New materials for organic electroluminescent devices

Abstract

The present invention relates to new compounds (materials) and to organic electronic devices such as OLEDs (organic light emitting diodes) that contain these compounds, for example as hole transport materials or hole injection materials. The invention also relates to mixtures containing these new compounds.

Description

[0001] New materials for organic electroluminescent devices

[0002] The present invention relates to novel compounds (materials) and organic electronic devices such as OLEDs (organic light-emitting diodes) containing these compounds, for example, as hole-transport and hole-injection materials. Furthermore, the present invention relates to mixtures containing these novel compounds.

[0003] The construction of organic electroluminescent devices (e.g., OLEDs or OLECs—organic light-emitting electrochemical cells), in which organic semiconductors are used as organic functional materials, is described, for example, in US Pat. Nos. 4,539,507, 5,151,629, EP 0676461, and WO 98 / 27136. In addition to fluorescent emitters, organometallic complexes that exhibit phosphorescence are increasingly being used as emitting materials (MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum mechanical reasons, up to four times the energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, there is still room for improvement, both for OLEDs exhibiting singlet emission and for OLEDs exhibiting triplet emission, particularly with regard to efficiency, operating voltage, and lifetime.

[0004] The properties of organic electroluminescent devices are not determined solely by the emitters used. The other materials used, such as host and matrix materials, hole-blocking materials, electron-transport materials, hole-transport materials, and electron or exciton-blocking materials, are also of particular importance. Improvements to these materials can lead to significant improvements in electroluminescent devices, for example, in terms of device lifetime, efficiency, and operating voltage.

[0005] In the prior art, triarylamine compounds such as spirobifluorenamines and fluorenamines are known as hole-transport and hole-injection materials in electronic devices. Compounds that can be used as hole-transport materials and that lead to significant improvements in the lifetime, efficiency, and operating voltage of organic electroluminescent devices are still being sought. These compounds should exhibit high temperature stability, high oxidation stability in solution, and high hole conductivity. High temperature stability is required so that the compounds can be evaporated undecomposed under high vacuum and so that a long lifetime of the organic electroluminescent devices can be achieved.High oxidation stability in solution facilitates the purification of the compounds and increases the storage stability of the compounds.

[0006] The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic, in particular an organic electroluminescent, device, and which, when used in this device, lead to good device properties, as well as to provide the corresponding organic electronic, in particular organic electroluminescent, device. In particular, the object of the present invention is to provide compounds which lead to a long lifetime, good efficiency, and low operating voltage in a phosphorescent or fluorescent, in particular phosphorescent, OLED. The properties of the hole-transport materials in particular have a significant influence on the lifetime and efficiency of the organic electronic, in particular organic electroluminescent, device.

[0007] In addition, the compounds should be as easy to process as possible, particularly exhibiting good solubility and film formation. For example, the compounds should exhibit increased oxidation stability and an improved glass transition temperature. Furthermore, the compounds should exhibit high thermal stability.

[0008] These tasks are solved by providing compounds according to formula (I):

[0009] where the symbols and indices have the following meaning:

[0010] L is, identically or differently at each occurrence, a single bond, or an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 2 can be substituted;

[0011] Ar is at each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 - 40 aromatic ring atoms, each substituted by one or more radicals R 3 can be substituted;

[0012] R, R 1 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, Si(R 4 )s, a straight-chain alkyl, alkoxy or thioalkoxy chain having 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy chain having 3 to 40 C atoms, an alkenyl or alkynyl chain having 2 to 40 C atoms, each of which is substituted by one or more radicals R 4 may be substituted, with one or more non-adjacent CH2 groups being substituted by C(R 4 )=C(R 4 ), Si(R 4 )2, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4may be replaced, and wherein one or more H atoms may be replaced by D, F, CI, Br or I, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted with one or more radicals R 4 may be substituted, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 4 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R 4 may be substituted; optionally two or more, preferably adjacent, radicals R, or two or more, preferably adjacent, radicals R 1 form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

[0013] R 2 , R 4is, identically or differently on each occurrence, H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; optionally two or more, preferably adjacent, radicals R 2 , or two or more, preferably adjacent R 4 form a mono- or polycyclic aliphatic ring system;

[0014] R 3is, on each occurrence, identically or differently, H, D, F, CN, -OH, -SH, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; optionally two or more, preferably adjacent, radicals R3 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; q, r, s and t are independently 3 or 4 and n, m, o and p are the same or different and are 0 or 1, with the proviso that at least one of the indices n, m, o or p is 1.

