are generally known to those skilled in the art and are described, for example, in KR2016041014 A, WO2017 / 122988 A1, KR2020052820 A, KR101978651 B1 and WO2018 / 110887 A1 or in Bulletin of the Chemical Society of Japan, 2021, 94(2).

[0433] 10 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071 described.

[0434] For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations are required.

[0435] 15 of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene,

[0436] 20 Methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-Methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl¬

[0437] 25 benzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, Methylbenzoat, NMP, p-Cymol, Phenetol, 1 ,4-Diiso- propylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Triethylenglycolbutyl- methylether, Diethylenglycoldibutylether, Triethylenglycoldimethylether, Diethylen- glycolmonobutylether, T ripropylenglycoldimethylether, T etraethylenglycoldimethyl-

[0438] 30 ether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1 ,1-Bis(3,4-dimethylphenyl)ethan oder Mischungen dieser Lösemittel.

[0439] 35 Foreignfiling text P24-180

[0440] -57-

[0441] The present invention therefore also relates to mixtures containing at least one compound according to formula (1) or according to the preferred embodiments and at least one further material and / or at least one solvent, in particular an organic solvent. Further materials may include, for example, further electron transport materials, emitters, matrix materials.

[0442] 5 or n dots, as explained in more detail below, can be used.

[0443] Another object is the use of the compounds according to the invention in an electronic device, in particular in an organic electroluminescence device. An electronic device within the meaning of the present

[0444] 10. The invention is a device which contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers which are composed entirely of inorganic materials.

[0445] 15

[0446] A further object of the invention is an electronic device, in particular an organic electroluminescent device, comprising one or more compounds according to the invention. The electronic device is preferably selected from the group consisting of organic electroluminescent compounds.

[0447] 20 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), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench

[0448] 25 Devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-Lasers) and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs), wherein the OLEDs may be fluorescent, phosphorescent, hyperfluorescent or hyperphosphorescent.

[0449] 30

[0450] The organic electroluminescent device contains a cathode, anode, and at least one emitting layer. In addition to these layers, it may contain further layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, and other layers.

[0451] 35 Foreignfiling text P24-180

[0452] -58- layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers. Interlayers, which may, for example, have an exciton blocking function, can also be introduced between two emitting layers. However, it should be noted that not every one of these layers is necessarily

[0453] 5 must be present. The organic electroluminescent device can contain one emitting layer, or it can contain several emitting layers. If several emission layers are present, they preferably exhibit several emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., in the emitting layers.

[0454] 10. Various emitting compounds are used that can fluoresce or phosphoresce. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem OLED, especially for white.

[0455] 15 emitting OLEDs. The compound according to the invention can be used in different layers, depending on the exact structure.

[0456] In a preferred embodiment of the invention, the invention can

[0457] 20. The compound is used as an electron transport material in an electron transport layer and / or in a hole-blocking layer of an organic electroluminescent device, wherein the electroluminescent device may be fluorescent or phosphorescent. An electron transport layer is understood to be a layer arranged between the emission layer and the cathode.

[0458] 25. A hole-blocking layer is understood to be a layer that directly borders the emission layer on the cathode side. Due to the low refractive index of the compounds according to the invention, they are particularly suitable for use in an electron transport layer, as they lead to improved light extraction there.

[0459] 30

[0460] A hole-blocking layer is typically used as a pure layer of a material. An electron transport layer is typically used either as a pure layer of a material or as a mixture with another electron transport material, for example, as a mixture with LiQ (lithium quinolinate).

[0461] 35 Foreignfiling text P24-180

[0462] -59-

[0463] The electron injection layer is typically a pure layer of the electron injection material, for example LiQ or LiF, as a very thin layer, for example with a layer thickness in the range of 1 to 5 nm, in direct contact with the cathode.

[0464] 5 According to a further embodiment, the compound of formula (1) or of the preferred embodiments is used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds, wherein the phosphorescent compounds can phosphoresce red, orange, yellow, green or blue. Alternatively

[0465] 10 it is a hyperphosphorescent emitting layer which, in addition to the phosphorescent compound, also has a fluorescent emitter.

