Organic electronic device

Abstract

The present application relates to an organic electronic device, in particular an organic electroluminescence device, which comprises an organic layer comprising at least one first compound of the formula (1) or (1A) and at least one second compound of the formula (2A), (2B), (2C), (2D), (2E) or (2F), and to a mixture or formulation comprising a first compound of the formula (1) or (1A) and a second compound of the formula (2A), (2B), (2C), (2D), (2E) or (2F), wherein the compounds of the formula (1) and (1A) are spirocarbazole-triazine derivatives.

Description

Technical Field

[0001] The present invention relates to an organic electronic device, particularly an organic electroluminescent device, the organic electronic device comprising an organic layer comprising at least one first compound of formula (1) or formula (1A) and at least one second compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), and a mixture or formulation comprising the first compound of formula (1) or formula (1A) and the second compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), wherein the compounds of formula (1) and formula (1A) are spirocarbazole-triazine derivatives. Background Technology

[0002] The structures of organic electronic devices, including electroluminescent devices (such as OLEDs—organic light-emitting diodes or OLECs—organic light-emitting electrochemical cells), are well-known, using organic semiconductors as functional materials. In addition to fluorescent emitters, the luminescent materials used here are increasingly organometallic complexes that exhibit phosphorescence rather than fluorescence. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can achieve up to four times improvements in energy efficiency and power efficiency. However, overall, OLEDs, especially those exhibiting triplet emission (phosphorescence), still require improvement, for example, in terms of efficiency, operating voltage, and lifetime. Device performance depends not only on the triplet emitter used. More specifically, other materials used, such as the matrix material, are also particularly important. Therefore, improvements to these materials can also lead to significant improvements in OLED performance.

[0003] The host materials used in organic electronic devices are well known to those skilled in the art. When referring to host materials used in phosphorescent emitters, the term "matrix material" is frequently used in the prior art. This usage of the term also applies to this invention. Currently, various host materials have been developed for both fluorescent and phosphorescent electronic devices.

[0004] Another way to improve the performance data of electronic devices, especially organic electroluminescent devices, is to use a combination of two or more materials, particularly a combination of host or matrix materials.

[0005] WO 2014 / 094963 A1 describes specific undeuterated spirocarbazole-triazine derivatives and their suitability for organic electronic devices.

[0006] These materials, especially when used as matrix materials, generally still require improvement. Therefore, one object of the present invention is to provide a matrix material suitable for use in organic electronic devices, particularly in fluorescent or phosphorescent OLEDs, which results in good device performance, especially in improving device lifetime, and to provide corresponding electronic devices. This is especially true when used in combination with low to moderate emitter concentrations, i.e., 3% to 20%, preferably 3% to 15%, more preferably 4% to 10%, and most preferably 4% to 8%, as device lifetime is particularly limited in these cases.

[0007] It has been found that electronic devices containing compounds of formula (1) or formula (1A) and compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F) have improvements over the prior art, especially when the compounds are used as matrix materials for phosphorescent dopants.

[0008] It has also been discovered that in the light-emitting layer of organic electronic devices, especially organic electroluminescent devices, this objective is achieved and the drawbacks of the prior art are eliminated by combining at least one compound of formula (1) or formula (1A) as a first host material and at least one compound of formula (2A), (2B), (2C), (2D), (2E), or (2F) as a second host material. Using this material combination to manufacture the light-emitting layer in organic electronic devices results in devices with excellent performance, particularly in terms of lifetime, and especially at equal or improved operating voltages and comparable efficiencies. Summary of the Invention

[0009] The present invention first provides an organic electronic device comprising an anode, a cathode, and at least one organic layer, wherein the organic layer comprises at least one compound of formula (1) or formula (1A) and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E), or formula (2F).