[0015] If one of the indices n, m, o or p is 1, this means that correspondingly one of the indices q, r, s or t is 13; if one of the indices n, m, o or p is 0, this means that correspondingly one of the indices q, r, s or t is 4.

[0016] The symbol “D” or “D-atom” stands for deuterium.

[0017] An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline.An aryl group with 6 to 30 C atoms is therefore preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, dibenzoanthracenyl, chrysenyl or perylenyl, whereby the attachment of the aryl group as a substituent is not restricted.

[0018] An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms in the ring system, wherein the ring system also comprises the aryl groups described above.

[0019] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0020] An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such asBiphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

[0021] An aromatic or heteroaromatic ring system with 5 - 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, 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,Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxa- zol, Isoxazol, 1 ,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3- Diazapyren, 1,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9, 10-Tetra- azaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1,2,3-Triazol, 1,2,4-Triazol, Benzo- triazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1 ,2,3- Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4- Triazin, 1 ,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0022] Furthermore, a straight-chain alkyl group having 1 to 40 C atoms, preferably 1 to 20 C atoms, more preferably 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 40 C atoms, preferably having 3 to 20 C atoms, more preferably having 3 to 10 C atoms, for example the radicals 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, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, 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-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-Diethyln-n-hexadec-1-yl-, 1,1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1- (n-Butyl)-cyclohex-l-yl-, 1-(n-hexyl)-cyclohex-1-yl-, 1-(n-octyl)-cyclohex-1-yl-, and 1-(n-decyl)-cyclohex-l-yl-. The term "cyclic alkyl group" includes a monocyclic, bicyclic, or polycyclic group.

[0023] A straight-chain alkyl group having 1-20 C atoms, preferably having 1-10 C atoms, or a branched alkyl group having 3-20 C atoms, preferably having 3-10 C atoms, in which one or more non-adjacent CFh groups can be replaced by O or S, and in which at least one H atom can be replaced by D, F or CN, is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.

[0024] For the purposes of the present invention, adjacent carbon atoms are carbon atoms that are directly linked to one another. Furthermore, "adjacent radicals" in the definition of radicals means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply accordingly, among other things, to the terms "adjacent groups" and "adjacent substituents."

[0025] The phrase "two or more residues can form a ring system" refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system. For the purposes of this description, it is understood, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0026] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme: The compounds of formula (I) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture according to the invention and to the organic electronic or electroluminescent device according to the invention.

[0027] In a preferred embodiment of the present invention, one of the indices n, m, o or p is 1 and the other indices are 0, wherein the compound is a compound according to one of the formulas (Ha), (Hb), (Hc), (Hd), (IIIa), (IIIb), (IIIe) or (II Id), wherein the enantiomeric forms are also included here:

[0028] Formula (llc) Formula (lld)

[0029]

[0030] Formula (III) Formula (II Id) where L, Ar, R and R 1 have the meaning given above, and wherein in the formulas (Ila) to (I Id) r is 3 and q, s and 14, in the formulas (IIIa) to (II Id) r is 13 and q, r and s are 4.

[0031] According to yet another embodiment of the present invention, L is selected from the group consisting of a single bond, an aromatic ring system having 6 to 25 aromatic ring atoms or a heteroaromatic ring system having 5 to 25 aromatic ring atoms, each of which is substituted by one or more radicals R 2may be substituted. More preferably, L is selected from the group consisting of a single bond, an aromatic ring system with 6 to 18 aromatic ring atoms, more preferably 6 to 12 aromatic ring atoms, or a heteroaromatic ring system with 5 to 18 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted. When L represents an aromatic or heteroaromatic ring system, it is preferably selected from the following formulas (L-1) to (L-82):

[0032] (L-1) to (L-82) can each be substituted with one or more radicals R 2 be substituted. The dashed line indicates the bond to N or the benzene ring, respectively. In (L-76) to (L-78), (L-80), and (L-82), a D atom is replaced by the dashed line. The residue R 2is preferably, identically or differently on each occurrence, H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 10 C atoms, more preferably 1 to 6 C atoms, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, preferably 5 to 18 C atoms, in which one or more H atoms may be replaced by D, F or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; optionally two or more, preferably adjacent, radicals R 2 form a mono- or polycyclic aliphatic ring system.