[0466] In this case, the proportion of matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%.

[0467] 15. The matrix material is particularly preferably between 85.0 and 97.0 vol.%, and may also be a mixture of two or more matrix materials. Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.%, and particularly preferably between 3.0 and 15.0 vol.%.

[0468] 20%.

[0469] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple emitting compounds. In this case as well,

[0470] 25. The emitting compounds are generally those compounds whose proportion in the system is smaller, and the matrix materials are those compounds whose proportion in the system is larger. In individual cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single emitting compound.

[0471] 30

[0472] It is preferred that the compounds according to the invention are used as a component of mixed-matrix systems, preferably for phosphorescent emitters. The mixed-matrix systems preferably comprise two or three different

[0473] 35 Foreignfiling text P24-180

[0474] -60-

[0475] Matrix materials, particularly preferably two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. Since the compounds according to the invention have electron-transporting properties, they are preferably combined with a hole-

[0476] 5 transporting compound combined. The two matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 and most preferably 1:4 to 1:1, with the hole-transporting matrix material usually being present in a higher proportion.

[0477] 10

[0478] According to a preferred embodiment, in the case of mixed-matrix systems, the two or more matrix materials are used as a mixture and applied by evaporation.

[0479] 15 The following material classes are preferably used in the above-mentioned layers of the device:

[0480] Phosphorescent emitters:

[0481] The term phosphorescent emitters typically encompasses compounds that

[0482] 20 in which light emission occurs via a spin-forbidden transition, for example, a transition from an excited triplet state or a state with a higher spin quantum number, for example, a quintet state. Compounds that emit light, preferably in the visible range, upon suitable excitation are particularly suitable as phosphorescent emitters.

[0483] 25. Furthermore, the compound contains at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and particularly preferably greater than 56 and less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferably used as phosphor emitters, in particular compounds containing iridium,

[0484] 30 contain platinum or copper. For the purposes of the present invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds. Examples of suitable phosphorescent emitters are listed in the following table.

[0485] 35 Foreignfiling text P24-180

[0486] -61 -

[0487] 5

[0488] 10

[0489] 15

[0490] 20

[0491] 25

[0492] 30

[0493] 35 Foreignfiling text P24-180

[0494] -62-

[0495] 5

[0496] 10

[0497] 15

[0498] 20

[0499] 25

[0500] 30

[0501] 35 Foreignfiling text P24-180

[0502] 5

[0503] 10

[0504] 15

[0505] 20

[0506] Fluorescent emitters:

[0507] 25

[0508] Preferred fluorescent compounds are selected from the class of arylamines. For the purposes of this invention, an arylamine or aromatic amine is understood to be a compound in which three substituted or unsubstituted aromatic or heteroaromatic ring systems are directly coupled to the nitrogen atom.

[0509] 30 bound. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples are aromatic anthracenemines, aromatic anthracenediamines, aromatic pyrenemines, aromatic pyrenediamines, aromatic chrysenemines, or aromatic chrysen-

[0510] 35 Foreignfiling text P24-180

[0511] -64- diamine. An aromatic anthracene is understood to be a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at position 9. An aromatic anthracenediamine is understood to be a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at positions 9 and 10. Aromatic pyrenamines,

[0512] Pyrenediamines, chrysenamines, and chrysendiamines are defined analogously, wherein the diarylamine groups on the pyrene are preferably bonded at the 1-position or the 1,6-position, respectively. Further preferred emitting compounds are indenofluorenamines and diamines, benzoindenofluorenamines and diamines, and dibenzoindenofluorenamines and diamines, as well as indenofluorene derivatives with fused aryl groups.

[0513] 10 groups. Pyrene arylamines are also preferred. Benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan or thiophene units are also preferred. Other suitable fluorescent emitters are DABNA and DABNA derivatives.

