Organic light-emitting device

Abstract

The present invention relates to an organic electronic device especially an organic light-emitting device comprising a light-emitting layer comprising a triazine of formula (1) and at least a hole-transporting OLED material selected from formulae (2), (3) or (4), and to a mixture of said OLED materials.

Description

[0001] P24-208 Sc

[0002] - 1 -

[0003] Organic light-emitting device

[0004] Subject-matter of the invention

[0005] The present invention relates to an organic electronic device especially an organic light5 emitting device comprising a light-emitting layer comprising a triazine of formula (1) and at least a hole-transporting host material selected from formulae (2), (3) or (4), and to a mixture of said host materials.

[0006] Background of the invention

[0007] 10 The structure of organic electroluminescent devices (e.g. OLEDs - organic light-emitting diodes or OLECs - organic light-emitting electrochemical cells) in which organic semiconductors are used as functional materials has long been known. Emitting materials used here, aside from fluorescent emitters, are increasingly organometallic complexes which exhibit phosphorescence rather than fluorescence. In general terms, however, there is still a need for improvement in OLEDs, especially also in OLEDs which exhibit triplet emission (phosphorescence), for example with regard to efficiency, operating voltage and lifetime.

[0008] The properties of organic electroluminescent devices are not only determined by the 20 emitters used. Also of particular significance here are especially the other materials used, such as host and matrix materials, hole blocker materials, electron transport materials, hole transport materials and electron or exciton blocker materials, and among these especially the host or matrix materials. Improvements to these materials can lead to distinct improvements to electroluminescent devices.

[0009] 25

[0010] Host materials for use in organic electronic devices are well known to the person skilled in the art. The term "matrix material" is also frequently used in the prior art when what is meant is a host material for phosphorescent emitters. This use of the term is also applicable to the present invention. In the meantime, a multitude of host materials has been developed both for fluorescent and for phosphorescent electronic devices.

[0011] A further means of improving the performance data of electronic devices, especially of organic electroluminescent devices, is to use combinations of two or more materials, especially host materials or matrix materials.

[0012] 35

[0013] JP2017107992 A2, US2019292169 A1, and WO23163479 A1 describe specific triazinedibenzofuran or triazine-dibenzothiophene electron transporting materials. P24-208 Sc

[0014] KR20180061075 A1, CN114163424 A, WO22173265 A1, US2022328773 A1 , US2023165021 A1, KR20230089575 A1 , US2024109926 A1 , and US2024099122 A1 describe specific host materials for organic light-emitting devices.

[0015] 5 However, there is still need for improvement in the case of use of these materials or in the case of use of mixtures of the materials, especially in relation to efficiency, operating voltage and / or lifetime of the organic electroluminescent device.

[0016] The problem addressed by the present invention is therefore that of providing a combination of host materials which are suitable for use in an organic electroluminescent device, especially in a phosphorescent OLED, and lead to good device properties, especially with regard to an improved lifetime and / or a low operating voltage, and that of providing the corresponding electroluminescent device.

[0017] 15 It has now been found that this problem is solved, and the disadvantages from the prior art are eliminated, by the combination of at least one compound of the formula (1) as first host material and at least one hole-transporting compound of the formula (2) or of the formula (3) or of the formula (4) as second host material in a light-emitting layer of an organic electroluminescent device. The use of such a material combination for

[0018] 20 production of the light-emitting layer in an organic electroluminescent device leads to very good properties of these devices, especially with regard to lifetime, especially with equal or improved efficiency and / or operating voltage. The advantages are especially also manifested in the presence of a light-emitting component in the emission layer, especially in the case of combination with emitters or in combination with arylamines, 25 e.g. of the formulae (l-A) or (l-B) or preferred embodiments thereof in the hole injection layer and / or hole transport layer and / or electron blocking layer.

[0019] Summary of the invention

[0020] The present invention therefore first provides an organic light-emitting device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of the formula (1) as host material 1 and at least one compound of the formulae (2), (3) or (4) as host material 2,

[0021]

[0022] formula (1), P24-208 Sc

[0023]

[0024]

[0025] formula (4),

[0026] where the symbols and indices used are as follows:

[0027] Y stands for O or S;

[0028] R at each instance is the same or different and is H or D;

[0029] R# is the same or different at each instance and stands for D, F, phenyl or partially or fully deuterated phenyl;

[0030] An , Ar2 at each instance are the same or different and are an aromatic ring system having 6 to 18 C atoms which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# radicals;

[0031] 35

[0032] R6at each instance is the same or different and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case P24-208 Sc

[0033] - 4 -

[0034] be substituted by one or more R7radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R7)2, C=O, NR7, O, S or CONR7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and which may be partially or completely deuterated in each case; it is 5 also possible here for two R6radicals together to form an aromatic,

[0035] heteroaromatic, aliphatic, or heteroaliphatic ring system;

[0036] Ars is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R7radicals;

[0037] 10 R7is the same or different at each instance and is D, F, Cl, Br, I, N(R8)2, CN, NO2, OR8, SR8, Si(R8)3, B(OR8)2, C(=O)R8, P(=O)(R8)2, S(=O)R8, S(=O)2R8, OSO2R8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R8radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R8)2, C=O, NR8, O, S or CONR8, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and which may be partially or completely deuterated in each case; at the same time, two or more R7radicals together 20 may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0038] R8is the same or different at each instance and is H, D, F or an aliphatic,

[0039] aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may 25 also be replaced by F;

[0040] s is the same or different at each instance and is 0, 1 , 2, 3 or 4;

[0041] t is the same or different at each instance and is 0, 1 , 2 or 3;

[0042] u is the same or different at each instance and is 0, 1 or 2,

[0043] with the proviso that at least one R6in formulae (2), (3) and (4) is D or at least one Ars is a deuterated substituent.

[0044] The invention therefore further provides a mixture comprising at least one compound of formula (1) and at least one compound of the formulae (2), (3) or (4),

[0045]

[0046] formula (1), P24-208 Sc

[0047]

[0048]

[0049] 25

[0050] where the symbols and indices used are as follows:

[0051] Y stands for O or S;

[0052] R at each instance is the same or different and is H or D;

[0053] R# is the same or different at each instance and stands for D, F, phenyl or partially or fully deuterated phenyl;

[0054] An , Ar2 at each instance are the same or different and are an aromatic ring system having 6 to 18 C atoms which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# radicals;

[0055] R6at each instance is the same or different and is D, F, CN, a straight-chain 35

[0056] alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R7radicals and where one or more P24-208 Sc

[0057] - 6 -

[0058] nonadjacent CH2 groups may be replaced by Si(R7)2, C=O, NR7, O, S or CONR7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and which may be partially or completely deuterated in each case; it is also possible here for two R6radicals together to form an aromatic,

[0059] 5 heteroaromatic, aliphatic, or heteroaliphatic ring system;

[0060] Ars is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R7radicals;

[0061] R7is the same or different at each instance and is D, F, Cl, Br, I, N(R8)2, CN, NO2, OR8, SR8, Si(R8)3, B(OR8)2, C(=O)R8, P(=O)(R8)2, S(=O)R8, S(=O)2R8, OSO2R8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R8radicals and 15 where one or more nonadjacent CH2 groups may be replaced by Si(R8)2, C=O, NR8, O, S or CONR8, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and which may be partially or completely deuterated in each case; at the same time, two or more R7radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring 20 system;

[0062] R8is the same or different at each instance and is H, D, F or an aliphatic,

[0063] aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F;

[0064] 25 s is the same or different at each instance and is 0, 1 , 2, 3 or 4;

[0065] t is the same or different at each instance and is 0, 1 , 2 or 3;

[0066] u is the same or different at each instance and is 0, 1 or 2,

[0067] with the proviso that at least one R6in formulae (2), (3) and (4) is D or at least one Ars is a deuterated substituent.

[0068] The invention further provides a process for producing the organic light-emitting devices and specific further mixtures, and specific material combinations. The corresponding preferred embodiments as described hereinafter likewise form part of the subject-matter of the present invention. The surprising and advantageous effects are achieved through 35 specific selection of the compounds of the formula (1) and the compounds of the formulae (2), (3) or (4). The surprising and advantageous effects are further achieved through specific selection of the compounds of the formula (1) and the compounds of the formulae (2), (3) or (4), preferably together with specific arylamines selected from P24-208 Sc

[0069] - 7 -

[0070] monoamines or diamines in the hole injection layer and / or hole transport layer and / or electron blocking layer as further described hereinbelow.

[0071] Detailed description of the invention

[0072] 5 In the present patent application, "D" or "D atom" denotes deuterium. The degree of deuteration, expressed in mol%, means the proportion of H atoms that are replaced by deuterium. Since the deuterated compounds are often a mixture of compounds that differ in the exact position and the exact proportion of D atoms, the degree of deuteration denotes the average proportion of H atoms that are replaced by D. With a degree of deuteration of 50 mol%, an average of 50 mol% of the H atoms in the compound are replaced by D, so that the degree of deuteration is average.

[0073] The organic light-emitting device of the invention is, for example, an organic lightemitting transistor (OLET), an organic field quench device (OFQD), an organic light15 emitting electrochemical cell (OLEC), an organic laser diode (O-laser) or an organic light-emitting diode (OLED). The organic light-emitting device or synonymously organic electroluminescent device of the invention is especially an organic light-emitting diode or an organic light-emitting electrochemical cell. The device of the invention is more preferably an OLED.

[0074] 20 The organic layer of the device of the invention that comprises the light-emitting layer comprising the material combination of at least one compound of the formula (1) and at least one compound of the formulae (2) or (3), as described or described above or hereinafter, preferably comprises, in addition to this light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an 25 electron transport layer (ETL), an electron injection layer (EIL) and / or a hole blocker layer (HBL), and / or an exciton blocking layer and / or charge generation layers. It is also possible for the device of the invention to include multiple layers from this group selected from EML, HIL, HTL, EBL, ETL, EIL and HBL.

[0075] The organic electroluminescent device of the invention may contain two or more lightemitting layers. At least one of the emitting layers is the light-emitting layer of the invention. It is particularly preferable when these emission layers in this case altogether exhibit a plurality of emission maxima between 380 nm and 750 nm, so that altogether white emission results. It should be noted that, for the production of white light, rather 35 than a plurality of emitter compounds, an emitter compound used individually which emits over a broad wavelength range may also be suitable. Systems with three emitting layers are particularly preferred, whereby the three layers show blue, green and orange or red emission. As an alternative to the combination described above, an emitting layer can also show yellow emission. Such combinations are known in the art. The organic P24-208 Sc

[0076] - 8 -

[0077] electroluminescence device according to the invention can also be a tandem electroluminescence device, in particular for white-emitting OLEDs.

[0078] However, the device may also comprise inorganic materials or else layers formed entirely from inorganic materials.

[0079] 5

[0080] It is preferable when the organic layer of the device of the invention comprises a hole injection layer and / or a hole transport layer and / or an electron blocking layer wherein the hole-injecting material and / or hole-transporting material and / or electron blocking material is a monoamine or diamine that does not contain a carbazole unit. A suitable selection of 10 monoamine or diamine compounds and preferred compounds is described hereinbelow.

[0081] It is preferable when the light-emitting layer comprising at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) comprises at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters having thermally activated delayed fluorescence. A suitable selection of matrix materials and emitters is described hereinafter.

[0082] It is preferable when the light-emitting layer comprising at least one compound of the 20 formula (1) and at least one compound of the formulae (2), (3) or (4) comprises at least one phosphorescent emitter. A suitable selection of phosphorescent emitters and preferred phosphorescent emitters is described hereinafter.