[0010] The symbols and markings used are as follows: Y is the same or different in each case and is CR. 1 Or N, provided that at least one Y group is N; X is the same or different in every case and is CR. 1 Or N; or two adjacent X's are S, O, or NR. 1 Thus forming a five-membered ring; or two adjacent X groups are groups of the following formula (2), formula (3) or formula (4),

[0011] Where ^ represents the corresponding adjacent X group in formula (1) or formula (1A); V is the same or different in each case and is C(R) 1 2. NR 1 O, S, BR 1 Si(R) 1 )2 or C=O; Z is the same or different in each case and is CR. 1 Or N; Ar may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R may be the same or different in each case and is selected from: H, D, F, Cl, Br, I, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 The atoms are either C≡C or O, and one or more of the hydrogen atoms may be replaced by D or F, or the atom has 6 to 60 aromatic ring atoms and may be replaced by one or more R atoms. 2 Aromatic ring systems with substituted groups; here, two adjacent substituents R can also form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be substituted by one or more R groups. 2 Group substitution; R 1 In each case, they may be the same or different and are selected from: H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 2 )2,C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3,Si(R 2 3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR2 C≡C, Si(R) 2 2. C=O, C=S, C=NR 2 P(=O)(R) 2 SO, SO2, NR 2 O, S or CONR 2 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and each of the aromatic or heteroaromatic ring systems may be replaced by one or more R atoms. 2 Group substitution, having 5 to 60 aromatic ring atoms and being substituted by one or more R groups 2 A group-substituted aryloxy or heteroaryloxy group; here, two adjacent R groups 1 The substituents may optionally form monocyclic or polycyclic aliphatic, aromatic, or heterocyclic ring systems, which may be formed by one or more R groups. 2 Group substitution; Ar 1 In each case, the same or different, and for those having 5 to 30 aromatic ring atoms and being capable of being separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; here, two Ar atoms bonded to the same nitrogen or phosphorus atom. 1 The group can also be formed by a single bond or by means of N(R) 2 ), C(R 2 2. Bridge bases of O or S are connected to each other; R 2 In each case, the same or different and selected from: H, D, F, CN, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein two or more adjacent R 2 Substituents can together form monocyclic or polycyclic aliphatic ring systems; m and n are the same or different in each case and are 0 or 1, provided that m+n≥1; p is the same or different in each case and is 0, 1, 2, 3 or 4; q is 0, 1, or 2; Equation (2A) Equation (2B) Equation (2C) Equation (2D) Equation (2E) Equation (2F) The symbols and markings used are as follows: A 1 For C(R) 7 2. NR 7 , O or S; L represents bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (2D-1) or formula (2D-2) in each case.

[0012] X2 is the same or different in each case and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the position connected to equation (2D); U 1 U 2 When it appears, it is a key, O, S, C(R). 7 )2 or NR 7 ; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 5 to 60 ring atoms and in each case can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 The groups can also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring systems together; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8)2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being able to be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; here, two or more R groups are substituted. 7 The groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8 In each case, the same or different and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; c, c1, and c2 are independently 0 or 1 in each case, and the sum of the labels is c + c1 + c2 = 1 in each case; d, d1, and d2 are independently 0 or 1 in each case, and the sum of the labels is d + d1 + d2 = 1 in each case; q, q1, and q2 are independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1 or 2; u1 and u2 are independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

[0013] The present invention also provides a method for producing organic electronic devices, preferably electroluminescent devices, as described above or preferably described below, wherein an organic layer is applied by vapor deposition or from a solution.

[0014] The present invention also provides a mixture comprising at least one compound of formula (1) or formula (1A) as described above or preferred later, and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F) as described above or preferred later, and optionally having other compounds, and / or a solvent, said other compounds being selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0015] The corresponding preferred embodiments described below also form part of the subject matter of this invention. Surprising and advantageous effects are achieved through a specific selection of compounds of formula (1) or formula (1A) and compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F). Detailed Implementation

[0016] In this patent application, "D" or "D atom" refers to deuterium. The degree of deuteration, expressed as mol%, refers to the proportion of hydrogen atoms replaced by deuterium. Since deuterated compounds are typically mixtures of compounds differing in the exact positions and proportions of deuterium atoms, the degree of deuteration refers to the average proportion of hydrogen atoms replaced by deuterium. Therefore, a degree of deuteration of 50 mol% means that an average of 50 mol% of hydrogen atoms in the compound are replaced by deuterium; thus, it is the average degree of deuteration.

[0017] The organic electronic devices of the present invention are preferably selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic electroluminescent devices, organic solar cells (OSC), organic optical detectors, and organic photosensors.

[0018] More preferably, the organic electronic device of the present invention is an organic electroluminescent device.

[0019] The organic electroluminescent device of the present invention, or the equivalent organic electroluminescent device or organic light-emitting device, is, for example, an organic light-emitting transistor (OLET), an organic field quenching device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device of the present invention is particularly an organic light-emitting diode or an organic light-emitting electrochemical cell. More preferably, the device of the present invention is an OLED.