[0033] In the context of the present invention, it is further preferred that Ar is, identically or differently, an aromatic ring system having 6 to 25 aromatic ring atoms or a heteroaromatic ring system having 5 - 25 aromatic ring atoms, each of which is substituted by one or more radicals R 3 can be substituted.

[0034] More preferably, Ar can be selected, the same or different, from (Ar-1) to (Ar-276), where (Ar-1) to (Ar-282) are substituted with one or more radicals R 3 can be substituted and the dashed line indicates the connection to N: At Ar-257 to Ar-259, Ar-261 and Ar-263, one D atom is replaced by the dashed line.

[0035] Very particularly preferably, Ar is selected, identically or differently at each occurrence, from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran, dibenzothiophene or carbazole, which are each substituted with one or more radicals R 3 can be substituted.

[0036] The rest R3 is preferably, identically or differently on each occurrence, H, D, F, CN, -OH, -SH, an aliphatic hydrocarbon radical having 1 to 10 C atoms, more preferably having 1 to 6 C atoms, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, in which one or more H atoms may be replaced by D, F or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; optionally two or more, preferably adjacent, radicals R 3 form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

[0037] According to yet another preferred embodiment of the present invention, the radical R 1at each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl chain having 1 to 20 C atoms, a branched or cyclic alkyl chain having 3 to 20 C atoms, in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 4 may be substituted. More preferred is the radical R 1at each occurrence, identically or differently, H, D, a straight-chain alkyl chain having 1 to 10 C atoms, more preferably having 1 to 6 C atoms, a branched or cyclic alkyl chain having 3 to 10 C atoms, more preferably having 3 to 6 C atoms, in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, particularly preferably having 5 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R 4 may be substituted. Examples of suitable compounds according to the invention according to formula (I) are listed below in Table 1.

[0038] Table 1 :

[0039]

[0040] The compounds of the invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any other substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge.

[0041] Scheme 1

[0042] Scheme 3 where R and Ar are as defined above and X represents a reactive leaving group, such as Cl. Example a) Spirosynthesis:

[0043] [

[0044] 24.08 g (90 mmol) of bromide is placed in 300 mL of THF at -78 °C. At this temperature, 40 mL of BuLi (2M in hexane) are added dropwise. After 1 hour, 16.9 g (94 mmol) of ketone in 200 mL of THF are added dropwise. The mixture is left to stir overnight at room temperature, poured onto ice-water, and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, and the residue, without further purification, is heated under reflux at 100 °C overnight with 94 mL of HCl and 1074 mL of AcOH. After cooling, the precipitated solid is filtered off with suction, washed once with 100 mL of water, three times with 100 mL of ethanol, and finally recrystallized from heptane. Yield: xx g (57 mmol), 84%; Purity approx. 98% after 1 H-NMR.

[0045] The following compounds can also be synthesized analogously:

[0046]

[0047] 52 g (130 mmol; 1.00 eq.) spirochloride, 41.7 g (130 mmol; 1.00 eq.) / V-[1,T-biphenyl]-4-yl[1,1'-biphenyl]-4-amine and 15.9 g (144 mmol; 1.10 eq.) sodium terpentoxide [CAS 14593-46-5] are placed in 2000 mL toluene and inertized for 30 minutes in an argon stream. Subsequently, 1.62 mg (3.94 mmol; 3 mol%) of dicyclohexyl-(2',6'-dimethoxy-biphenyl-2-yl)-phosphane (SPhos) and 886 mg (3.94 mmol; 3 mol%) of palladium acetate [3375-31-3] were added and the mixture was heated to reflux for 18 hours. After complete conversion and cooling to room temperature, water was added to the reaction mixture. After separation of the phases and extraction of the aqueous phase with toluene [CAS 108-88-3], the combined organic phases were concentrated and treated with heptane. The precipitated solid was isolated. Purification by Soxhlet extraction, recrystallization, and vacuum sublimation yielded the desired product (55 g; 81 mmol; 63% of theory).