[0083] An aryl group in the context of this invention contains 6 to 40 aromatic ring atoms, 25 preferably carbon atoms. A heteroaryl group in the context of this invention contains 5 to 40 aromatic ring atoms, where the ring atoms include carbon atoms and at least one heteroatom, with the proviso that the sum total of carbon atoms and heteroatoms adds up to at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group is understood here to mean either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a fused aryl group, i.e. derived from naphthalene, anthracene, phenanthrene, triphenylene, but also includes aromatic ring systems such as biphenyl, terphenyl, quaterphenyl, dimethylfluorenyl, diphenylfluorenyl or spirobifluorenyl. A heteroaryl group is understood here to mean a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused heteroaryl group, for example 35 derived from dibenzofurane, dibenzothiophene, carbazole, quinoline or isoquinoline, but also includes heteroaromatic ring systems such as bipyridyl. An aryl group having 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl, biphenyl, terphenyl or triphenylenyl with no restriction in the attachment of the aryl group as substituent. The aryl or heteroaryl group in the context of this invention may bear one or P24-208 Sc

[0084] - 9 -

[0085] more radicals, where the substituent is described below. If no such substituent is described, the aryl group or heteroaryl group is not substituted. The aryl and heteroaryl groups are preferably partially deuterated or fully deuterated.

[0086] 5 An aryl group (synonymously used an aromatic ring system) or a heteroaryl group (synonymously used a heteroaromatic ring system) which has 5-40 ring atoms and may be joined to the aromatic or heteroaromatic system via any desired positions is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, 10 perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7- quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, 20 pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, 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, 25 phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1.2.3-triazole, 1 ,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5- oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1.3.4-thiadiazole, 1 ,3,5-triazine, 1 ,2,4-triazine, 1 ,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1.2.3.4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole. An aromatic ring system having 6 to 18 carbon atoms as ring atoms is preferably selected from phenyl, 1 ,2-biphenyl, 1 ,3-biphenyl, 1 ,4-biphenyl, dimethylfluorenyl, naphthyl, phenanthryl and triphenylenyl, which may be substituted by one or more radicals, where the substituent is described hereinafter.

[0087] A preferred heteroaromatic ring system having 10 to 18 ring atoms is preferably selected 35 from dibenzofuranyl and dibenzothiophenyl, which may be substituted by one or more radicals, where the substituent is described hereinafter.

[0088] A cyclic alkyl group in the context of this invention is understood to mean a monocyclic, bicyclic or polycyclic group. P24-208 Sc

[0089] - 10 -

[0090] In the context of the present invention, a straight-chain, branched or cyclic Ci- to C20- alkyl group is understood to mean, for example, the methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, 5 neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1- bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1 , 1 -dimethyl-n-hept-1 -yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n- 10 dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n- octadec-1-yl, 1 , 1-diethyl-n-hex-1-yl, 1 , 1-diethyl-n-hept-1-yl, 1 , 1-diethyl-n-oct-1-yl, 1,1- diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1 , 1 -diethyl-n-tetradec-1 -yl, 1 , 1-diethyl-n- hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex- 1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl 15 radicals.

[0091] The abbreviation An is an aromatic ring system having 6 to 18 C atoms, preferably 12 to 18 C atoms, which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# 20 radicals, where the R# radical is defined as described above or hereinafter.

[0092] The abbreviation Ar2 is an aromatic ring system having 6 to 18 C atoms which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# radicals, where the R# radical 25 is defined as described above or hereinafter.

[0093] The abbreviation Ars is the same or different at each instance and is an aryl group or heteroaryl group which has 5 to 40 ring atoms and may be substituted by one or more R7radicals, where the R7radical is defined as described above or hereinafter.

[0094] 30

[0095] In the context of the present invention, a straight-chain, branched or cyclic alkenyl group is understood to mean ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.

[0096] In the context of the present invention, a straight-chain, branched or cyclic alkynyl group 35 is understood to mean ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0097] When the host materials of the light-emitting layer comprising at least one compound of the formula (1) as described above or described as preferred hereinafter and at least one compound of the formulae (2), (3) or (4) as described above or described hereinafter P24-208 Sc

[0098] - 11 -

[0099] are used for a phosphorescent emitter, it is preferable when the triplet energy thereof is not significantly less than the triplet energy of the phosphorescent emitter. In respect of the triplet level, it is preferably the case that Ti (emitter) - Ti(matrix) < 0.2 eV, more preferably < 0.15 eV, most preferably < 0.1 eV. Ti(matrix) here is the triplet level of the 5 matrix material in the emission layer, this condition being applicable to each of the two matrix materials, and Ti(emitter) is the triplet level of the phosphorescent emitter. If the emission layer contains more than two matrix materials, the abovementioned relationship is preferably also applicable to every further matrix material.

[0100] There follows a description of the host material 1 and its preferred embodiments that is / are present in the device of the invention. The preferred embodiments of the host material 1 of the formula (1) are also applicable to the mixture of the invention.

[0101] Preferred compounds of formula (1) are compounds of formulae (1a), (1b) and (1c),

[0102]

[0103] where An , Ar2, and R have a meaning as described before or preferably described 35 before or hereinafter. P24-208 Sc

[0104] - 12 -

[0105] The invention further provides the organic light-emitting device as described above, wherein the host material 1 conforms to at least one of the formulae (1a), (1b), and (1c) as described above.

[0106] 5 In a particularly preferred embodiment of the light-emitting device or mixture according to the invention, the host material 1 is selected from compounds of formula (1a) as described before.

[0107] In a preferred embodiment of the light-emitting device or mixture according to the invention, the host material 1 is selected from compounds of formula (1b) as described before.

[0108] Preferred compounds of formula (1a) are compounds of formulae (1d), and (1e),

[0109]

[0110] before or hereinafter.

[0111] Preferred compounds of formula (1b) are compounds of formulae (1f), (1g), and (1 h),

[0112]

[0113] formula (1f), P24-208 Sc

[0114] - 13 -

[0115]

[0116] where An, Ar2, and R have a meaning as described before or preferably described before or hereinafter.

[0117] 15

[0118] Preferred compounds of formula (1c) are compounds of formulae (1 i),

[0119]

[0120] formula (1 i),

[0121] where An , Ar2, and R have a meaning as described before or preferably described 25 before or hereinafter.

[0122] In compounds of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1 i), Y is preferably O.

[0123] In compounds of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1 i), An is preferably selected from the group of Ar-1 to Ar-5,

[0124]

[0125] P24-208 Sc

[0126] - 14 -

[0127]

[0128] Ar-4 Ar-5

[0129] 5 where each group Ar-1 to Ar-5 may be substituted by one or more R# radicals and where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h), and (1i).

[0130] In groups Ar-1 to Ar-10 or preferred groups Ar-1 to Ar-10, R# is preferably at each occurrence independently D, phenyl or partially or fully deuterated phenyl. In groups Ar-1 to Ar-10 or preferred groups Ar-1 to Ar-10, R# is preferably D.

[0131] In compounds of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1 i), Ar2 is preferably selected from the group of Ar-6 to Ar-10,

[0132] 15

[0133]

[0134] 20

[0135]

[0136] Ar-10

[0137] where each group Ar-6 to Ar-10 may be substituted by one or more R# radicals and where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1 d), 25 (1e), (1f), (1g), (1h), and (1i).

[0138] Preferred groups of Ar-1, and preferred groups of Ar-7 are the following two groups

[0139]

[0140] , where each group may be substituted by one or more R# radicals, where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1 h), and (1i) and R# has a meaning as described before.

[0141] Preferred groups of Ar-2, and preferred groups of Ar-8 are the following groups

[0142] 35

[0143]

[0144] P24-208 Sc

[0145] - 15 -

[0146]

[0147] 5

[0148] where each group may be substituted by one or more R# radicals, where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1i) and R# has a meaning as described before.

[0149] Preferred groups of Ar-4, and preferred groups of Ar-9 are the following groups

[0150]

[0151] each group may be substituted by one or more R# radicals, where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1i) and R# has a

[0152] 15

[0153] meaning as described before.

[0154] Preferred groups of Ar-5, and preferred groups of Ar-10 are the following groups

[0155]

[0156] each group may be substituted by one or more R# radicals, where the dashed bond is the bond to the rest of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1 h), and (1i) and R# has a meaning as described before.

[0157] 25

[0158] In a preferred embodiment of the host material 1 according to compounds of formulae (1), (1a), (1b), (1c), (1 d), (1e), (1 f), (1g), (1 h), and (1i) as described before or preferably described, the cyano group is linked in meta- or para-position to the remainder of formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) or (1i).

[0159] In a preferred embodiment of the light-emitting device or mixture according to the invention, the host material 1 according to compounds of formulae (1), (1a), (1b), (1c), (1 d), (1e), (1 f), (1g), (1 h), and (1i) as described before or preferably described before is partially or fully deuterated.

[0160] 35

[0161] If the compounds of formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h) and (1i) are deuterated compounds, it is possible in their preparation, if the preparation is chosen by reacting a non-deuterated compound of one of formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), and (1i), with a source of deuteration or if deuterated starting compounds P24-208 Sc

[0162] - 16 -

[0163] are chosen in the preparation which are a mixture of deuterated starting compounds, to obtain a mixture of deuterated products of the same basic chemical structure which differ only in the degree of deuteration and / or the deuteration patterns.

[0164] 5 Such mixtures of deuterated compounds of the same basic chemical structure of formula (1), which differ only in the degree of deuteration and / or the deuteration patterns, are understood by the term “at least one compound of formula (1)”. The same applies for compounds of formulae (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), and (1i).

[0165] 10 In a preferred embodiment of the at least one compound of formulae (1), (1a), (1b), (1c), (1d), (1e), (1 f), (1g), (1 h), and (1i) as previously described or preferably described, the average degree of deuteration is at least 30 mol% to 100 mol%, more preferably

[0166] 50 mol% to 90 mol%, further more preferably 70 mol% to 90 mol%.

[0167] 15 Corresponding deuteration methods are known to the person 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), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063- 1071.

[0168] 20 A suitable method of deuterating a compound by exchange of one or more hydrogen atoms for deuterium atoms is a treatment of the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source. The term “deuterium source” means any compound that contains one or more deuterium atoms and is able to release them under suitable conditions.

[0169] 25

[0170] The platinum catalyst is preferably dry platinum on charcoal, preferably 5% dry platinum on charcoal. The palladium catalyst is preferably dry palladium on charcoal, preferably 5% dry palladium on charcoal. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4 or toluene-d8. A 30 preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D2O with a fully deuterated organic solvent, where the fully deuterated solvent here is not restricted. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8. The 35 reaction is preferably conducted with heating, more preferably with heating to temperatures between 100°C and 200°C.ln addition, the reaction is preferably conducted under pressure. P24-208 Sc

[0171] - 17 -

[0172] Examples of suitable host materials of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1 h), and (1i) are the structures given below in table 1.