[0514] 15

[0515] Matrix materials for fluorescent emitters:

[0516] Preferred matrix materials for fluorescent emitters are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenyl-spirobifluorene), in particular

[0517] 20 of the oligoarylenes containing condensed aromatic groups, hole-conducting compounds, electron-conducting compounds, in particular ketones, phosphine oxides and sulfoxides, or benzanthracenes. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers thereof.

[0518] 25 compounds, the ketones, the phosphine oxides and the sulfoxides. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds. An oligoarylene within the meaning of this invention shall be understood to be a compound in which at least three aryl or

[0519] 30 arylene groups are bonded together.

[0520] Matrix materials for phosphorescent emitters:

[0521] Preferred matrix materials for phosphorescent emitters include, besides the Ver-

[0522] 35 bonds of formula (1) aromatic ketones, aromatic phosphine oxides or foreignfiling text P24-180

[0523] -65- aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g. B. CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indeno-carbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaborols or boron esters, triazine derivatives, dibenzofuran or dibenzothiophene derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, Diazaphosphole derivatives, above

[0524] 5 bridged carbazole derivatives, triphenylene derivatives or lactams.

[0525] Electron-transporting materials:

[0526] Suitable electron-transporting materials include, in addition to the compounds according to the present invention, for example those described in Y. Shirota et al., Chem.

[0527] 10 Rev. 2007, 107(4), 953-1010 disclosed compounds or other materials as they are used in these layers according to the prior art. Any materials used as electron transport materials in the electron transport layer according to the prior art can be used as materials for the electron transport layer. In particular, aluminum-

[0528] 15 complexes, for example Alqs, zirconium complexes, for example Zrq4, lithium complexes, for example Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphol derivatives

[0529] 20 and phosphine oxide derivatives. Preferred electron transport and electron injection materials remain the compounds explicitly shown on pages 73-75 of W02020 / 109434A1.

[0530] Hole transporting materials:

[0531] 25 Compounds that are preferably used in hole-transporting layers of the OLEDs according to the invention are indenofluorenamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with fused aromatics, monobenzoindenofluorenamines, dibenzoindenofluorenamines, spirobifluorenamines, fluorenamines, spirodibenzopyranamines, dihydroacridine derivatives, and spirodibenzofurans.

[0532] 30 and spirodibenzothiophenes, phenanthrene diarylamines, spirotribenzotropolones, spirobifluorenes with meta-phenyldiamine groups, spirobisacridines, xanthenediarylamines, and 9,10-dihydroanthracene spiro compounds with diarylamine groups. Preferred hole-transporting compounds are also those explicitly shown on pages 76-80 of W02020 / 109434A1.

[0533] 35 Foreignfiling text P24-180

[0534] -66-

[0535] Metals with low work function, metal alloys, or multilayer structures made of different metals are preferred as cathodes for electronic devices, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Furthermore, the following are also suitable:

[0536] 5. Alloys of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver. In multilayer structures, additional metals with a relatively high work function, such as silver (Ag) or aluminum (Al), can also be used in addition to the metals mentioned above. In these cases, combinations of the metals, such as calcium (Ca / Ag), magnesium (Mg / Ag), or barium (Ba / Ag), are typically used.

[0537] 10. It may also be preferable to introduce a thin interlayer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. For this purpose, alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides, are suitable.

[0538] Fifteen carbonates are suitable (e.g., LiF, U₂O, BaF₂, MgO, NaF, CsF, CS₂CO₃, etc.). Lithium quinolinate (LiQ) can also be used. The layer thickness is preferably between 0.5 and 5 nm.

[0539] Materials with a high work function are preferred as anodes. Preferably, the

[0540] The anode has a work function greater than 4.5 eV compared to a vacuum. Metals with high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Alternatively, metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or semi-transparent to either prevent irradiation of the organic

[0541] 25. Materials (organic solar cell) or the extraction of light (OLED, O-LASER). Preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive, doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode can also be made of

[0542] 30 several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0543] 35 Foreignfiling text P24-180

[0544] -67-

[0545] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated using a sublimation process. The materials are applied in vacuum sublimation systems at an initial pressure of less than 10⁻⁶. 5 mbar, preferably less than 10 6 mbar vaporized. However, it is also possible that the initial pressure is still

[0546] 5 is less, for example less than 10' 7 mbar.