[0048] Analogously, we obtain:

[0049]

[0050] Example c) Boronic acid

[0051] A solution of 109 g (270 mmol) of compound (a) in 1500 ml of diethyl ether, cooled to -78 °C, is treated dropwise with 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at -78 °C for 30 min. The mixture is allowed to warm to room temperature, cooled again to -78 °C, and then quickly treated with a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether. After warming to -10 °C, the mixture is hydrolyzed with 135 ml of 2 N hydrochloric acid. The organic phase is separated, washed with water, dried over sodium sulfate, and evaporated to dryness. The residue is taken up in 300 ml of n-heptane, and the colorless solid is filtered off with suction, washed with n-heptane, and dried in vacuo.

[0052] Yield: 96 g (232 mmol), 86% of theory; purity: 96% by HPLC.

[0053] 26 g (63 mmol) of compound (c), 32.4 g (63 mmol), / V-[1,T-biphenyl]-4-yl- / V-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine, 21.1 g (94 mmol) of potassium phosphate monohydrate, and 1.6 g (1.9 mmol) of XPhos Palladacylce Gen.3 are dissolved in 60 ml of THF / water (4:1) and stirred at 60°C for 16 hours. The reaction mixture is then concentrated on a rotary evaporator, and the residue is dissolved in dichloromethane. The organic phase is washed twice with water, and the aqueous phases are extracted twice with dichloromethane. The organic phases are combined, dried over sodium sulfate, filtered, and concentrated to dryness on a rotary evaporator. The residue is extracted several times over hot aluminum oxide (toluene / heptane 1:1) and crystallized to an HPLC purity of >99.9%. Finally, the product is sublimated (10 -6 bar, 325 °C) as a solid.

[0054] Yield: 35 g (46 mmol), 74% of theory; purity: 98% by HPLC.

[0055] The following connections can be made in an analogous manner:

[0056]

[0057]

[0058] In a flask, 23 g (30.4 mmol) of compound (b) benzene-D6 (120 ml) and trifluoromethanesulfonic acid (19 ml, 212 mmol) were added, stirred at 60 °C for 4 hours, then 600 ml of distilled water and NaHCO3 were added dropwise. The organic layer was then extracted with MgSO4. The water was removed preparatively. The concentrated organic layer was purified by passing it through silica gel. Finally, the product was obtained after sublimation (10 -6 bar) as a solid.

[0059] Yield: 22 g (27 mmol, 92%) with a purity of > 99.9%.

[0060] Analogously, the following connection can be established:

[0061] 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.

[0062] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0063] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A 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, whereby the fully deuterated solvent is not limited here. 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 reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0064] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,Methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these solvents.

[0065] The present invention therefore also relates to mixtures comprising at least one compound of formula (I), in particular of formulas (II) and (III), and at least one further material and / or at least one solvent, in particular an organic solvent. Further materials that can be used include, for example, further hole-transport materials, emitters, matrix materials, or p-dopants—as explained in more detail below.

[0066] The present invention further provides an organic electronic device comprising an anode, a cathode, and at least one organic layer containing at least one compound of formula (I), in particular at least one compound of Table 1, or a mixture according to the invention. The at least one organic layer may comprise at least one electron-blocking layer, hole-injecting layer, or hole-transporting layer.

[0067] Preferably, the organic electronic device is an organic electroluminescent device.

[0068] The organic electroluminescent device according to the invention (synonymously with organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEG, LEEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is in particular an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0069] The organic layer of the device according to the invention preferably contains, in addition to a light-emitting layer (EML), a hole-injection layer (HIL), a hole-transport layer (HTL), a hole-blocking layer (HBL), an electron-transport layer (ETL), an electron-injection layer (EIL), an exciton-blocking layer, an electron-blocking layer, and / or charge-generation layers. The device according to the invention can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Interlayers, which, for example, have an exciton-blocking function, can also be introduced between two emitting layers.