[0173] Table 1 :

[0174] 5

[0175] 15

[0176] "

[0177] 20 >

[0178] 25 <&

[0179] <> 35

[0180]

[0181] P24-208 Sc

[0182] - 18 -

[0183] 5

[0184] 15

[0185] 20

[0186] 25

[0187] 35

[0188]

[0189] P24-208 Sc

[0190]

[0191] P24-208 Sc

[0192] 5

[0193] 15 20 25

[0194] 35

[0195]

[0196] P24-208 Sc

[0197] 5

[0198] 15 20 25

[0199] 35

[0200]

[0201] P24-208 Sc

[0202]

[0203] P24-208 Sc

[0204] - 23 -

[0205] >

[0206] >

[0207] "

[0208] <

[0209] " "

[0210]

[0211] P24-208 Sc

[0212] - 24 -

[0213] >

[0214] >

[0215] " >

[0216] >

[0217]

[0218] P24-208 Sc

[0219] 5

[0220] 15 20 25

[0221] 35

[0222]

[0223] P24-208 Sc

[0224] 5

[0225] 15 20 25

[0226] 35

[0227]

[0228] P24-208 Sc

[0229] 5

[0230] 15 20 25

[0231] 35

[0232]

[0233] P24-208 Sc

[0234] 5

[0235] 15 20 25

[0236] 35

[0237]

[0238] P24-208 Sc

[0239] - 29 -

[0240] 5

[0241] 15 20 25

[0242] 35

[0243]

[0244] P24-208 Sc

[0245] 5

[0246] 15 20 25

[0247] 35

[0248]

[0249] P24-208 Sc

[0250] 5

[0251] 15 20 25

[0252] 35

[0253]

[0254] P24-208 Sc

[0255] - 32 -

[0256] 5

[0257] 15

[0258] 20

[0259] 25

[0260] 35

[0261]

[0262] P24-208 Sc

[0263] - 33 -

[0264] 5

[0265] 15

[0266] 20

[0267] 25

[0268] 35

[0269]

[0270] P24-208 Sc

[0271] - 34 -

[0272] 5

[0273] 15

[0274] 20

[0275] 25

[0276] 35

[0277]

[0278] P24-208 Sc

[0279] - 35 -

[0280] 5

[0281] 15 20

[0282] 25

[0283]

[0284] P24-208 Sc

[0285] 5

[0286] 15 20

[0287] 25

[0288]

[0289] P24-208 Sc

[0290] - 37 -

[0291] 5

[0292] 15 20

[0293] 25

[0294]

[0295] P24-208 Sc

[0296] - 38 -

[0297] 5

[0298] 15

[0299] 20

[0300] 25

[0301] 35

[0302]

[0303] P24-208 Sc

[0304] 5

[0305] 15 20 25

[0306] 35

[0307]

[0308] P24-208 Sc

[0309] - 40 -

[0310] 5

[0311] 15

[0312] 20

[0313] 25

[0314] 35

[0315]

[0316] P24-208 Sc

[0317] - 41 -

[0318] 5

[0319] 15

[0320] 20

[0321] 25

[0322] 35

[0323]

[0324] P24-208 Sc

[0325] 5

[0326] 15 20 25

[0327] 35

[0328]

[0329] P24-208 Sc

[0330] 5

[0331] 15 20 25

[0332] 35

[0333]

[0334] P24-208 Sc

[0335] - 44 -

[0336] 5

[0337] 15

[0338] 20

[0339] 25

[0340] 35

[0341]

[0342] P24-208 Sc

[0343] - 45 -

[0344] <

[0345] "

[0346] <

[0347] "

[0348] "

[0349] >

[0350]

[0351] P24-208 Sc

[0352] < > >>>>

[0353] 5

[0354] 15

[0355] >

[0356] 20

[0357] > 25

[0358] >

[0359] 35

[0360]

[0361] P24-208 Sc

[0362] <

[0363] " 5

[0364] >< ><

[0365] > 15

[0366] 20

[0367] &

[0368] 25

[0369] > > <

[0370] "

[0371] 35

[0372]

[0373] P24-208 Sc

[0374] - 48 -

[0375] 5

[0376] 15

[0377] 20

[0378] 25

[0379] 35

[0380]

[0381] P24-208 Sc

[0382]

[0383] P24-208 Sc

[0384] - 50 - >

[0385] 5

[0386] >

[0387] > 15

[0388] > <

[0389] 2

[0390] 0

[0391] ><>

[0392] 25

[0393] 35 >

[0394]

[0395] P24-208 Sc

[0396] - 51 -

[0397] "

[0398] >

[0399] " " <

[0400] <

[0401] "

[0402] " >

[0403]

[0404] P24-208 Sc

[0405] - 52 -

[0406] 5

[0407] 15

[0408] 20

[0409]

[0410] Particularly suitable compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), 25 (1 h), and (1i) are the compounds E1 to E30 of table 2.

[0411]

[0412] P24-208 Sc

[0413] - 53 -

[0414] 5

[0415] 15

[0416] 20 25

[0417]

[0418] 35 P24-208 Sc

[0419] - 54 -

[0420] 5

[0421] 15

[0422] 20

[0423] 25

[0424] 35

[0425]

[0426] P24-208 Sc

[0427] 5

[0428]

[0429] The compounds in Tables 1 and 2 are shown in part as fully deuterated compounds for the sake of simplification, whereby these are generally intended to denote compounds that have a degree of deuteration of at least 50mol%. The degree of deuteration for said fully deuterated compounds in Tables 1 and 2 is therefore between 50 and 100mol% or has a preferred deuteration degree as described herein. For partially deuterated 15 compounds, a D atom means that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0430] The preparation of the compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1i) or of the compounds from table 1 and of the compounds E1 to E30 and E31 and E32 as shown in the experimental section is known to those skilled in the 20

[0431] art. The compounds may be prepared by synthesis steps known to the person skilled in the art, for example halogenation, preferably bromination, and a subsequent organometallic coupling reaction, for example Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling.

[0432] 25 The compounds of formula (1) may be prepared according to the following schemes, the symbols used having the meanings given above.

[0433] Scheme 1:

[0434]

[0435] P24-208 Sc

[0436] - 56 -

[0437] Scheme 2: D means Deuterium

[0438]

[0439]

[0440] There follows a description of the host material 2 and its preferred embodiments that is / are present in the device of the invention. The host material 2 is partially or fully deuterated which means that at least one R6in formulae (2), (3) and (4) is D or at least 20

[0441] one Ars in formulae (2), (3) and (4) is a deuterated substituent. The preferred embodiments of the host material 2 of the formulae (2), (3) or (4) are also applicable to the mixture of the invention. In one embodiment of the invention, for the device of the invention, compounds of the formula (2) or of the formula (3) or of the formula (4) as described above are selected, and these are used in the light-emitting layer with 25

[0442] compounds of the formula (1) as described above or described as preferred or with the compounds from table 1 or the compounds E1 to E30 or E31 and E32.

[0443] Preferred compounds of formula (2) are compounds of formula (2a),

[0444]

[0445] formula (2a),

[0446] where Ars, R6, s and t have a meaning as described before or preferably described before. P24-208 Sc

[0447] Preferred compounds of formula (3) are compounds of formulae (3a) to (3e),

[0448]

[0449] P24-208 Sc

[0450] - 58 -

[0451] where Ars, R6, s and u have a meaning as described before or preferably described before.

[0452] Preferred compounds of formula (3) are compounds of formulae (3a1) to (3e1),

[0453]

[0454] 35 P24-208 Sc

[0455] - 59 -

[0456]

[0457] where Ars, R6, R7, s and u have a meaning as described before or preferably described before and r is 0, 1, 2, 3, 4 or 5.

[0458] 20 Preferred compounds of formula (4) are compounds of formula (4a),

[0459] formula (4a),

[0460]

[0461] where Ars, R6, s and t have a meaning as described before or preferably described before.

[0462] In compounds of the formulae (3a1), (3b1), (3d), (3d1) or (3e1), r is preferably independently on each occurrence 1, 2, 3, 4 or 5 where a maximum of one R7radical 35

[0463] may be different from D.

[0464] In compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or (4a), s is preferably independently on each occurrence 1, 2, 3 or 4 where a maximum of one R6radical or one R7radical may be different from D. P24-208 Sc

[0465] - 60 -

[0466] In compounds of the formulae (2), (2a), (4) or (4a), t is preferably independently on each occurrence 1, 2 or 3 where a maximum of one R6radical may be different from D.

[0467] In compounds of the formulae (3), (3a), (3b), (3c), (3d), (3e) (3a1), (3b1), (3d), (3d1), or (3e1), u is preferably 1 or 2 where a maximum of one R6radical may be different from D.

[0468] 5 The sum total of the R6radicals being different from D in compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or (4a) is preferably not more than 4, especially preferably not more than 2 and more preferably not more than 1.

[0469] In a preferred embodiment of the compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d 1 ), (3e1), (4) or (4a) that can be combined in accordance with the invention with compounds of the formula (1) or preferred compounds of the formula (1), as described above, R6is the same or different at each instance and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 15 carbon atoms, where the alkyl group may in each case be substituted by one or more R7radicals, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and may be substituted in each case by one or more R7radicals.

[0470] 20 In a preferred embodiment of the compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d 1 ), (3e1), (4) or (4a) that can be combined in accordance with the invention with compounds of the formula (1) or preferred compounds of the formula (1), as described above, R6is the same or different at each instance and is selected from the group consisting of D or an aromatic or heteroaromatic 25 ring system which has 6 to 30 ring atoms and may be substituted by one or more R7radicals. R6is preferably selected on each occurrence from D, a partially or fully deuterated phenyl group. R6is most preferably selected on each occurrence from D.

[0471] In a preferred embodiment of the compounds of the formulae (3a1), (3b1), (3d), (3d1) or (3e1) that can be combined in accordance with the invention with compounds of the formula (1) or preferred compounds of the formula (1), as described above, R7within (R7)r and (R7)sis the same or different at each instance and is selected from the group consisting of D, or an aromatic or heteroaromatic ring system which may be partially or completely deuterated in each case. R7within (R7)rand (R7)sis most preferably selected 35 on each occurrence from D.

[0472] Preferably, Ars in compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or (4a) is independently selected from phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, triphenylenyl, terphenyl, especially P24-208 Sc

[0473] - 61 -

[0474] ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorenyl which may be joined via the 1, 2, 3 or 4 position, spirobifluorenyl which may be joined via the 1, 2, 3 or 4 position, naphthyl, especially 1- or2-bonded naphthyl, or radicals derived from indole,

[0475] 5 benzofuran, benzothiophene, carbazole which may be joined via the 1 , 2, 3 or 4 position, dibenzofuran which may be joined via the 1 , 2, 3 or 4 position, dibenzothiophene which may be joined via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more R7radicals. Ars is preferably deuterated, but not further substituted.

[0476] More preferably, at least one Ars in compounds of the formulae (2), (2a), (3), (3a), (3b),

[0477]

[0478]

[0479]

[0480] where R10is H or R7and where R7has a meaning as described before or preferably described before or below. It is preferred that at least one R10is D.

[0481] In a preferred embodiment of the compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d 1 ), (3e1), (4) or (4a) that can be combined in accordance with the invention with above-detailed compounds of host material 1, as described above, R7is the same or different at each instance and is selected from the 35 group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, or an aromatic heteroaromatic ring system which has 5 to 40 ring atoms, and which may be partially or completely deuterated in each case. P24-208 Sc

[0482] - 62 -

[0483] In a particularly preferred embodiment of the compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or (4a) that can be combined in accordance with above-detailed compounds of host material 1, as described above, R7is the same or different at each instance and is D, CN or an 5 aromatic or heteroaromatic ring system having 6 to 24 ring atoms, especially having 6 to 18 ring atoms. Preferred embodiments of R7are D, CN, phenyl or biphenyl, which are preferably deuterated. More preferably, R7is D.

[0484] Preferred embodiments of R10are H and D.

[0485] 10

[0486] The preparation of the compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) and (4a) is generally known, and some of the compounds are commercially available.