[0547] An electronic device is also preferred, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation.

[0548] 10. The materials are subjected to a pressure between 10' 5mbar and 1 bar are applied. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0549] 15

[0550] A further preferred electronic device is characterized in that one or more layers are formed from a solution, e.g. by spin coating, or by any printing process, e.g. screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging,

[0551] 20. Thermal transfer printing) or inkjet printing. Soluble compounds according to formula (1) or the preferred embodiments are required for this. High solubility can be achieved by suitable substitution of the compounds.

[0552] 25 It is further preferred that, to produce an electronic device according to the invention, one or more layers of solution and one or more layers are applied by a sublimation process.

[0553] The compounds according to the invention, when used in an OLED, lead to

[0554] 30. The use of materials according to the invention results in very good device properties with regard to efficiency, lifetime, and operating voltage, particularly in the electron transport and / or hole-blocking layer of an OLED. This applies to both phosphorescent and fluorescent OLEDs. In particular, the efficiency of the OLED can be improved with the materials according to the invention.

[0555] 35 Foreignfiling text P24-180

[0556] -68-

[0557] OLEDs can be improved because their low refractive index leads to improved light extraction from the OLED.

[0558] Examples

[0559] 5 Example a) 2-Chloro-1",3"-dihydro-3'H-dispiro[fluorene-9,T-indene-2 , ,2"-inden]

[0560] 10

[0561] 23.9 g (90 mmol) of 2-bromo-4'-chloro-1,1'-biphenyl are placed in 300 mL of THF at -78 °C. At this temperature, 40 mL of n-butyllithium (2 M in hexane) are added dropwise. After 1 h, 21 g (94 mmol) of 1',3'-dihydro-2,2'-spirobi[indene]-1(3H)-one in 200 mL of THF are added dropwise. The mixture is stirred overnight at room temperature.

[0562] 15 ml of the solution were added to ice water and extracted with dichloromethane. The combined organic phases were washed with water and dried over sodium sulfate. The solvent was removed under vacuum, and the residue was heated under reflux overnight at 100 °C with 94 mL HCl and 1000 mL AcOH without further purification. After cooling, the precipitated solid was filtered off and washed.

[0563] 20. This was reacted once with 100 ml water, three times with 100 ml ethanol each, and finally recrystallized from heptane. Yield: 23 g (57 mmol), 84%; purity approx. 98% by 1H-NMR.

[0564] 25. Similarly, the following compounds can be synthesized:

[0565] 30

[0566] 35 Foreignfiling text P24-180

[0567] 5

[0568] 10

[0569] 15

[0570] 20

[0571] Example b) (1",3"-Dihydro-3 , H-dispiro[fluoren-9,T-inden-2',2"-indene]-2-yl)- boronic acid

[0572] A solution of 109 g (270 mmol) of 2-chloro-1",3"-dihydro-3'H- cooled to -78 °C

[0573] 30 dispiro[fluorene-9,1'-indene-2',2"-indene] in 1500 ml of diethyl ether is added dropwise to 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred for 30 min at -78 °C. It is allowed to come to room temperature, cooled again to -78 °C, and then rapidly mixed with a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether. After warming to -10 °C, the mixture is treated with

[0574] 35 135 ml of 2 N hydrochloric acid is hydrolyzed. The organic phase is separated, with foreign filing text P24-180.

[0575] -70-

[0576] Washed with water, dried over sodium sulfate, and concentrated to dryness. The residue is dissolved in 300 ml of n-heptane, the colorless solid is filtered off, washed with n-heptane, and dried under vacuum. Yield: 96 g (232 mmol), 86% of theory; purity: 96% by HPLC.