[0020] In one embodiment of the present invention, the organic layer of the organic electronic device of the present invention comprises a light-emitting layer, the light-emitting layer containing at least one compound of formula (1) or formula (1A) as described above or preferably described below, and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F).

[0021] In addition to the light-emitting layer (EML), the organic layer of the device of the present invention preferably also includes 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 a charge generation layer. The light-emitting layer comprises a material combination of at least one compound of formula (1) or formula (1A) as described above or below, and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E), or formula (2F). The device of the present invention may also include two or more layers selected from this group, preferably layers selected from EML, HIL, HTL, ETL, EIL, and HBL. Similarly, an intermediate layer, for example, having an exciton blocking function, may be introduced between two light-emitting layers.

[0022] If multiple emitting layers are present, these emitting layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in overall white emission; in other words, multiple luminescent or phosphorescent compounds are used in the emitting layers. Two or more fluorescent and / or phosphorescent compounds may also be present in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. As an alternative to the combination described above, the emitting layers may also exhibit yellow emission. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially for white emitting OLEDs.

[0023] The device may also include inorganic materials or layers formed entirely of inorganic materials.

[0024] Preferably, the luminescent layer comprising at least one compound of formula (1) or formula (1A) and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F) comprises at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0025] Particularly preferred is a phosphorescent layer comprising a compound of at least one of formula (1) or formula (1A) and at least one of formulas (2A), (2B), (2C), (2D), (2E), or (2F). The phosphorescent layer is characterized in that, in addition to comprising a host material combination of a compound of formula (1) or formula (1A) as described above and a compound of formula (2A), (2B), (2C), (2D), (2E), or (2F), the phosphorescent layer also comprises at least one phosphorescent emitter. Suitable emitter selection and preferred emitters are described below.

[0026] In the context of this invention, aryl groups contain 6 to 40 ring atoms, preferably carbon atoms. Heteroaryl groups in the context of this invention contain 5 to 40 ring atoms, wherein the ring atoms include carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O, and / or S. Here, aryl groups or heteroaryl groups refer to: simple aromatic rings, i.e., phenyl, derived from benzene; or simple heteroaryl rings, for example derived from pyridine, pyrimidine, or thiophene; or fused aryl or heteroaryl groups, for example derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Therefore, aryl groups having 6 to 18 carbon atoms are preferably phenyl, naphthyl, phenanthrene, or biphenylidene, and there is no limitation on the connection of aryl groups as substituents. In the context of this invention, aryl or heteroaryl groups may contain one or more groups, wherein suitable groups are described below. If such groups are not described, the aryl or heteroaryl group is unsubstituted.

[0027] In the context of this invention, aromatic ring systems contain 6 to 60 or 6 to 40 ring atoms, preferably carbon atoms. Aromatic ring systems also include aryl groups as described above.

[0028] The aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, biphenyl, naphthyl, phenanthryl and triphenylide.

[0029] In the context of this invention, heteroaromatic ring systems contain 5 to 40 ring atoms and at least one heteroatom. Preferred heteroaromatic ring systems have 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0030] In the context of this invention, aromatic or heteroaromatic ring systems refer to systems that do not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups may be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirodifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, piracene, etc., should thus also be considered aromatic or heteroaromatic ring systems in the context of this invention, as well as systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaromatic groups are directly linked to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also included in the definition of aromatic or heteroaromatic ring systems.

[0031] Aromatic or heteroaromatic ring systems having 5 to 40 or 6 to 60 ring atoms and being linked at any position via an aromatic or heteroaromatic system should be understood to refer to groups derived, for example, from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, leucine, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, terphenylidene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans monobenzo[a]indo[a]fluorene, cis or trans dibenzo[a]indo[a]fluorene, triphenyl ... Polyindene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiazole, phenanthreneimidazole, pyridiniumimidazole, quinoxaline Imidazole, thiazolium, benzo[a]azole, naphtho[a]azole, anthraxazole, phenanthro[a]azole, isothiazolium, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3 - Triazole, 1,2,4-triazole, benzotriazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0032] The electron-rich heteroaryl ring system is characterized by containing at least one electron-rich heteroaryl group, and is particularly preferred to have no electron-deficient heteroaryl groups.