[0487] 15 Suitable compounds of the formula (2) are known, for example, from the following publications: W02019 / 229011 A1, table 3, pages 137 to 162, which may also be partly or fully deuterated or US2023172065 A, on pages 413 to 434.

[0488] Suitable compounds of the formula (2) or (3) are known, for example, from the following 20 publications: US2023172061 A1, pages 51 to 71 or KR20230154750 A1, on pages 39 to 49, compounds [B-1] to [B-101] and [B-120] to [B-234] or on pages 49 to 53, compounds [C-1] to [C-102],

[0489] Suitable compounds of the formula (4) are known, for example, from the following 25 publication: WO2021 / 180625 A1, table 3, pages 131 to 137, and in table 4, pages 137 to 139, which may also be partly or fully deuterated.

[0490] As host material 2 is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds of the same basic chemical structure, 30 which differ only in the degree of deuteration and / or the deuteration pattern. The remarks on deuterated mixtures and on the preparation of deuterated materials, as previously described for host material 1 , apply here accordingly.

[0491] In a preferred embodiment of the host material 2 as described before or preferably 35 described before, the latter is a mixture of deuterated compounds of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) and (4a) as described above, wherein the average deuteration level of these compounds is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, more preferably 70 mol% to 90 mol%. P24-208 Sc

[0492] For a combination with the compounds of host material 1 as described above or described as preferred, suitable compounds are in particular those of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) and (4a), as 5 described above or described as preferred, or corresponding compounds in the tables that follow that are covered by these formulae.

[0493] Further examples of suitable host materials of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) and (4a) that can be combined in accordance with the invention with above-detailed compounds of host material 1, as described above, are the structures shown hereinafter in tables 3 and 4 below.

[0494] Table 3:

[0495] 15

[0496] 20

[0497] 25

[0498]

[0499] 35 P24-208 Sc

[0500] 5

[0501] 15 20 25

[0502] 35

[0503]

[0504] P24-208 Sc

[0505]

[0506] P24-208 Sc

[0507]

[0508] P24-208 Sc

[0509]

[0510] P24-208 Sc

[0511] 5

[0512] 15 20 25

[0513]

[0514] 35 P24-208 Sc

[0515] 5

[0516] 15 20 25

[0517] 35

[0518]

[0519] P24-208 Sc

[0520] - 70 -

[0521] 5

[0522] 15

[0523] 20

[0524] 25

[0525] 35

[0526]

[0527] P24-208 Sc

[0528] 5

[0529] 15 20 25

[0530] 35

[0531]

[0532] P24-208 Sc

[0533]

[0534] P24-208 Sc

[0535] 5

[0536] 15 20 25

[0537] 35

[0538]

[0539] P24-208 Sc

[0540] 5

[0541] 15 20 25

[0542]

[0543] 35 P24-208 Sc

[0544] 5

[0545] 15 20 25

[0546] 35

[0547]

[0548] P24-208 Sc

[0549] 5

[0550] 15 20 25

[0551] 35

[0552]

[0553] P24-208 Sc

[0554] 5

[0555] 15 20 25

[0556] 35

[0557]

[0558] P24-208 Sc

[0559] 5

[0560] 15 20 25

[0561] 35

[0562]

[0563] P24-208 Sc

[0564] - 79 -

[0565] 5

[0566]

[0567] 15 n in the above Table 3 means the number of D atoms in the respective compound and is D1 to Dmax, preferably D4 to Dmax. The item n = D1 means that one H atom in the respective compound is replaced by a D atom. Dmax means the maximum number of D atoms that is possible in the respective compound. The maximum number Dmax can vary from compound to compound. Depending on the compound, Dmax can assume the 20 following values: 20, 24, 26, 28, 30, 31, 32, 34, 35, 36, 37, 38 and 40.

[0568] Particularly suitable compounds of the formulae (2), (3) and / or (4) that can be combined in accordance with the invention with above-detailed compounds of the invention, as described above, and are used in the electroluminescent device of the invention or in the 25 mixture, are the compounds H1 to H45 in table 4.

[0569] Table 4:

[0570] 35

[0571]

[0572] P24-208 Sc

[0573] 5

[0574] 15 20 25

[0575]

[0576] 35 P24-208 Sc

[0577] 5

[0578] 15 20 25

[0579]

[0580] 35 P24-208 Sc

[0581] 5

[0582] 15 20 25

[0583]

[0584] 35 P24-208 Sc

[0585] 5

[0586] 15 20 25

[0587]

[0588] 35 P24-208 Sc

[0589] 5

[0590] 15

[0591] 20

[0592]

[0593] The compounds in Tables 3 and 4 are shown in part as fully deuterated compounds for the sake of simplification, whereby these are generally intended to denote compounds that have a degree of deuteration of at least 50 mol%. The degree of deuteration for said 25 fully deuterated compounds in Tables 3 and 4 is therefore between 50 and 100 mol% or has a preferred deuteration degree as described herein. For partially deuterated compounds, a D atom means that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0594] The aforementioned host materials 1 and the embodiments thereof that have been described as preferred may be combined in the device of the invention in any desired manner with the aforementioned matrix material / host materials, the matrix material / host materials of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (4) and (4a), and the embodiments thereof that have been described as preferred from table 3 or the

[0595] 35 compounds H1 to H45 from table 4.

[0596] This applies for the light-emitting device according to the invention as well as the mixture according to the invention. P24-208 Sc

[0597] - 85 -

[0598] Very particularly preferred mixtures of the compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h) and (1i) with the host materials of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (4) or (4a) for the device of the invention are obtained by combination of the compounds H1 to H45 with the compounds E1 to E30, E31, and E32.

[0599] 5 The following table 5 shows preferred mixtures. The first mixture M1, for example, is a combination of compound H1 with E1.

[0600] Table 5:

[0601] 15

[0602] 20

[0603] 25

[0604] 35

[0605]

[0606] P24-208 Sc

[0607] - 86 -

[0608] 5

[0609] 15

[0610] 20

[0611] 25

[0612] 35

[0613]

[0614] P24-208 Sc

[0615] - 87 - 5

[0616] 15

[0617] 20

[0618] 25

[0619] 35

[0620]

[0621] P24-208 Sc

[0622] - 88 - 5

[0623] 15

[0624] 20

[0625] 25

[0626] 35

[0627]

[0628] P24-208 Sc

[0629] - 89 -

[0630] 5

[0631] 15

[0632] 20

[0633] 25

[0634]

[0635] 35 The concentration of the total of all host materials 1 as described above or described as preferred in the mixture of the invention or in the light-emitting layer of the device of the invention is typically in the range from 10% by weight to 95% by weight, preferably in the range from 15% by weight to 90% by weight, more preferably in the range from 15% by P24-208 Sc

[0636] - 90 -

[0637] weight to 80% by weight, even more preferably in the range from 20% by weight to 70% by weight, very especially preferably in the range from 40% by weight to 80% by weight and most preferably in the range from 50% by weight to 70% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0638] 5

[0639] The concentration of the total of all host materials 2 as described above or described as preferred in the mixture of the invention or in the light-emitting layer of the device of the invention is typically in the range from 5% by weight to 90% by weight, preferably in the range from 10% by weight to 85% by weight, more preferably in the range from 20% by 10 weight to 85% by weight, even more preferably in the range from 30% by weight to 80% by weight, very especially preferably in the range from 20% by weight to 60% by weight and most preferably in the range from 30% by weight to 50% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0640] 15 The present invention also relates to a mixture comprising at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) as described before or preferably described before which comprises at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters having thermally activated delayed fluorescence.

[0641] 20

[0642] The present invention also relates to a mixture comprising at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) as described before or preferably described before which comprises at least one phosphorescent emitter.

[0643] 25 The present invention also relates to a mixture consisting of at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) as described before or preferably described before and one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters having thermally activated delayed fluorescence and a phosphorescent emitter.

[0644] 30 The present invention also relates to a mixture consisting of at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) as described before or preferably described before and a phosphorescent emitter.

[0645] The term “phosphorescent emitters” typically encompasses compounds where the light 35 is emitted through a spin-forbidden transition from an excited state having higher spin multiplicity, i.e. a spin state > 1, for example through a transition from a triplet state or a state having an even higher spin quantum number, for example a quintet state. This is preferably understood to mean a transition from a triplet state. P24-208 Sc

[0646] - 91 -

[0647] Suitable phosphorescent emitters (= triplet emitters) are especially compounds which, when suitably excited, emit light, preferably in the visible region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic 5 number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the abovementioned metals are regarded as phosphorescent emitters.

[0648] 10

[0649] In general, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to those skilled in the art in the field of organic electroluminescent devices are suitable.

[0650] 15 Preferred phosphorescent emitters are compounds containing iridium or platinum.

[0651] Preferred phosphorescent emitters according to the present invention conform to the formula (I)

[0652]

[0653] where the symbols and indices for this formula (I) are defined as follows:

[0654] n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0655] X is the same or different at each instance and is N or CR,

[0656] R is the same or different at each instance and is H, D, F, CN or a branched or linear 30 alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated, branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be partly or fully substituted by deuterium, or an aromatic heteroaromatic ring system which has 5 to 60 ring atoms and may be partly or fully substituted by deuterium.

[0657] 35

[0658] In emitters of the formula (I), n is preferably 1 and m is preferably 2.

[0659] In emitters of the formula (I), preferably, one X is selected from N and the other X are CR, or all X are the same or different at each instance and are CR. P24-208 Sc

[0660] - 92 -

[0661] In emitters of the formula (I), at least one R is preferably different from H. In emitters of the formula (I), preferably two R are different from H and have one of the other definitions given above for the emitters of the formula (I).

[0662] 5 The invention accordingly further provides an organic electroluminescent device as described above or described as preferred, characterized in that the light-emitting layer, as well as the host materials 1 and 2, comprises at least one phosphorescent emitter conforming to formula (I) as described above.

[0663] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in table 5, and on pages 127 to 129 in table 6. The emitters are incorporated into description by this reference.

[0664] Particularly preferred examples of phosphorescent emitters are listed in table 6 below.

[0665] 15 Table 6:

[0666] 20

[0667] 25

[0668] 35

[0669]

[0670] P24-208 Sc

[0671] 5

[0672] 15

[0673] 20

[0674] 25

[0675] 35

[0676]

[0677] P24-208 Sc

[0678] 5

[0679] 15

[0680] 20

[0681] 25

[0682] 35

[0683]

[0684] P24-208 Sc

[0685] - 95 -

[0686] In the mixtures of the invention or in the light-emitting layer of the device of the invention, any mixture as described preferably a combination of E1 to E30, E31, and E32 with H1 to H45, particularly selected from M1 to M600 is preferably combined with a compound of the formula (I).

[0687] 5

[0688] The light-emitting layer in the organic electroluminescent device of the invention, comprising at least one phosphorescent emitter, is preferably an infrared-emitting or yellow-, orange-, red-, green-, blue- or ultraviolet-emitting layer, more preferably a yellow- or green-emitting layer and most preferably a green-emitting layer.

[0689] 10

[0690] A yellow-emitting layer is understood here to mean a layer having a photoluminescence maximum within the range from 540 to 570 nm. An orange-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 570 to 600 nm. A red-emitting layer is understood to mean a layer having a photoluminescence 15 maximum within the range from 600 to 750 nm. A green-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 490 to 540 nm. A blue-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined here by measuring the

[0691] 20 photoluminescence spectrum of the layer having a layer thickness of 50 nm at room temperature, where the layer comprises the inventive combination of the host material 1 of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h) or (1i) and of the host material 2 consisting of at least one of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or (4a), and the corresponding emitter.