[0577] 5. The following connections can be made in an analogous manner:

[0578] 10

[0579] 15

[0580] 20

[0581] 25

[0582] 30

[0583] Example c) 2-(1",3"-Dihydro-3 , H-dispiro[fluorene-9,1 , -inden-2 , ,2"-inden]-2-yl)-4,6-diphenyl-1,3,5-triazine

[0584] 35 Foreignfiling text P24-180

[0585] 5

[0586] 9.90 g (37.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 16.8 g (40.7 mmol) of (1",3"-dihydro-3'H-dispiro[fluoren-9,T-inden-2',2"-indene]-2-yl)boronic acid are dissolved in 120 ml of 1,4-dioxane and 120 ml of toluene. The solution is heated to 40 °C and 430 mg (0.372 mmol) of tetrakis(triphenylphosphine)palladium(0) are added. 5.62 g (41.0

[0587] 10 mmol of potassium carbonate are dissolved in 45 ml of distilled water and added dropwise at 40 °C. The reaction mixture is heated under reflux for 2.5 h. After cooling to room temperature, ethyl acetate and water are added. The aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with saturated NaCl solution and treated with Na₂SC>4.

[0588] 15. The solvent is removed under reduced pressure. The residue is separated by chromatography (heptane:toluene = 1:1), followed by recrystallization from heptane. Yield: 22.2 g (39 mmol), 91% of theory; purity: 98% by HPLC.

[0589] 20

[0590] Similarly, the following compounds can be synthesized:

[0591] 25

[0592] 30

[0593] 35 Foreignfiling text P24-180

[0594] 30

[0595] 35 Foreignfiling text P24-180

[0596] 30

[0597] 35 Foreignfiling text P24-180

[0598] 5

[0599] 10

[0600] 15

[0601] 20

[0602] 25

[0603] 30

[0604] 35 Foreignfiling text P24-180

[0605] 35 Foreignfiling text P24-180

[0606] 35 Foreignfiling text P24-180

[0607] 5

[0608] 10

[0609] 15

[0610] 20

[0611] 25

[0612] 30

[0613] 35 Foreignfiling text P24-180

[0614] 5

[0615] 10

[0616] 15

[0617] 20

[0618] 25

[0619] 30

[0620] 35 Foreignfiling text P24-180

[0621] 5

[0622] 10

[0623] 15

[0624] 20

[0625] 25

[0626] 30

[0627] 35 Foreignfiling text P24-180

[0628] -80-

[0629] Manufacturing of OLEDs

[0630] The following examples B1 to B10 (see Tables 1 and 2) present the data for various OLEDs.

[0631] 5. Pretreatment for examples B1 to B10: Glass plates coated with 50 nm thick structured ITO (indium tin oxide) are coated with 20 nm PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), sourced as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Germany, spin-coated from aqueous solution) for improved processing.

[0632] Ten coated glass plates form the substrates onto which the OLEDs are applied.

[0633] OLEDs generally have the following layer structure: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) /

[0634] 15 Emission layer (EML) / optional hole-blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs can be found in Table 1. The materials used to manufacture the

[0635] The materials used in 20 OLEDs are shown in Table 2.

[0636] All materials, except for PEDOT:PSS, are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host material) and an emitting dopant.

[0637] 25. Substance (doping agent, emitter) that is added to the matrix material(s) by cover vapor deposition in a specific volume fraction. A specification such as IC1:H14:TEG1 (55%:35%:10%) means that the material IC1 is present in a volume fraction of 55%, H14 in a volume fraction of 35%, and TEG1 in a volume fraction of 10% in the layer. Similarly, the electron concentration can also be specified.

[0638] 30 transport layers consist of a mixture of two materials.

[0639] The OLEDs are characterized according to standard procedures. This includes measuring the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in imp / W), and external quantum efficiency (EQE, measured in percent).