[0070] A hole-injection layer is understood to be a layer that directly borders the anode. A hole-transport layer is understood to be a layer that is present between the anode and the emitting layer, but not directly bordering the anode, and preferably not directly bordering the emitting layer either. An electron-blocking layer is understood to be a layer that is present between the anode and the emitting layer and directly bordering the emitting layer. An electron-blocking layer preferably has a high-energy LUMO and thus prevents electrons from escaping from the emitting layer.

[0071] In addition to the cathode, anode, and emitting layer, the electronic device may contain further layers. These may be selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers, and / or organic or inorganic p / n junctions. It should be noted, however, that not all of these layers are necessarily present, and the choice of layers always depends on the compounds used and, in particular, on whether the electroluminescent device is fluorescent or phosphorescent.

[0072] The sequence of layers of the electronic device is preferably as follows: -Anode-

[0073] -Hole injection layer- -Hole transport layer- -Optional additional hole transport layers- -Emitting layer-

[0074] -optional hole blocking layer-

[0075] -Electron transport layer- -Electron injection layer- -Cathode-,

[0076] It should be pointed out again that not all of the above-mentioned

[0077] Layers must be present, and / or that additional layers

[0078] The present invention further provides for the use of the compounds according to formula (I), in particular Table 1, or the mixture comprising compounds according to formula (I) in an organic electronic device, preferably an organic electroluminescent device. Preferably, the compounds mentioned or the formulation are used in an electron-blocking, hole-injecting, or hole-transporting layer.

[0079] If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e. different emitting compounds which can fluoresce or phosphoresce are used in the emitting layers. A plurality of fluorescent and / or phosphorescent compounds can also be present in one emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0080] It is preferred that the compound of formula (I) is used as a hole-transport material and / or as a hole-injection material. The emitting layer may be a fluorescent emitting layer or a phosphorescent emitting layer. Preferably, the emitting layer is a blue phosphorescent or green phosphorescent layer. If the device comprising the compound of formula (I), in particular of formula (II) and (III), contains a phosphorescent emitting layer, it is preferred that this layer contains two or more, preferably exactly two, different matrix materials (mixed matrix system). Preferred embodiments of mixed matrix systems are described in more detail below.

[0081] If the compound according to formula (I), in particular formula (II) and (III) is used as a hole transport material in a hole transport layer, a hole injection layer or an electron blocking layer, the compound can be used as a pure material, ie in a proportion of 100%, for example in the hole transport layer, or it can be used in combination with one or more other compounds.

[0082] According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I), in particular of formula (II) and (III), additionally contains one or more further hole-transporting compounds. These further hole-transporting compounds are preferably selected from triarylamine compounds, particularly preferably from mono-triarylamine compounds. They are very particularly preferably selected from the preferred embodiments of hole-transport materials specified further below. In the preferred embodiment described, the compound of formula (I) and the one or more further hole-transporting compounds are preferably each present in a proportion of at least 10%, particularly preferably each present in a proportion of at least 20%.

[0083] According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I), in particular of formula (II) and (III), additionally contains one or more p-dopants. According to the present invention, p-dopants preferably used are those organic electron acceptor compounds that can oxidize one or more of the other compounds in the mixture.

[0084] Quinodimethane compounds are particularly preferred as p-dopants,

[0085] Azaindenofluorenediones, azaphenalenes, azatriphenylenes, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a bonding site. Also preferred are transition metal oxides as dopants, preferably oxides of rhenium, molybdenum, and tungsten, particularly preferably Re2O7, MoO3, WO3, and ReO5.

[0086] Even more preferred are complexes of bismuth in the oxidation state (III), in particular bismuth(III) complexes with electron-poor ligands, in particular carboxylate ligands.

[0087] The p-dopants are preferably distributed largely evenly throughout the p-doped layers. This can be achieved, for example, by co-evaporating the p-dopant and the hole-transport material matrix. The p-dopant is preferably present in a proportion of 1 to 10% in the p-doped layer.

[0088] Furthermore, preferred p-dopants are the compounds explicitly shown on pages 86 - 87 of the published patent application WO2021 / 156323A1.