[0033] Electron-deficient heteroaryl groups are six-membered heteroaryl groups having at least one nitrogen atom or five-membered heteroaryl groups having at least two heteroatoms, one of which is a nitrogen atom and the other is an oxygen, sulfur, or substituted nitrogen atom, wherein in each case other aryl or heteroaryl groups may also be fused to these groups. On the other hand, electron-rich heteroaryl groups are five-membered heteroaryl groups having only one heteroatom selected from oxygen, sulfur, and substituted nitrogen, which may be fused to other aryl groups and / or other electron-rich five-membered heteroaryl groups. Thus, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, or indocarbazole. Electron-rich heteroaryl groups are also called electron-rich heteroaromatic groups.

[0034] abbreviations Ar and Ar 1 In each case, they may be the same or different and represent having 5 to 40 ring atoms and can be represented by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 1 Group or R 1 Substituents are defined as described above or below.

[0035] In the context of this specification, the phrase "two or more groups together can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system" should specifically refer to the fact that the two groups are connected to each other by chemical bonds in the event of formal elimination of two hydrogen atoms. This is illustrated by the following scheme: .

[0036] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group bonds to the position where a hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme: .

[0037] In the context of this invention, cyclic alkyl groups should be understood to refer to monocyclic, bicyclic, or polycyclic groups.

[0038] In the context of this invention, C1 to C1 are straight-chain, branched, or cyclic. 20Alkyl groups should be understood to refer to groups such as: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4 ... 2-heptyl, 3-heptyl, 4-methylcyclopentyl, 2-methylpentyl, 2-heptyl, 3-heptyl, 4-methylcyclopentyl, 2-methylcyclopentyl, 2-heptyl, 2-heptyl, 3-heptyl, 4-methylcyclopentyl, 2-methylcyclopentyl, 2-heptyl, 2-heptyl, 3-heptyl, 4-methylcyclopentyl, 2-methylcyclopentyl, 2-heptyl, 2-heptyl, 4-methylcyclopentyl, 2-methylcyclopentyl, 2-heptyl, 2-heptyl, 2-heptyl, 4-methylcyclopentyl, 2-methylcyclopentyl, 2-heptyl, 2-heptyl, 2 -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-di Methyl-n-octyl-1-yl, 1,1-dimethyl-n-decyl-1-yl, 1,1-dimethyl-n-dodecyl-1-yl, 1,1-dimethyl-n-tetradecyl-1-yl, 1,1-dimethyl-n-hexadecyl-1-yl, 1,1-dimethyl-n-octadecyl-1-yl, 1,1-diethyl-n-hexyl-1-yl, 1,1-diethyl-n-heptyl-1-yl, 1,1-diethyl-n-octyl-1-yl, 1,1-diethyl-n-decyl -1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)-cyclohexyl-1-yl, 1-(n-butyl)-cyclohexyl-1-yl, 1-(n-hexyl)-cyclohexyl-1-yl, 1-(n-octyl)-cyclohexyl-1-yl and 1-(n-decyl)-cyclohexyl-1-yl.

[0039] The alkenyl group is an alkyl group containing at least one double bond as described above.

[0040] The alkynyl group is an alkyl group containing at least one triple bond, as described above.

[0041] In the context of this invention, phosphorescent emitters are compounds that exhibit luminescence from excited states with high spin multiplicity (i.e., spin > 1), particularly from excited triplet states. In the context of this application, all luminescent complexes containing transition metals or lanthanides are considered phosphorescent emitters. More precise definitions are given below.

[0042] When the host material of the luminescent layer comprising at least one compound of formula (1) or (1A) as described above or preferably described below, and at least one compound of formula (2A), (2B), (2C), (2D), (2E), or (2F) as described above or described below, is used in a phosphorescent emitter, it is preferable that its triplet energy is not significantly less than the triplet energy of the phosphorescent emitter. Regarding the triplet energy level, it is preferable that T1(emissor) - T1(matrix) ≤ 0.2 eV, more preferably ≤ 0.15 eV, and most preferably ≤ 0.1 eV. T1(matrix) here refers to the triplet energy level of the matrix material in the luminescent layer, and this condition applies to each of the two matrix materials, and T1(emissor) refers to the triplet energy level of the phosphorescent emitter. If the luminescent layer contains more than two matrix materials, the above relationship preferably also applies to each of the other matrix materials.