[0692] 25

[0693] The photoluminescence spectrum of the layer is recorded, for example, with a commercial photoluminescence spectrometer.

[0694] The photoluminescence spectrum of the emitter chosen is generally measured in 30 oxygen-free solution, 10'5molar, at room temperature, a suitable solvent being any in which the chosen emitter dissolves in the concentration mentioned. Particularly suitable solvents are typically toluene or 2-methyl-THF, but also dichloromethane. Measurement is effected with a commercial photoluminescence spectrometer. The triplet energy Ti in eV is determined from the photoluminescence spectra of the emitters. First the peak 35 maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV by: E(Ti in eV) = 1240 / E(Ti in nm) = 1240 / PLmax. (in nm). P24-208 Sc

[0695] - 96 -

[0696] Preferred phosphorescent emitters are accordingly yellow emitters, preferably of the formula (I) or from table 6, the triplet energy Ti of which is preferably ~2.3 eV to ~2.1 eV.

[0697] Preferred phosphorescent emitters are accordingly green emitters, preferably of the 5 formula (I) or from table 6, the triplet energy Ti of which is preferably ~2.5 eV to ~2.3 eV.

[0698] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (I) or from table 6 as described above, the triplet energy Ti of which is preferably ~2.5 eV to ~2.3 eV.

[0699] Most preferably, green emitters, preferably of the formula (I) or from table 6, as described above, are selected for the mixture of the invention or emitting layer of the invention.

[0700] 15 It is also possible for fluorescent emitters to be present in the light-emitting layer of the device of the invention or in the mixture of the invention.

[0701] Preferred fluorescent emitting compounds are selected from the class of the arylamines, where preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably having at least 14 ring atoms.

[0702] 20 Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9 position. An aromatic anthracenediamine is 25 understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 positions. Aromatic pyreneamines, pyrenediamines, chryseneamines and chrysenediamines are defined analogously, where the diarylamino groups are bonded to the pyrene preferably in the 1 position or 1,6 positions. Further preferred emitting compounds are indenofluoreneamines or- diamines, benzoindenofluoreneamines or -diamines, and dibenzoindenofluoreneamines or -diamines, and indenofluorene derivatives having fused aryl groups. Likewise preferred are pyrenearylamines. Likewise preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives joined to furan units or to thiophene units. The light-emitting device or the 35 mixture of the invention may additionally also comprise materials that exhibit TADF (thermally activated delayed fluorescence).

[0703] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device may have three or four different matrix materials, P24-208 Sc

[0704] - 97 -

[0705] preferably three different matrix materials. These corresponding mixed matrix systems may consist of the matrix materials described for the host material 1 and the host material 2, but they may also comprise, as a third or fourth matrix material, for example alongside a host material 1 or host material 2, wide-band-gap materials, bipolar host 5 materials, electron transport materials (ETM) or hole transport materials (HTM).

[0706] Preferably, the mixed matrix system is optimized for an emitter of the formula (I), or for an emitter from table 6.

[0707] A wide-band gap material is understood herein to mean a material within the scope of 10 the disclosure of US 7,294,849 which is characterized by a band gap of at least 3.5 eV, the band gap being understood to mean the gap between the HOMO and LUMO energy of a material.

[0708] The present invention also relates to a mixture consisting of a compound of the formula 15 (1), one compound of formula (2) or of the formula (3) or of the formula (4) and a third matix material and all three host materials are different from each other. The third host material may be selected as described before or may be selected from any of the compounds of formulae (1) to (4) or any preferred embodiment thereof.

[0709] 20 In one embodiment of the present invention, the mixture, aside from the constituents of the host material 1 and the host material 2 as described above or described with preference, does not comprise any further constituents, i.e. functional materials. These are material mixtures that are used as such for production of the light-emitting layer. These mixtures are also referred to as premix systems that are used as the sole material 25 source in the vapor deposition of the host materials for the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, it is possible in a simple and rapid manner to achieve the vapor deposition of a layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

[0710] 30

[0711] In an alternative embodiment of the present invention, the mixture, aside from the constituents of the host material 1 and the host material 2 and optionally a third host material, as described above or described with preference, also comprises a phosphorescent emitter, as described above. In the case of a suitable mixing ratio in the 35 vapor deposition, this mixture may also be used as the sole material source.

[0712] Preference is given to premix systems consisting of two matrix materials, namely one compound of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h) or (1i) and one P24-208 Sc

[0713] - 98 -

[0714] compound of one of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b 1 ), (3d), (3d1), (3e1), (4) or (4a).

[0715] Preference is given to premix systems consisting of three matrix materials, namely one compound of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h) or (1i) and two 5 compounds of one of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b 1 ), (3d), (3d1), (3e1), (4) or (4a).

[0716] The components or constituents of the light-emitting layer of the device of the invention may thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or described as preferred, optionally with the phosphorescent emitter, as described above or described as preferred, are provided for that purpose in a formulation containing at least one solvent. Suitable formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. Suitable and preferred solvents are, 15 for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 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- 20 dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, 25 tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2- isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1- bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1- methylnaphthalene, 1 -ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

[0717] A suitable formulation is a formulation containing at least one compound according to the invention, as described above, or a mixture according to the invention, as described below, and at least one solvent. The solvent can be a solvent mentioned above or a 35 mixture of these solvents.

[0718] The light-emitting layer in the device of the invention, according to the preferred embodiments and the emitting compound, contains preferably between 99.9% and 1% by volume, further preferably between 99% and 10% by volume, especially preferably P24-208 Sc

[0719] - 99 -

[0720] between 98% and 60% by volume, very especially preferably between 97% and 80% by volume, of matrix material composed of at least one compound of the formulae (1), (1a), (1b), (1c), (1 d), (1e), (1f), (1g), (1h) or (1i) and at least one compound of one of the formulae (2), (2a), (3), (3a), (3b), (3c), (3d), (3e), (3a1), (3b1), (3d), (3d1), (3e1), (4) or 5 (4a) according to the preferred embodiments, based on the overall composition of emitter and matrix material. Correspondingly, the light-emitting layer in the device of the invention preferably contains between 0.1% and 99% by volume, further preferably between 1% and 90% by volume, more preferably between 2% and 40% by volume, most preferably between 3% and 20% by volume, of the emitter based on the overall composition of the light-emitting layer composed of emitter and matrix material. If the compounds are processed from solution, preference is given to using the corresponding amounts in % by weight rather than the above-specified amounts in % by volume.

[0721] The present invention also relates to an organic electroluminescent device as described 15 above or described as preferred, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL) and / or an electron blocking layer (EBL), the hole-injecting material and / or hole-transporting material and / or electron blocking layer of which belongs to the class of monoamines or diamines that do not contain a carbazole unit. The hole-injecting material and / or hole-transporting material and / or 20 electron blocking material particularly preferably comprises a monoamine or diamine containing a fluorenyl or bispirofluorenyl group, but no carbazole unit. The hole-injecting material and / or hole-transporting material and / or electron blocking material particularly preferably comprises a monoamine containing a fluorenyl or bispirofluorenyl group, but no carbazole unit.

[0722] 25

[0723] Preferred hole-injecting materials and / or hole-transporting materials and / or electron blocking materials which are used in accordance with the invention in the organic layer

[0724]

[0725] P24-208 Sc

[0726] - 100 -

[0727]

[0728] where the following applies to the symbols and indices occurring within formulae (l-A) and (l-B):

[0729] 15 Ar10, Ar11, Ar12are on each occurrence, identically or differently, an aromatic ring system having 6 to 40 aromatic ring atoms or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R12, where two or more radicals Ar10, Ar11, Ar12may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R12;

[0730] 20

[0731] L12is on each occurrence, identically or differently, a single bond, an aromatic having 6 to 30 aromatic ring atoms or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R13;

[0732] 25 k12 is an integer selected from 1 to 3;

[0733] E is the same or different at each instance and are selected from a single bond, Si(R12)2, O, S, NR12, and C(R12)2;

[0734] i10, i11 , i12 are on each occurrence, identically or differently, 0 or 1;

[0735] T21, T22are the same or different at each instance and are selected from a single bond, O, S, NR21, and C(R21)2;

[0736] 35 R12, R13, R20a, R20b, R20C, R20d, R21stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(R19)2,C(=O)Ar*, P(=O)(Ar*)2, S(=O)Ar*, S(=O)2Ar*, NO2, Si(R19)3, B(OR19)2, OSO2R19, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R19, P24-208 Sc

[0737] - 101 -

[0738] where in each case one or more non-adjacent CH2 groups may be replaced by R19C=CR19, 0=0, Si(R19)2, Ge(R19)2, Sn(R19)2, C=O, C=S, C=Se, P(=O)(R19), SO, SO2, O or S and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic ring system having 6 to 40 aromatic ring atoms or heteroaromatic ring 5 system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R19; two or more radicals R12, two or more radicals R13, two or more radicals R20a, two or more radicals R20b, two or more radicals R20c, two or more radicals R20dor two or more radicals R21may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R19;

[0739] R19stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(R’)2, C(=O)Ar*, P(=O)(Ar*)2, S(=O)Ar*, S(=O)2Ar*, NO2, Si(R )3, B(OR')2, OSO2R , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a 15 cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R , where in each case one or more non-adjacent CH2 groups may be replaced by R C=CR , 0=0, Si(R )2, Ge(R )2, Sn(R )2, C=O, C=S, C=Se, P(=O)(R ), SO, SO2, O or S and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic ring system having 6 to 40 aromatic ring atoms or 20 heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R ; where two radicals R19may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R ;

[0740] 25 Z11and Z21stand on each occurrence, identically or differently, for a group represented by formula A

[0741]

[0742] Formula A

[0743] where R90stands on each occurrence, identically or differently, for a straightchain alkyl having 1 to 40 C atoms or branched or a cyclic alkyl having 3 to 40 C atoms, each of which may be substituted by one or more radicals R’, where in each case one or 35

[0744] more non-adjacent CH2 groups may be replaced by R’C=CR’ or 0=0, and where one or more H atoms may be replaced by D, an aromatic ring system having 6 to 40 aromatic ring atoms or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R’, preferably, R90stands on P24-208 Sc

[0745] - 102 -

[0746] each occurrence, identically or differently, for a straight-chain alkyl having 1 to 40 C atoms or branched or a cyclic alkyl having 3 to 40 C atoms, each of which may be substituted by one or more radicals R’, where in each case one or more non-adjacent CH2groups may be replaced by R’C=CR’ or C=C, and where one or more H atoms may 5 be replaced by D, more preferably, R90stands on each occurrence, identically or differently, for a straight-chain alkyl having 1 to 40 C atoms or branched alkyl having 3 to 40 C atoms, each of which may be substituted by one or more radicals R’, where in each case one or more non-adjacent CH2 groups may be replaced by R’C=CR’ or C=C, and where one or more H atoms may be replaced by D;

[0747] L90is a single bond, an aromatic having 6 to 30 aromatic ring atoms or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R’, preferably L90is a single bond or an aromatic having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R’, 15 more preferably, L90is a single bond;

[0748] t10 is an integer selected from 0 to 10;

[0749] t20 is an integer selected from 0 to 10;

[0750] 20

[0751] * is a binding site with the rest of the formula (l-A) or (l-B);

[0752] Ar* is, on each occurrence, identically or differently, an aromatic ring system having 6 to 40 aromatic ring atoms or heteroaromatic ring system having 5 to 40 aromatic ring 25 atoms, which may in each case also be substituted by one or more radicals R ;

[0753] R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, aryl or heteroaryl amine group having 6 to 24 ring atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms or heteroaromatic ring system having 5 to 24 aromatic ring atoms; and

[0754] 35 m21, m22, m23 and m24 are on each occurrence, identically or differently, 0, 1, 2, 3 or 4;

[0755] and with the condition that a compound of the formula (l-A) or of the formula (l-B) do not contain a carbazole unit. P24-208 Sc

[0756] - 103 -

[0757] A preferred compound of formula (l-A) is represented by formula (l-A-1),

[0758]

[0759] formula (l-A-1),

[0760] where Ar12, L12, k12, Ar10, Ar11, Z11and t10 have a meaning as described above, with the condition that a compound of the formula (l-A-1) does not contain a carbazole unit.