[0089] According to a preferred embodiment, the device contains a hole-injection layer that corresponds to one of the following embodiments: a) it contains a triarylamine and a p-dopant; or b) it contains a single electron-deficient material (electron acceptor). According to a preferred embodiment of embodiment a), the triarylamine is a mono-triarylamine, in particular one of the preferred triarylamine derivatives mentioned below. According to a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative, as described in US 2007 / 0092755.

[0090] The compound of formula (I), in particular of formula (II) and (III), can be present in a hole-injection layer, in a hole-transport layer, and / or in an electron-blocking layer of the device. If the compound is present in a hole-injection layer or in a hole-transport layer, it is preferably p-doped, i.e., it is present in the layer mixed with a p-dopant, as described above. The compound of formula (I), in particular of formula (II) and (III), is preferably present in an electron-blocking layer. In this case, it is preferably not p-doped. Furthermore, in this case, it is preferably present as a single compound in the layer, without the admixture of any further compound.

[0091] According to an alternative preferred embodiment, the compound of formula (I), in particular of formula (II) and (III), is used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds. The phosphorescent emitting compounds are preferably selected from blue phosphorescent and green phosphorescent compounds.

[0092] In this case, the proportion of the matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.% and particularly preferably between 85.0 and 97.0 vol.%.

[0093] Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.% and particularly preferably between 3.0 and 15.0 vol.%.

[0094] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple emitting compounds. In this case, too, the emitting compounds are generally those compounds whose proportion is the smaller in the system, and the matrix materials are those compounds whose proportion is the larger in the system. In individual cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single emitting compound.

[0095] It is preferred that the compounds of formula (I) are used as a component of mixed-matrix systems, preferably for phosphorescent emitters. The mixed-matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. It is further preferred if one of the materials is selected from compounds with a large energy difference between HOMO and LUMO (wide-bandgap materials). In a mixed-matrix system, the compound of formula (I) preferably represents the matrix material with hole-transporting properties.Accordingly, when the compound of formula (I) is used as a matrix material for a phosphorescent emitter in the emitting layer of an OLED, a second matrix compound having electron-transporting properties is present in the emitting layer. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, and most preferably 1:4 to 1:1.

[0096] According to a preferred embodiment, in the case of mixed-matrix systems, the two or more matrix materials contained in the mixed-matrix system, at least one of which preferably corresponds to one of the formulas (I), are used as a mixture and applied by evaporation.

[0097] However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components can also be combined mainly or completely in a single mixed-matrix component, with the other mixed-matrix component(s) fulfilling other functions.

[0098] The following material classes are preferably used in the above-mentioned layers of the device:

[0099] Phosphorescent emitters:

[0100] The term phosphorescent emitters typically encompasses compounds in which light emission occurs through a spin-forbidden transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state. Particularly suitable as phosphorescent emitters are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium, platinum, or copper.

[0101] For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0102] Examples of suitable phosphorescent emitters are listed in Table 2 below:

[0103] Table 2:

[0104]

[0105] Fluorescent emitters:

[0106] Preferred fluorescent-emitting compounds are selected from the class of arylamines. An arylamine or an aromatic amine within the meaning of this invention is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines and diamines, benzoindenofluorenamines and diamines, and dibenzoindenofluorenamines and diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives bonded to furan units or thiophene units. Matrix materials for fluorescent emitters:.

[0107] Preferred matrix materials for fluorescent emitters are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene), in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes, polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, in particular ketones, phosphine oxides, and sulfoxides; atropisomers, boronic acid derivatives, or benzanthracenes. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds.An oligoarylene in the sense of this invention is to be understood as a compound in which at least three aryl or arylene groups are bonded to one another.

[0108] Matrix materials for phosphorescent emitters:

[0109] Preferred matrix materials for phosphorescent emitters, in addition to the compounds of formula (I), are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g., CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0110] Electron-transporting materials:

[0111] Suitable electron-transporting materials are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials as used in these layers according to the prior art.

[0112] All materials that are used as electron-transport materials in the electron-transport layer according to the state of the art can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example, Alq3; zirconium complexes, for example, Zrq4; lithium complexes, for example, Liq; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0113] Preferred electron transport and electron injection materials are still the compounds explicitly shown on pages 73-75 of W02020 / 109434A1.