[0043] When the host material of the luminescent layer comprising at least one compound of formula (1) or (1A) as described above or preferably described below, and at least one compound of formula (2A), (2B), (2C), (2D), (2E), or (2F) as described above or preferably described below, is used in a phosphorescent emitter, the HOMO (highest occupied molecular orbital) energy (hereinafter abbreviated as hTMM-HOMO (calculated)) of the hole transport material of formula (2A), (2B), (2C), (2D), (2E), or (2F) as described above or preferably described below, calculated by the method described in the experimental section, satisfies the following conditions: The hTMM-HOMO (calculated) is ≥ -5.50 eV, preferably ≥ -5.37 eV, and more preferably ≥ -5.27 eV.

[0044] When the host material of the luminescent layer comprising at least one compound of formula (1) or (1A) as described above or preferably described below, and at least one compound of formula (2A), (2B), (2C), (2D), (2E) or (2F) as described above or preferably described below, is used in a phosphorescent emitter, the HOMO (highest occupied molecular orbital) energy hTMM-HOMO (calculated) of the hole transport material of formula (2A), (2B), (2C), (2D), (2E) or (2F) as described above or preferably described below, and the HOMO energy (hereinafter abbreviated as emitter-HOMO (calculated)) of the phosphorescent emitter as described below by the method described in the experimental section, satisfy the following conditions: The calculated HOMO of the luminescent material is ≤ 0.35 eV, preferably ≤ 0.23 eV, and more preferably ≤ 0.15 eV.

[0045] The compounds of formula (1) or formula (1A) and their preferred embodiments are described below. These preferred embodiments are also applicable to mixtures of the present invention, formulations of the present invention, and organic electronic devices or electroluminescent devices of the present invention.

[0046] In the first embodiment, the compounds of formula (1) and formula (1A) are deuterated compounds.

[0047] In a first preferred embodiment, the spirocarbazole basic framework has at least one deuterium atom. The spirocarbazole basic framework herein comprises a spirodifluorene group and a fused carbazole group, including a 6-membered ring formed by the X group. Therefore, at least one of the R groups of the spirodifluorene group and / or the R group of the 6-membered ring formed by the X group... 1 One of the groups is a deuterium atom.

[0048] In a second preferred embodiment, the aromatic or heteroaromatic ring system Ar and / or the R of a 6-membered ring formed by a Y group 1 At least one of the groups is a deuterium atom.

[0049] In a third preferred embodiment, at least one of the R groups of the spirodifluorene group and / or the R group of a 6-membered ring formed by the X group. 1 One of the groups is a deuterium atom, and the R is an aromatic or heteroaromatic ring system Ar and / or a 6-membered ring formed by a Y group. 1 At least one of the groups is a deuterium atom.

[0050] When the deuterated compound of formula (1) or formula (1A) contains at least one R 2 When the group is present, in addition to the three preferred embodiments described above, R 2 At least one of the groups may also be a deuterium atom.

[0051] In this embodiment, the degree of deuteration of the compound of formula (1) or formula (1A) is generally in the range of 1 mol% to 100 mol%, preferably in the range of 10 mol% to 100 mol%, more preferably in the range of 50 mol% to 95 mol%, and most preferably in the range of 70 mol% to 90 mol%.

[0052] In the second embodiment, the compounds of formula (1) and formula (1A) are undeuterated compounds.

[0053] Preferred embodiments of the compound of formula (1) are compounds of formulas (5) to (11), and preferred embodiments of the compound of formula (1A) are compounds of formula (12).

[0054] The symbols and notations used have the definitions given above. In these formulas, V is preferably NR. 1 C(R) 1 2. O or S. When V=C(R) 1 When )2, two R values ​​can be preferred. 1 The groups together form a ring, thereby forming a spirocyclic system.

[0055] In a preferred embodiment of the invention, p is the same or different in each case and is 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0056] It is also preferred that q is 0 or 1, and more preferably 0.

[0057] A particularly preferred embodiment of the structure of formulas (5) to (12) is the structure of formulas (5a) to (12a) below.

[0058] The symbols and markings used have the definitions given above.