[0640] 35 Foreignfiling text P24-180

[0641] -81 - as a function of the luminance, calculated from current-voltage-luminance characteristic curves (IUL characteristics) assuming a Lambertian emission characteristic, and the lifetime are determined. The electroluminescence spectra are measured at a luminance of 1000 cd / m². 2 The CIE 1931 x and y color coordinates were determined and calculated from them. The value U1000 in Table 2 denotes the voltage.

[0642] 5, which are for a luminance of 1000 cd / m² 2 SE1000 and LE1000 denote the current and power efficiency respectively, which is required at 1000 cd / m². 2 EQE1000 denotes the external quantum efficiency at an operating luminance of 1000 cd / m². 2 The lifetime LD is defined as the time after which the luminance, when operating at constant current, decreases from the initial luminance to a certain level.

[0643] 10. A certain proportion of L1 decreases. A value of LO;jO = ​​4000 cd / m² 2and L1 = 70% in Table 2 means that the lifetime specified in column LD corresponds to the time after which the initial luminance of 4000 cd / m² 2 at 2800 cd / m² 2 decreases. Analogously, LO;jO = ​​20 mA / cm². 2 , L1 = 80%, that the luminance when operating at 20mA / cm 2 After a certain period, LD drops to 80% of its initial value.

[0644] 15

[0645] The data for the various OLEDs are summarized in Table 3. Examples B1-B7 show data for OLEDs according to the invention.

[0646] 20 The examples and comparisons presented here demonstrate improved quantum efficiency (Table 3).

[0647] Table 1: Structure of OLEDs

[0648] 25

[0649] 30

[0650] 35 Foreignfiling text P24-180

[0651] 5

[0652] 10

[0653] Table 2: Structural formulas of the materials for the OLEDs

[0654] 15

[0655] 20

[0656] 25

[0657] 30

[0658] 35 Foreignfiling text P24-180

[0659] -83-

[0660] 30

[0661] 35 Foreignfiling text P24-180

[0662] 5

[0663] 10

[0664] 15

[0665] 20

[0666] 25

[0667] 30

[0668] 35 Foreignfiling text P24-180

[0669] -85-

[0670] Table 3: Results of the OLEDs

[0671] 5

[0672] 10

[0673] 15

[0674] 20

[0675] 25

[0676] 30

[0677] 35

Claims

Foreignfiling text P24-180 -86- Patent claims 1. Compound according to formula (1) Formula 1) 15 where the compound may also be partially or completely deuterated and the symbols and indices have the following meanings: ETU, whether occurring in the same or different form, contains an electron-deficient heteroaryl group with 5 to 18 aromatic ring atoms, some of which are partially 20 or may be completely deuterated and / or substituted by one or more Ar residues and / or by one or more R residues; L is the same or different in each occurrence, a single bond or 25 a phenylene group which may be partially or completely deuterated and / or substituted by one or more R residues; Ar, in each occurrence, is either the same or different, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms. 30 which may be partially or completely deuterated and / or substituted by one or more residues R; R is the same or different in each occurrence F, CI, Br, I, CN, Si(R 2 )s, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 20 carbon atoms, 35 a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 Foreignfiling text P24-180 -87- to 20 C atoms, an alkenyl or alkynyl group with 2 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may each be partially or completely deuterated and / or with one or more R groups 2 can be substituted, with one or more non-adjacent CH2 groups being replaced by C(R 2 )=C(R 2 ), Si(R 2)2, C=NR 2 , 5 P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 which may be replaced by an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic rings 10 atoms, which may be partially or completely deuterated and / or have one or more R groups 2 may be substituted; optionally, two or more adjacent residues R may form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; 15 R 1is the same or different H, D, F, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl group is in each case partially 20 or may be completely deuterated and / or contain one or more residues R 2 can be substituted, or a phenyl group that can be partially or completely deuterated; optionally, two R groups can be used. 1 , which bind to the same carbon atom, forming a mono- or polycyclic, aliphatic or aromatic ring system; 25 R 2 is the same or different in each occurrence H, D, F, CN, an aliphatic hydrocarbon residue with 1 to 20 C atoms, which may be partially or completely deuterated, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or 30 several H atoms can be replaced by D, F, CI, Br, I or CN and can be substituted by one or more alkyl groups, each with 1 to 4 carbon atoms, which can be partially or completely deuterated; optionally, two or more, preferably 35 Foreignfiling text P24-180 -88- adjacent remains R 2 form a mono- or polycyclic, aliphatic ring system; n, m, o, p are the same or different at each occurrence 0 or 1 with the proviso that n + m + o + p = 1 or 2; 5q is 0 to (4 - o); r is 0 to (4 - p); 10 s is 0 to (4 - m); t is 0 to (4 - n).