[0761] In compounds of formula (l-A) or (l-A-1), Ar12is preferably selected from the groups Ar12-

[0762]

[0763] 35 P24-208 Sc

[0764] - 104 -

[0765]

[0766] where R12and * have a meaning as described before, Z and Z1are at each occurrence independently N or C with the condition that two adjacent Z or two adjacent Z1are not both N, Esis S or O, preferably O, a is 1 , 2 or 3, b is 1 , 2, 3 or 4, c is 1 , 2, 3 or 4, d is 1 , 2, 3 or 4 and e is 1 , 2, 3, 4 or 5.

[0767] In preferred compounds of formula (l-A) and (l-A-1), t10 is 0 and Z11does not occur.

[0768] In a preferred embodiment, Ar12-3 is selected from Ar12-3-1 or Ar12-3-2,

[0769] 35 P24-208 Sc

[0770] - 105 -

[0771]

[0772] where R12, a, b, c, d and * have a meaning as described before.

[0773] 20

[0774] In a preferred embodiment, Ar12-4 is selected from Ar12-4-1 or Ar12-4-2,

[0775]

[0776] where R12, a, b, Z1and * have a meaning as described before, where Z1is preferably C.

[0777] 35 In a preferred embodiment compounds of formulae (l-A) or (l-A-1) are selected from compounds of formulae (l-A-2) to (l-A- 5), which may be partially or fully deuterated, P24-208 Sc

[0778] - 106 -

[0779]

[0780] 15 formula (l-A-4) formula (l-A-5),

[0781] where L12 in formulae (l-A-2) to (l-A-5) is an aromatic ring system having 6 to 30 aromatic ring atoms or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R13, where R13, Ar10and Ar11have a 20

[0782] meaning as described before or as preferably described below and R12has at each occurrence independently a meaning as described before but excluding H and R12is at each occurrence independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms or phenyl where both alkyl and aryl may be substituted by one or more D atoms, with the condition that a compound of the formulae (l-A-2) to (l-A-5) does not 25

[0783] contain a carbazole unit.

[0784] In compounds of the formulae (l-A), (l-A-1), (l-A-2) to (l-A-5), the linker L12is preferably, identically or differently, a single bond or is selected from the group consisting of benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl and dibenzothiophenyl, which may each be substituted by one or more radicals R13. More preferably, L12is, identically or differently, a single bond or are selected from the group consisting of benzene, biphenyl, terphenyl, naphthyl, dibenzofuranyl and dibenzothiophenyl, which may be substituted by one or more radicals R13. Even more preferably, L12stands for a single bond, benzene or biphenyl, 35

[0785] which may be substituted by one or more radicals R13. R13is preferably D.

[0786] In compounds of the formulae (l-A-2) to (l-A-5), R12is preferably methyl or phenyl which may be substituted by one or more D atoms. P24-208 Sc

[0787] - 107 -

[0788] In compounds of the formulae (l-A-2) to (l-A-5), R12is preferably independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms or an arylalkyl group having 6 to 30 carbon atoms where said alkyl, aryl and arylalkyl groups may be substituted by one or more D atoms.

[0789] 5 In compounds of the formulae (l-A-2) to (l-A-5), R12is preferably independently tertbutyl, phenyl or phenyl substituted with tert.-butyl where these groups may be partially or fully deuterated.

[0790] In a preferred embodiment of Ar12-5, a is 0, e is 1 or 2 and R12is preferably independently tert-butyl, phenyl or phenyl substituted with tert.-butyl where these groups may be partially or fully deuterated.

[0791] In a preferred embodiment of Ar12-3, Ar12-3-1, Ar12-3-2, a is 1, b is 1, c is 1, d is 1 and R12is preferably independently tert-butyl, phenyl or phenyl substituted with tert.-butyl 15 where these groups may be partially or fully deuterated.

[0792] In one embodiment of the compounds of the formulae (l-A), (l-A-1), (l-A-2), (l-A-3), (l-A-

[0793]

[0794] is preferably selected from the groups of formulae (A-1) to (A-39), which may be partially or fully deuterated,

[0795]

[0796] P24-208 Sc

[0797] - 108 -

[0798]

[0799]

[0800]

[0801] A-9 A-10 35 P24-208 Sc

[0802] - 109 -

[0803]

[0804] P24-208 Sc

[0805] - 110 -

[0806]

[0807]

[0808]

[0809] 35 P24-208 Sc

[0810]

[0811] P24-208 Sc

[0812] - 112 -

[0813]

[0814] 15

[0815] 20

[0816]

[0817]

[0818] where the dotted line represents the remainder of formulae (l-A), (l-A-1), (l-A-2), (l-A-3), (l-A-4) and (l-A-5) , and where R4is at each occurrence independently a straight-chain or branched alkyl group or phenyl where both alkyl and aryl may be substituted by one or 25

[0819] more D atoms or the two substituents R4may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more D atoms.

[0820] In preferred compounds of formula (l-B), t20 is 0 and Z21does not occur.

[0821] A preferred compound of the formula (l-B) is represented by formula (l-B-1),

[0822] 35 P24-208 Sc

[0823]

[0824] e a meaning as described before, with the condition that a compound of the formulae (l-B-1) does not contain a carbazole unit. It is preferable tha a compound of the formula (l-B) has one or two substituents R20a, R20b, R20cor R20dwhich are different from H or D and which may 15 be preferably selected independently from a straight-chain or branched alkyl group, an aryl group having 6 to 18 carbon atoms or an arylalkyl group having 6 to 30 carbon atoms where said alkyl, aryl and arylalkyl groups may be substituted by one or more D atoms.

[0825] 20 In a preferred embodiment of compounds of the formula (l-B-1), R21is at each occurrence independently an aryl group having 6 to 40 carbon atoms which may be substituted by one or more D atoms.

[0826] In compounds of the formulae (l-A), (l-A-1), (l-A-2) to (l-A-5), (l-B) and (l-B-1), the symbols Ar10, Ar11and R21are on each occurrence, identically or differently, preferably 25

[0827] selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, benzofuranyl, and benzothiophenyl, and combinations of two or three of these groups, which are each optionally substituted by one or more radicals R12, where R12is preferably D.

[0828] In compounds of formulae (l-A), (l-A-1), (l-A-2) to (l-A-5), (l-B) and (l-B-1), the symbols Ar10, Ar11and R21are on each occurrence, identically or differently, particularly

[0829] 35

[0830] preferably selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'- diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, P24-208 Sc

[0831] - 114 -

[0832] benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, each of which may optionally be substituted by 5 one or more radicals R12, where R12is preferably D.

[0833] Preferred hole-injecting materials and / or hole-transporting materials and / or electron blocking materials which are used in accordance with the invention in the organic layer of the device of the invention and which may be partially or fully deuterated are

[0834] 10 described in table 7.

[0835] Table 7: The following compounds may be partially or fully deuterated

[0836] 15

[0837] 20

[0838] 25

[0839] 30

[0840] 35

[0841]

[0842] P24-208 Sc

[0843] - 115 -

[0844] >

[0845] >

[0846] <

[0847] >

[0848] >

[0849] "

[0850]

[0851] P24-208 Sc

[0852] - 116 -

[0853] "

[0854] >

[0855] >

[0856] <

[0857]

[0858] P24-208 Sc

[0859] - 117 -

[0860] 5

[0861] 15 20 25

[0862] 35

[0863]

[0864] P24-208 Sc

[0865] - 118 -

[0866] > >

[0867] "

[0868] "

[0869]

[0870] P24-208 Sc

[0871] - 119 -

[0872] <

[0873] "

[0874]

[0875] P24-208 Sc

[0876] - 120 -

[0877] 5

[0878] 15 20 25

[0879] 35

[0880]

[0881] P24-208 Sc

[0882] - 121 -

[0883] 5

[0884] 15

[0885] "

[0886] 20

[0887] 25

[0888] >

[0889] 35

[0890]

[0891] P24-208 Sc

[0892] - 122 - <"

[0893] 5

[0894] 15

[0895] 20

[0896] "

[0897] 25

[0898]

[0899] 35

[0900] Processes for synthesis of compounds of the formulae (l-A) and (l-B) and their preferred embodiments as described before or of the compounds of table 7 are known in the prior art, especially in the publications cited in the table below: P24-208 Sc

[0901] - 123 -

[0902] 5

[0903] 15

[0904] 20

[0905]

[0906] The sequence of layers in the organic electroluminescent device of the invention is preferably as follows:

[0907] 25

[0908] anode / hole injection layer / hole transport layer / emitting layer / hole blocker layer / electron transport layer / electron injection layer / cathode.

[0909] This sequence of the layers is a preferred sequence.

[0910] At the same time, it should be pointed out again that not all the layers mentioned need be present and / or that further layers may additionally be present.

[0911] Materials used for the electron transport layer may be any materials as used according to the prior art as electron transport materials in the electron transport layer. Especially suitable are aluminum complexes, for example Alqs, zirconium complexes, for example 35

[0912] Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. P24-208 Sc

[0913] - 124 -

[0914] Suitable cathodes of the device of the invention are metals having a low work function, metal alloys or multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline 5 earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals having a relatively high work function, for example Ag or Al, in which case combinations of the metals such as Ca / Ag, Mg / Ag or Ba / Ag, for example, are generally used. It may also be preferable to introduce a thin interlayer of a material 10 having a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm. 15

[0915] Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. AI / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, 20 at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the emission of light (OLED, O-I-ASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is further given to conductive doped organic materials, especially 25 conductive doped polymers. In addition, the anode may also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0916] The organic electroluminescent device of the invention, in the course of production, is 30 appropriately (according to the application) structured, contact-connected and finally sealed, since the lifetime of the devices of the invention is shortened in the presence of water and / or air.

[0917] The production of the device of the invention is not restricted here. It is possible that one 35 or more organic layers, including the light-emitting layer, are coated by a sublimation method. In this case, the materials are applied by vapor deposition in vacuum sublimation systems at an initial pressure of less than 10'5mbar, preferably less than 10'6mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10'7mbar. P24-208 Sc

[0918] - 125 -

[0919] The organic electroluminescent device of the invention is preferably characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of a carrier gas sublimation. In this case, the materials are applied at a pressure between 10'5mbar and 1 bar. A special case of this method is the OVJP 5 (organic vapor jet printing) method, in which the materials are applied directly by a nozzle and thus structured (for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0920] The organic electroluminescent device of the invention is further preferably characterized in that one or more organic layers comprising the composition of the invention are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble host materials 1 and 2 and phosphorescent emitters are 15 needed. Processing from solution has the advantage that, for example, the light-emitting layer can be applied in a very simple and inexpensive manner. This technique is especially suitable for the mass production of organic electroluminescent devices.

[0921] In addition, hybrid methods are possible, in which, for example, one or more layers are 20 applied from solution and one or more further layers are applied by vapor deposition.

[0922] These methods are known in general terms to those skilled in the art and can be applied to organic electroluminescent devices.