[0114] Hole transporting materials:

[0115] Further compounds which, in addition to the compounds of the formula (I) according to the invention, in particular of the formulas (II) and (III), are preferably used in hole-transporting layers of the OLEDs according to the invention, are indenofluorenamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with condensed aromatics, monobenzoindenofluorenamines, dibenzoindenofluorenamines, spirobifluorene amines, fluorene amines, spiro-dibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrene diarylamines, spiro-tribenzotropolones, spirobifluorenes with meta-phenyldiamine groups, spiro-bisacridines, xanthene diarylamines, and 9,10-dihydroanthracene spiro compounds with diarylamino groups. Preferred hole-transporting compounds are still the compounds explicitly shown on pages 76-80 of W02020 / 109434A1.

[0116] Particularly suitable for use in layers with hole-transporting

[0117] Function of any OLEDs, not only the OLEDs according to the definitions of the present application, are the following compounds HT-1 to HT-18:

[0118] Compounds HT-1 to HT-18 are generally suitable for use in hole-transporting layers. Their use is not limited to specific OLEDs, such as those described in the present application.

[0119] Compounds HT-1 to HT-18 can be prepared according to the methods disclosed in the patent applications cited in parentheses in the above table in connection with the compounds. The further teaching regarding the use and preparation of the compounds disclosed in these patent applications is hereby explicitly incorporated and should preferably be combined with the above-mentioned teaching regarding the use of the above-mentioned compound as a hole-transporting material. The compounds exhibit excellent properties when used in OLEDs, in particular excellent lifetime and efficiency.

[0120] Metals with a low work function, metal alloys, or multilayer structures made of different metals are preferred as the cathode of the electronic device, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can be used, such as Ag or Al, in which case combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0121] Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0122] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 -7 mbar.

[0123] Also preferred is an electronic device characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) process or by means of carrier gas sublimation. The materials are deposited at a pressure between 10 -5mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0124] Also preferred is an electronic device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble compounds according to formula (I), in particular formulas (II) or (III), are required for this purpose. High solubility can be achieved by suitable substitution of the compounds.

[0125] It is further preferred that, to produce an electronic device according to the invention, one or more layers are applied from solution and one or more layers are applied by a sublimation process. Device Examples

[0126] 1) General manufacturing process for OLEDs and characterization of OLEDs

[0127] Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm form the substrates on which the OLEDs are applied.

[0128] OLEDs generally have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / hole blocking layer (HBL) / electron transport layer, optionally with a second layer (ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs is shown below.

[0129] All materials are thermally evaporated in a vacuum chamber. The emission layer consists of at least one matrix material (host material) and an emissive dopant (dopant, emitter), which is mixed with the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as TMM-1:TMM-2:TEG (32%:60%:8%) means that the TMM-1 material is present in the layer at a volume fraction of 32%, TMM-2 at a volume fraction of 60%, and TEG at a volume fraction of 8%. Similarly, the electron transport layer and the hole injection layer also consist of a mixture of two materials. The structures of the materials used in the OLED are shown in Table 5.

[0130] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of luminance, calculated from current-voltage-luminance curves assuming a Lambertian radiation pattern, and the lifetime are determined. The EQE @ 10 mA / cm 2 refers to the external quantum efficiency, which at 10mA / cm 2 is reached. The specification U @ 10 mA / cm 2 refers to the operating voltage at 10 mA / cm 2 The lifetime LT is defined as the time after which the luminance drops from the initial luminance to a certain level when operating at a constant current density. A value of LT90 means that the specified lifetime corresponds to the time after which the luminance has dropped to 90% of its initial value. The value @80 mA / cm 2 means that the lifetime in question is 80 mA / cm 2 is measured.

[0131] 1) Use in the EBL of green-phosphorescent OLEDs

[0132] OLEDs are manufactured with the following structure:

[0133] Example 1 containing the compound HT-B according to the invention shows a significantly improved voltage and better lifetime with similar efficiency than the comparative example C1, which contains the comparative compound HT-A. 2) Use in HIL and HTL of blue-phosphorescent OLEDs

[0134] OLEDs are manufactured with the following structure:

[0135] Example 2 containing the compound HT-B according to the invention shows both improved efficiency and voltage as well as improved lifetime than Comparative Example C2 containing the comparative compound HT-A.