2. Compound according to claim 1, selected from the compounds of the formulas 15 (2a) to (2d), (3a) to (3d) and (4a) to (4d), 20 25 30 Foreignfiling text P24-180 5 10 15 20 25 30 Foreignfiling text P24-180 5 10 15 20 wherein the compounds may also be partially or completely deuterated, in formulas (2a) to (2d) t = 0, 1, 2 or 3, in formulas (3a) to (3d) s = 0, 1, 2 or 3, in formulas (4a) to (4d) q = 0, 1, 2 or 3 and the other symbols and indices used have the meanings mentioned in claim 1. 25 3. Compound according to claim 1 or 2, characterized in that the indices q, r, s and t are the same or different at each occurrence 0 or 1 and that the sum of the indices q + r + s + t is 0, 1 or 2. 30 4. Compound according to one or more of claims 1 to 3, characterized in that ETU is selected from the structures (ET11-1) to (ET11-33), Foreignfiling text P24-180 -91- Foreignfiling text P24-180 -92- 10 15 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), and where the structures may also be substituted by one or more Ar and / or R residues and / or be partially or completely deuterated. 20 5. Compound according to one or more of claims 1 to 4, characterized in that ETU is selected from the structures of formulas (ETU-4a) to (ETU-24a), 25 30 35 Foreignfiling text P24-180 5 10 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), Ar the in 20 claims 1 has the meanings mentioned and the structures may also be partially or completely deuterated.

6. Compound according to one or more of claims 1 to 5, characterized in that Ar, whether the same or different, exhibits an aromatic component at each occurrence. 25 or heteroaromatic ring system with 6 to 18 aromatic ring atoms, each of which may be partially or completely deuterated and / or substituted by one or more R groups. 30 7. Compound according to one or more of claims 1 to 6, characterized in that Ar is selected in each occurrence, either identically or differently, from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran or dibenzothiophene, each of which is also partially or completely deuterated 35 Foreignfiling text P24-180 -94- may be and / or may be substituted by one or more residues R.