[0923] 25 The invention therefore further provides a process for producing the organic electroluminescent device of the invention as described above or described as preferred, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by gas phase deposition, especially by a sublimation method and / or by an OVPD (organic vapor phase deposition) method and / or with the aid of a carrier gas sublimation, or from solution, especially by spincoating or by a printing method.

[0924] In the case of production by means of gas phase deposition, there are in principle two ways in which the organic layer, preferably the light-emitting layer, of the invention can 35 be applied or vapor-deposited onto any substrate or the prior layer. Firstly, the materials used can each be initially charged in a material source and ultimately evaporated from the different material sources ("co-evaporation"). Secondly, the various materials can be premixed (premix systems) and the mixture can be initially charged in a single material source from which it is ultimately evaporated ("premix evaporation"). In this way, it is P24-208 Sc

[0925] - 126 -

[0926] possible in a simple and rapid manner to achieve the vapor deposition of the lightemitting layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

[0927] 5 The following methods are possible:

[0928] A process for producing the organic electroluminescent device of the invention as described above or described as preferred, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or hole blocker layer, is applied by gas phase deposition, especially by a sublimation method and / or by an OVPD (organic vapor phase deposition) method and / or with the aid of a carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.

[0929] A process for producing the organic electroluminescent device of the invention, as described above or described as preferred, characterized in that the light-emitting layer 15 of the organic layer is applied by gas phase deposition, wherein the at least host material 1 is deposited from the gas phase together with the host material 2 and further materials that form the light-emitting layer, successively or simultaneously from at least two material sources.

[0930] 20 A process for producing the device of the invention, characterized in that the lightemitting layer of the organic layer is applied by gas phase deposition, wherein the at least one host material 1 and the at least one host material 2 is deposited from the gas phase together as premix, successively or simultaneously with the light-emitting materials selected from the group of the phosphorescent emitters, fluorescent emitters 25 and / or emitters that exhibit TADF (thermally activated delayed fluorescence).

[0931] The electronic devices of the invention, especially organic electroluminescent devices, are notable for one or more of the following surprising advantages over the prior art:

[0932] 1. Organic light-emitting devices comprising compounds of formula (1) or the preferred embodiments recited above and at least one compound of formulae (2), (3) or (4) or at least one of the preferred embodiments cited above have a very good lifetime.

[0933] 35 2. Organic light-emitting devices comprising compounds of formula (1) or the preferred embodiments recited above and hereinafter and at least one compound of formulae (2), (3) or (4) or at least one of the preferred embodiments cited above, have excellent efficiency. In this context, compounds of the invention having P24-208 Sc

[0934] - 127 -

[0935] structures of formula (1) or the preferred embodiments recited above and hereinafter bring about a low operating voltage when used in electronic devices.

[0936] These abovementioned advantages are not accompanied by an inordinately high 5 deterioration in the further electronic properties.

[0937] It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Any feature disclosed in the present invention, unless stated otherwise, should therefore be considered as an example from a generic series or as an equivalent or similar feature.

[0938] All features of the present invention may be combined with one another in any manner, 15 unless particular features and / or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

[0939] The technical teaching disclosed with the present invention may be abstracted and 20 combined with other examples.

[0940] The invention is illustrated in detail by the examples which follow, without any intention of restricting it thereby.

[0941] Examples

[0942] 25 Synthesis examples

[0943] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared by means of synthesis methods known to those skilled in the art. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature.

[0944] a) 2-([1,1'-biphenyl]-4-yl)-4-(8-chlorodibenzo[b,d]furan-1-yl)-6- (dibenzo[b,d]furan-4-yl)-1,3,5-triazine:

[0945] 35 P24-208 Sc

[0946] - 128 -

[0947]

[0948] 2-(8-Chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (34.4g, 100.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazin (43.3 g, 105.0 mmol) and sodium carbonate (22.26 g, 210.0 mmol) are suspended in 600 ml of ethylene glycol dimethyl ether and 300 ml of water and the mixture is inertized for 30 min. Subsequently, tri-o-tolylphosphine (913 mg, 3.0 mmol) and then palladium (II) acetate (112 mg, 0.5 mmol) are added, and the reaction mixture is heated under reflux for 20 h. After cooling, the precipitated solids are filtered off with suction and washed 15

[0949] with ethanol. The crude product is recrystallized from m-xylene. Yield: 50 g (83 mmol, 80 %) of solids, 98% by HPLC.

[0950] The following compounds are prepared analogously:

[0951] 20

[0952] 25

[0953]

[0954] 35 P24-208 Sc

[0955] - 129 -

[0956] 5 "

[0957] "

[0958] 15

[0959] <<

[0960] 20

[0961] <

[0962] 25

[0963] 35

[0964]

[0965] P24-208 Sc

[0966] - 130 -

[0967] <

[0968] 5

[0969] <

[0970] 15

[0971] "

[0972] 20

[0973] <

[0974] 25

[0975] "

[0976] "

[0977] 35

[0978]

[0979] P24-208 Sc

[0980] 5

[0981] 15

[0982] 20

[0983]

[0984] 25

[0985] The following literature known compounds can be used analogously as starting material 1 and starting material 2.

[0986]

[0987] 35 P24-208 Sc

[0988] - 132 -

[0989] >

[0990] 5

[0991] >

[0992] 15

[0993] >< 20

[0994] "

[0995] 25

[0996] <

[0997] 35

[0998]

[0999] P24-208 Sc

[1000] - 133 -

[1001] Table for starting material 2:

[1002] 5 < <

[1003] 15

[1004] < 20

[1005] <

[1006] 25

[1007]

[1008] 35 P24-208 Sc

[1009] - 134 -

[1010] >

[1011] 5

[1012] "

[1013] >

[1014] 15

[1015] 20

[1016] 25

[1017] <

[1018] 35

[1019] "

[1020]

[1021] P24-208 Sc

[1022] - 135 -

[1023] b) 2-([1,T-biphenyl]-4-yl)-4-(dibenzo[b,d]furan-4-yl)-6-(8-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)dibenzo[b,d]furan-1-yl)-1,3,5-triazine:

[1024]

[1025] An initial charge of 2-([1,1'-biphenyl]-4-yl)-4-(8-chlorodibenzo[b,d]furan-1-yl)-6- (dibenzo[b,d]furan-4-yl)-1,3,5-triazine (52 g, 88.0 mmol), bis(pinacolato)diboron [73183- 34-3] (25.39 g, 100.0 mmol) and potassium acetate (28.82 g, 293.6 mmol) in 1,4- dioxane (700 ml) is inertized with argon for 2 min. Subsequently, XPhos [564483-18-7] (456 mg, 0.96 mmol) and Pd2(dba)3 [51364-51-3] (435 mg, 0.48 mmol) are added and the reaction mixture is stirred under reflux for 26 h. After cooling, the solvent is removed 15

[1026] by rotary evaporation and the residue is worked up by extraction with toluene / water. The organic phase is dried over Na2SO4 and concentrated to dryness by rotary evaporation. The residue is boiled under reflux with ethyl acetate for 2 h, and the solids are filtered off with suction and washed with ethyl acetate. Yield: 52 g (80.2 mmol, 87 %) of solids; 97 % by 1H NMR.

[1027] 20

[1028] The following compounds can be prepared analogously: Rather than X-Phos, it is also possible to use S-Phos or tricyclohexylphosphine as ligand, or Pd(dppf)Cl2 x CH2CI2 [95464-05-4] for borylation of functional bromide groups. Purification can be effected using column chromatography, or recrystallization can be effected using standard 25

[1029] solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The following compounds are prepared analogously:

[1030] 35

[1031]

[1032] P24-208 Sc

[1033] - 136 -

[1034] 5

[1035] "

[1036] 15

[1037] 20

[1038] 25

[1039]

[1040] 35 P24-208 Sc

[1041] - 137 -

[1042] 5

[1043] >

[1044] "

[1045] 15

[1046] > "

[1047] 20

[1048] <

[1049] 25

[1050] <

[1051] 35

[1052]

[1053] P24-208 Sc

[1054] - 138 -

[1055] 5

[1056] < "

[1057] 15

[1058] >

[1059] 20

[1060] <

[1061] 25

[1062]

[1063] c) 4-(9-(4-([1,T-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)dibenzo[b,d]furan-2- yl)benzonitrile:

[1064]

[1065] P24-208 Sc

[1066] - 139 -

[1067] To an initial charge of 2-[1,1'-biphenyl]-4-yl-4-phenyl-6-[8-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-1-dibenzofuranyl]-1,3,5-triazine (17.5 g, 29.1 mmol), 4- bromobenzonitrile (5.2 g, 29.1 mmol) and Na2COs(6.17 g, 58.2 mmol) in a flask are added toluene (300 ml) and water (100 ml), and the mixture is inertized with argon for 30 5 min. Subsequently, tetrakis(triphenylphosphine)palladium(0) [14221-01-3] (1.00 g, 0.87 mmol) is added and the mixture is heated under reflux for 36 h. After cooling, the reaction mixture is worked up by extraction with toluene and water, the combined organic phases are dried over Na2SO4, and the filtrate is concentrated to dryness by rotary evaporation. The residue is suspended in 350 ml of hot EtOH and stirred under reflux for 1 h, and the solids are filtered off with suction after cooling. The crude product is subjected to hot extraction with toluene / heptane (1:1) twice, then recrystallized three times from n-butyl acetate and finally sublimed under high vacuum.

[1068] Yield: 11,6(20.1 mmol, 69%); purity: >99.9 % by HPLC.

[1069] 15 The following compounds can be prepared analogously: The catalyst system used here, rather than tetrakis(triphenylphosphine)palladium(0), may also be Pd2(dba)3with SPhos [657408-07-6] (palladium source and ligand) or bis(triphenylphosphine)palladium(ll) chloride [13965-03-2], Purification can also be effected using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, 20 butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetra hydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N- methylpyrrolidone, etc.

[1070] 25

[1071] 35

[1072]

[1073] P24-208 Sc

[1074] - 140 -

[1075] "

[1076] 5

[1077] 15

[1078] >

[1079] 20

[1080] "

[1081] 25

[1082] 35

[1083]

[1084] P24-208 Sc

[1085] - 141 -

[1086] 5

[1087] 15 20 25

[1088]

[1089] 35 P24-208 Sc

[1090] - 142 -

[1091] 5

[1092] 15 20 25

[1093]

[1094] 35 P24-208 Sc

[1095] - 143 -

[1096] 5

[1097] 15

[1098] 20

[1099]

[1100] d) 4-(9-(4-([1, -biphenyl]-4-yl-d9)-6-(phenyl-d5)-1,3,5-triazin-2-yl)dibenzo[b,d]furan- 2-yl-1,3,4,6,7,8-d6)benzonitrile-d4:

[1101]

[1102] 35

[1103] The amount of 8.9 g (15.5 mmol; 1.00 eq) 4-(9-(4-([1,1'-biphenyl]-4-yl)-6-phenyl-1,3,5- triazin-2-yl)dibenzo[b,d]furan-2-yl)benzonitrile and 20.0 g Pt 5% on activated charcoal are suspended in 400 g (502 mmol; 1.00 eq) deuterium oxide [CAS 7789-20-0] and 200 P24-208 Sc

[1104] - 144 -

[1105] g (778 mmol; 1.55 eq) toluene-d8 [CAS 2037-26-5], The reaction mixture is stirred for 5 days at 165°C and increased internal pressure. After cooling, it is extracted twice with tetra hydrofuran and the combined organic phases are washed with saline and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. The

[1106] 5 product shown above in mixture with proportions of H / D isotopome rs and H / D isotopologues is obtained after further purification by extraction, recrystallization and

[1107] sublimation (p = 5 x 10'7mbar).