Claims

Patent claims 1. Compound according to formula (I) Formula (I) where the symbols and indices have the following meaning: L is, identically or differently at each occurrence, a single bond, or an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 2 can be substituted; Ar is at each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 - 40 aromatic ring atoms, each substituted by one or more radicals R 3 can be substituted; R, R 1 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, Si(R 4)3, a straight-chain alkyl, alkoxy or thioalkoxy chain with 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy or Thioalkoxy chain with 3 to 40 C atoms, an alkenyl or alkynyl chain with 2 to 40 C atoms, each with one or more radicals R 4 may be substituted, with one or more non-adjacent CH2 groups being substituted by C(R 4 )=C(R 4 ), Si(R 4 )2, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4 may be replaced, and wherein one or more H atoms may be replaced by D, F, CI, Br or I, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted with one or more radicals R 4 may be substituted, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 4may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R 4 may be substituted; optionally two or more, preferably adjacent, radicals R, or two or more, preferably adjacent, radicals R 1 form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R 2 , R 4 is, on each occurrence, identically or differently, H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; optionally two or more, preferably adjacent, radicals R 2, or two or more, preferably adjacent R 4 form a mono- or polycyclic aliphatic ring system; R 3 is, at each occurrence, identically or differently, H, D, F, CN, -OH, -SH, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; optionally two or more, preferably adjacent, radicals R3 can form a mono- or polycyclic, aliphatic ring system; q, r, s and t are independently 3 or 4 and n, m, o and p are the same or different and are 0 or 1, with the proviso that at least one of the indices n, m, o or p is 1.

2. A compound according to claim 1, wherein one of the indices n, m, o or p is 1 and the other indices are 0, and wherein the compound is a compound according to one of the formulas (IIa), (IIIb), (IIe), (IId), (IIIa), (IIIb), (IIIe) or (IIld): where L, Ar, R and R 1 have the meaning given in claim 1, and wherein in the formulas (IIa) to (II Id) r is 3 and q, s and 14 and in the formulas (IIIa) to (II Id) r is 13 and q, r and s are 3.

3. A compound according to claim 1 or 2, wherein L is a single bond, an aromatic ring system having 6 to 25 aromatic ring atoms or a heteroaromatic ring system having 5 to 25 aromatic ring atoms, each of which is substituted by one or more radicals R 2 can be substituted.

4. A compound according to one or more of claims 1 to 3, wherein Ar is the same or different and is an aromatic ring system having 6 to 25 aromatic ring atoms or a heteroaromatic ring system having 5 to 25 aromatic ring atoms, each of which is substituted by one or more radicals R 3 can be substituted.

5. A compound according to claim 4, wherein Ar on each occurrence is, identically or differently, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorene, spirobifluorene, spiroxanthene, dibenzofuran, dibenzothiophene or carbazole, each of which is substituted with one or more radicals R 3 can be substituted.

6. A compound according to one or more of claims 1 to 5, wherein R 1at each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl chain having 1 to 20 C atoms, a branched or cyclic alkyl chain having 3 to 20 C atoms, in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 4 can be substituted.

7. A mixture comprising at least one compound according to one or more of claims 1 to 6 and at least one further material and / or at least one solvent.

8. An organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound according to one or more of claims 1 to 6 or a mixture according to claim 7.

9. Organic electronic device according to claim 8, wherein the one organic layer comprises at least one electron-blocking layer, hole-injecting or hole-transporting layer which contains at least one compound according to one or more of claims 1 to 6 or a mixture according to claim 7.

10. An organic electronic device according to claim 8 or 9, wherein the device is an organic electroluminescent device.

11. The organic electronic device according to claim 10, which is an electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

12. Use of a compound according to one or more of claims 1 to 6 or of a mixture according to claim 7 in an organic electronic device.

13. Use of a compound according to claim 12, wherein the organic electronic device is an organic electroluminescent device.

14. Use of a compound according to claim 13, wherein the organic electroluminescent device comprises at least one electron-blocking layer, hole-injecting layer or hole-transporting layer.

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