8. Compound according to one or more of claims 1 to 7, characterized in that R 1 is selected the same or different for each occurrence 5 from the group consisting of H, D, a straight-chain alkyl group with 1 to 6 C atoms or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein one or more H atoms in the alkyl group may also be replaced by D; in which case two R groups may be 1 , which bind to the same carbon atom, also form a ring together. 10 9. Compound according to one or more of claims 1 to 8, characterized in that the following applies to the symbols and indices used: ETU is, in each occurrence, the same or different, an electron-deficient 15 Heteroaryl group with 5 to 14 aromatic ring atoms, which may be partially or completely deuterated and / or substituted by one or more Ar and / or R residues; ETU has no more than four heteroatoms in the heteroaryl group; 20 L is, in each instance, either a single bond or a meta- or para-phenylene group, which may be partially or completely deuterated and / or substituted by one or more R residues; 25 Ar, in each instance, is the same or different aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which may be partially or completely deuterated and / or substituted by one or more R groups; 30 R is selected from the group consisting of F, CN, Si(R) in each instance, either the same or different. 2)s, a straight-chain alkyl group with 1 to 10 C atoms, a branched or cyclic alkyl group with 3 to 10 C atoms or an alkenyl group with 2 to 10 C atoms, wherein 35 Foreignfiling text P24-180 -95- the alkyl or alkenyl group may be partially or completely deuterated and / or have one or more R groups 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2 substi¬ 5 can be tuated; optionally, two adjacent residues R can form a mono- or polycyclic, aliphatic or aromatic ring system; R 1 is selected from the same or different sources for each occurrence 10. Group consisting of H, D, a straight-chain alkyl group with 1 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, wherein the alkyl group may also be partially or completely deuterated; in each case, two R groups may be present. 1 , which bind to the same carbon atom, also form a ring together; 15 q, r, s, t are the same or different at each occurrence 0, 1 or 2, where the sum of the indices q + r + s + t = 0, 1 , 2, 3 or 4. 20 10. Compound according to one or more of claims 1 to 9, characterized in that the following applies to the symbols and indices: ETU is the same or different at each occurrence selected from the following structures (ETll-1) to (ETll-33), 25 30 35 Foreignfiling text P24-180 -96- Foreignfiling text P24-180 -97- 10 15 where the dashed bond represents the bond to L or, for L = single bond, the bond to the corresponding carbon atom in formula (1), and where the structures may also be substituted by one or more Ar groups and / or be partially or completely deuterated; 20 L is, in each instance, either a single bond or a meta-phenylene group, which may be partially or completely deuterated; 25 Ar, in each instance, is the same or different aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, which may be partially or completely deuterated and / or substituted by one or more R groups; 30 R is selected from the group consisting of F, CN, Si(R) in each instance, either the same or different. 2)s, a straight-chain alkyl group with 1, 2, 3 or 4 C atoms or a branched or cyclic alkyl group with 3, 4, 5 or 6 C atoms, wherein the alkyl group is in each case partially 35 may be wise or completely deuterated, or an aromatic or Foreignfiling text P24-180 -98- heteroaromatic ring system with 6 to 13 aromatic ring atoms, which may be partially or completely deuterated and / or with one or more R groups 2 may be substituted; R 1 is selected from the same or different sources for each occurrence 5. Group consisting of H, D, a straight-chain alkyl group with 1 to 6 C atoms or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein one or more Hl atoms in the alkyl group may also be replaced by D; two R groups may be present 1 , which bind to the same carbon atom, also form a ring together; 10 q, r, s, t is either the same or different 0 or 1 for each occurrence, where the sum of the indices q + r + s + t = 0, 1 or 2.

11. Combination according to one or more of claims 1 to 10, wherein 15 indicates that the following applies to the symbols and indices: ETU is the same or different at each occurrence selected from structures (ETU-4a) to (ETU-24a), where structure (ETU-10a) 20 is preferred, 35 Foreignfiling text P24-180 5 where the dashed bond represents the bond to the corresponding carbon atom in formula (1) and the structures may also be partially or completely deuterated; 10 L is a single bond; Ar is chosen from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, in each occurrence, either the same or different. 15 Triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran, dibenzothiophene or carbazole, each of which may also be partially or completely deuterated and / or substituted by one or more R groups; 20 R 1 is selected from the group consisting of H, D or an optionally deuterated methyl group, either the same or different for each occurrence; q, r, s, t is 0 in each case. 25 12. Method for producing a compound according to one or more of claims 1 to 11, comprising the steps: 30 (a) Provision of the basic structure of the compound of formula (1), which carries a reactive leaving group instead of the -L-ETU group; and (b) Introduction of the group -L-ETU by a coupling reaction. 35 Foreignfiling text P24-180 -100- 13. Use of a compound according to one or more of claims 1 to 11 in an electronic device, in particular in an organic electroluminescent device.

14. Electronic device, in particular organic electroluminescent device 5 direction, comprising at least one connection according to one or more of claims 1 to 11.

15. Electronic device according to claim 14, characterized in that it is an organic electroluminescent device and the connection 10. The material according to one or more of claims 1 to 11 is used as an electron transport material in an electron transport layer and / or in a hole-blocking layer as a matrix material in an emitting layer. 15 20 25 30 35

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