[1108] "

[1109] The yield is 4,7g (7,8 mmol), corresponding to 51 % of t he theory (degree of deuteration > 74 mol%).

[1110] Analogously, the following compounds can be obtained:

[1111] The following compounds are prepared analogously:

[1112] 15

[1113] " > <

[1114] <

[1115] 20

[1116] 25

[1117] 35

[1118]

[1119] P24-208 Sc

[1120] - 145 -

[1121] <

[1122] 5

[1123] 15

[1124] "

[1125] 20

[1126] <

[1127] 25

[1128] <

[1129] <

[1130] 35

[1131]

[1132] P24-208 Sc

[1133] - 146 -

[1134] > 5

[1135] 15

[1136] <

[1137] 20

[1138] 25

[1139] >

[1140] "

[1141] <

[1142] 35

[1143]

[1144] The products in this section d) are shown as fully deuterated compounds for the sake of simplification, whereby these are generally intended to denote compounds that have a degree of deuteration of at least 50 mol%. The degree of deuteration for said fully P24-208 Sc

[1145] - 147 -

[1146] deuterated compounds is therefore between 50mol% and 100 mol% or has a preferred deuteration degree of 50 mol% to 90 mol% or 70 mol% to 90 mol%.

[1147] Production of the OLEDs

[1148] 5 Production of vapor processed OLED devices

[1149] The use of the material combinations according to the invention in OLEDs is presented in the following examples Ex1 to Ex14 (see Tables 8 and 9).

[1150] Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated with an oxygen plasma, followed by an argon plasma before coating. These plasma treated glass plaques form the substrates to which the OLEDs are applied.

[1151] The OLEDs basically have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / 15 hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The detailed stack sequence is shown in table 8. The materials used for the OLED fabrication are presented in table 10, unless previously described.

[1152] The data of the OLEDs are summarized in table 9.

[1153] 20

[1154] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material and one emitting dopant, which is mixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as E1:H1:TEG1 (37%:55%:8%) here 25 means that material E1 is present in the layer in a proportion by volume of 37%, material H1 is present in the layer in a proportion by volume of 55%, and material TEG1 is present in the layer in a proportion by volume of 8%. Analogously, the electron-transport layer and hole-injection layer may also consist of a mixture of two or more materials.

[1155] The OLED devices are characterized by standard methods. For this purpose, electroluminescence spectra and current-voltage-luminance (IVL) characteristics are measured, from which the external quantum efficiency (EQE) is calculated. The calculation is performed assuming Lambertian emission characteristics. EQE10 denotes the external quantum efficiency measured at a current density of 10 mA / cm2.

[1156] 35 For every example (Ex) or comparative example (V), a relative EQE (rel. EQE) will be calculated in comparison to the comparative example V1 by using the following formula: rel. EQE (Ex orV) = 100 * (EQE10(Ex or V) / EQE10(V1)).

[1157] The lifetime LT is defined as the time in hours (h) after which the luminance in cd / m2drops from the starting luminance (L0) to a certain proportion L1 (in %) in the course of P24-208 Sc

[1158] - 148 -

[1159] operation with a constant current density jo in mA / cm2. A figure of L1 / L0=90% means that the lifetime reported in the LT column corresponds to the time in hours after which the starting luminance (L0) falls to 90% of its starting value.

[1160] 5 For every example (Ex) or comparative example (V), a relative lifetime (rel. LT) will be calculated in comparison to the comparative example V1 by using the following formula: rel. LT (Ex or V) = 100 * (LT(Ex or V) / LT(V1)).

[1161] Use of mixtures according to the invention in OLEDs

[1162] The material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[1163] Table 8:

[1164] 15 20

[1165] 25 35

[1166]

[1167] P24-208 Sc

[1168] - 149 -

[1169] 5

[1170] 15 20 25

[1171] 35

[1172]

[1173] P24-208 Sc

[1174] - 150 -

[1175] Table 9: Data of the OLEDs

[1176] 5

[1177] 15

[1178] 20

[1179]

[1180] Table 10: Materials used, if not already described

[1181] 25

[1182] " <

[1183] " 35

[1184]

[1185] P24-208 Sc

[1186] 5

[1187] 15

[1188] 20

[1189] 25

[1190] 35

[1191]

[1192] P24-208 Sc

[1193] - 152 -

[1194] 5

[1195]

[1196] The following mixtures M-1 to M-252 can be deuterated as disclosed before and are expected to improve the life time of an OLED comprising them. The first mixture M-1, for 15

[1197] example, is a combination of compound A1 with B1.

[1198] 20

[1199] 25

[1200] 35

[1201]

[1202] P24-208 Sc

[1203] - 153 - 5

[1204] 15

[1205] 20

[1206] 25

[1207] 35

[1208]

[1209] P24-208 Sc

[1210] - 154 - 5

[1211]

[1212] 15

[1213] 20

[1214] 25

[1215]

[1216] 35 P24-208 Sc

[1217] - 155 -

[1218] 5

[1219] 15 20 25

[1220] 35

[1221]

[1222] P24-208 Sc

[1223] - 156 -

[1224] 5

[1225] 15 20 25

[1226]

[1227] 35

Claims

P24-208 Sc- 157 -Claims1. Organic light-emitting device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one 5 light-emitting layer contains at least one compound of the formula (1) as host material 1 and at least one compound of the formulae (2), (3) or (4) as host materialwhere the symbols and indices used are as follows:P24-208 Sc- 158 -Y stands for O or S;R at each instance is the same or different and is H or D;R# is the same or different at each instance and stands for D, F, phenyl or partially or fully deuterated phenyl;5 An , Ar2 at each instance are the same or different and are an aromatic ring system having 6 to 18 C atoms which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# radicals;R6at each instance is the same or different and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R7radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R7)2, C=O, NR7, O, S or 15 CONR7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and which may be partially or completely deuterated in each case; it is also possible here for two R6radicals together to form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system;Ars is the same or different at each instance and is an aromatic or20 heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R7radicals;R7is the same or different at each instance and is D, F, Cl, Br, I, N(R8)2, CN, NO2, OR8, SR8, Si(R8)3, B(OR8)2, C(=O)R8, P(=O)(R8)2, S(=O)R8, S(=O)2R8, OSO2R8, a straight-chain alkyl group having 1 to 20 carbon atoms or an 25 alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R8radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R8)2, C=O, NR8, O, S or CONR8, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and which may be partially or completely deuterated in each case; at the same time, two or more R7radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;R8is the same or different at each instance and is H, D, F or an aliphatic, 35 aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F;s is the same or different at each instance and is 0, 1 , 2, 3 or 4;t is the same or different at each instance and is 0, 1 , 2 or 3;P24-208 Sc- 159 -u is the same or different at each instance and is 0, 1 or 2,with the proviso that at least one R6in formulae (2), (3) and (4) is D or at least one Ars is a deuterated substituent.5 2. An organic light-emitting device according to Claim 1, where the host material 1 corresponds to at least one compound of formulae (1a), (1b) or (1c),where An , Ar2 and R have a meaning according to claim 1.

3. An organic light-emitting device according to Claim 1 or 2, where the cyano group is linked in meta- or para-position to the remainder of formula (1), (1a), (1b) or (1c).

4. An organic light-emitting device according to one or more of Claims 1 to 3, where the host material of formula (1) is selected from one or more of compounds E1 to E30:P24-208 Sc- 160 -5152025P24-208 Sc- 161 -5152025P24-208 Sc- 162 -515205. An organic light-emitting device according to one or more of Claims 1 to 4 where the host material of formula (3) corresponds to one of the formulae (3a) to (3e),formula (3b);P24-208 Sc- 163 -where Ars, R6, s and u have a meaning according to claim 1.

6. An organic light-emitting device according to one or more of Claims 1 to 3, where the host material 2 is selected from one or more of compounds H1 to H45:2535P24-208 Sc- 164 -515 20 2535P24-208 Sc- 165 -515 20 2535P24-208 Sc- 166 -515 20 2535P24-208 Sc- 167 -515 20 2535P24-208 Sc- 168 -515207. Organic light-emitting device device according to one or more of Claims 1 to 6, characterized in that it is an electroluminescent device selected from organic lightemitting transistors (OLETs), organic field quench devices (OFQDs), organic light25 emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

8. Organic light-emitting device according to one or more of Claims 1 to 7, characterized in that this organic layer comprises, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron transport layer (ETL), an electron injection layer (EIL) and / or a hole blocker layer (HBL) and / or an exciton blocking layer and / or charge generation layers.

9. Organic light-emitting device according to one or more of Claims 1 to 8,35characterized in that the light-emitting layer, as well as the at least one host material 1 and the at least one host material 2, comprises at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters having thermally activated delayed fluorescence.P24-208 Sc- 169 -10. Organic light-emitting device according to one or more of Claims 1 to 9, characterized in that the light-emitting layer, as well as the at least one host material 1 and the at least one host material 2, contains at least one phosphorescent emitter.

511. Organic light-emitting device according to one or more of Claims 1 to 10, characterized in that the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL) and / or an electron blocking layer (EBL), the hole-injecting material and / or hole-transporting material and / or electron blocking material of which is a monoamine or diamine that does not contain a carbazole unit.

12. Process for producing an organic light-emitting device according to one or more of Claims 1 to 11, characterized in that the organic layer is applied by gas phase deposition or from solution.15 13. Mixture comprising at least one compound of the formula (1) and at least one compound of the formulae (2), (3) or (4) as host material 2,formula (3),P24-208 Sc- 170 -formula (4),where the symbols and indices used are as follows:Y stands for O or S;R at each instance is the same or different and is H or D;R# is the same or different at each instance and stands for D, F, phenyl or partially or fully deuterated phenyl;15 An , Ar2 at each instance are the same or different and are an aromatic ring system having 6 to 18 C atoms which may be substituted by one or more R# radicals or is a dibenzofurane or dibenzothiophene group where each group may be substituted by one or more R# radicals;R6at each instance is the same or different and is D, F, CN, a straight-chain 20 alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R7radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R7)2, C=O, NR7, O, S or 25 CONR7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and which may be partially or completely deuterated in each case; it is also possible here for two R6radicals together to form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system;Ars is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R7radicals;R7is the same or different at each instance and is D, F, Cl, Br, I, N(R8)2, CN, NO2, OR8, SR8, Si(R8)3, B(OR8)2, C(=O)R8, P(=O)(R8)2, S(=O)R8, S(=O)2R8, OSO2R8, a straight-chain alkyl group having 1 to 20 carbon atoms or an 35 alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R8radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R8)2, C=O, NR8, O, S or CONR8, or an aromatic or heteroaromatic ring systemP24-208 Sc- 171 -which has 5 to 40 ring atoms and which may be partially or completely deuterated in each case; at the same time, two or more R7radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;5 R8is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F;s is the same or different at each instance and is 0, 1 , 2, 3 or 4;t is the same or different at each instance and is 0, 1 , 2 or 3;u is the same or different at each instance and is 0, 1 or 2,with the proviso that at least one R6in formulae (2), (3) and (4) is D or at least one Ars is a deuterated substituent.15 14. Mixture according to Claim 13, characterized in that the mixture comprises at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters having thermally activated delayed fluorescence.20 15. Mixture according to Claim 13, characterized in that the mixture consists of a compound of the formula (1), one compound of the formula (2) or of the formula (3) or of the formula (4) and a third matrix material and all three host materials are different from each other.2535

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