[0059] In a preferred embodiment of the invention, R may be the same or different in each case and is selected from: H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a group having 6 to 30 aromatic ring atoms and being capable of being bonded by one or more non-aromatic R groups. 2 Aromatic ring systems with substituted substituents. In a particularly preferred embodiment of the invention, R may be the same or different in each case and is selected from: H, straight-chain alkyl groups having 1 to 4 carbon atoms, and branched or cyclic alkyl groups having 3 to 8 carbon atoms, especially H. When the compounds of the invention are used as monomers for the production of polymers, it is also preferable that both substituents R are Br or I and polymerization is carried out via these groups.

[0060] In another preferred embodiment of the invention, R 1 In each case, they may be the same or different and are selected from: H, D, F, Br, CN, N (Ar) 1 )2,C(=O)Ar 1 , P(=O)(Ar 1 )2, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, or an alkenyl or alkynyl group having 2 to 10 carbon atoms, each of which may be substituted by one or more R 2Group substitution, wherein one or more non-adjacent CH2 groups may be replaced by O, and one or more hydrogen atoms may be replaced by D or F, or having 5 to 30 aromatic ring atoms and in each case being replaced by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, R 1 In each case, they may be the same or different and are selected from: H, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 4 carbon atoms or a branched or cyclic alkyl group having 3 to 8 carbon atoms, each of which can be generated by one or more R 2 Group substitution, or having 5 to 18 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

[0061] When R is an aromatic ring system and / or when R 1 When it is a aromatic or hybrid aromatic cyclic system, R and / or R 1 Preferably, the same or different groups in each case and selected from the same groups as those specified below as suitable as Ar.

[0062] Meanwhile, in compounds processed by vacuum evaporation, the alkyl group preferably has no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, suitable compounds also include those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or those substituted with oligomeric aromatic groups, such as o-terphenyl, m-terphenyl, or p-terphenyl, or branched terphenyl, or tetraphenyl groups.

[0063] In one preferred embodiment of the invention, n=1 and m=0. In another preferred embodiment of the invention, n=0 and m=1. In yet another preferred embodiment of the invention, n=m=1.

[0064] The preferred group Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which can be generated by one or more R groups. 1Group substitution. Suitable groups Ar are selected from: benzene; o-biphenyl, m-biphenyl, or p-biphenyl; o-terphenyl, m-terphenyl, p-terphenyl, or branched terphenyl; o-tetraphenyl, m-tetraphenyl, p-tetraphenyl, or branched tetraphenyl; 1-fluorenyl, 2-fluorenyl, or 3-fluorenyl; 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl, or 4-spirodifluorenyl; 1-naphthyl or 2-naphthyl; pyrrole; furan; thiophene; indole; benzofuran; benzothiophene; 1-carbazole, 2-carbazole azoles or 3-carbazoles; 1-dibenzofuran, 2-dibenzofuran or 3-dibenzofuran; 1-dibenzothiophene, 2-dibenzothiophene or 3-dibenzothiophene; indoxacarbazole; indoloxacarbazole; 2-pyridine, 3-pyridine or 4-pyridine; 2-pyrimidine, 4-pyrimidine or 5-pyrimidine; pyrazine; pyridazine; triazine; anthracene; phenanthrene; biphenylene oxide; pyrene; benzanthracene; and combinations of two or three of these groups, each of which may be oxidized by one or more R... 1 Group substitution. More preferably, Ar is an aromatic ring system, particularly selected from: benzene; o-biphenyl, m-biphenyl, or p-biphenyl; o-terphenyl, m-terphenyl, p-terphenyl, or branched terphenyl; and o-tetraphenyl, m-tetraphenyl, p-tetraphenyl, or branched tetraphenyl. When another (Het-Ar) group is attached to the Ar group in more detail below, i.e., when n=m=1, the (Het-Ar) group can be attached to Ar at any position.

[0065] In a preferred embodiment of the invention, Ar is an aromatic ring system, meaning it does not contain any heteroaryl groups. This applies when n=1 and another (Het-Ar) group, as described below, is attached to Ar, as well as when n=0.

[0066] In another preferred embodiment of the invention, when Ar contains more than one aryl group, the aromatic groups in the Ar group are not para-linked, that is, the compound is preferably not para-biphenyl, para-terphenyl or para-tetraphenyl, but instead has, for example, a corresponding ortho- or meta-linked structure.

[0067] Preferably, Ar contains a carbazole, pyrrole, imidazole or benzimidazole group, which is connected to other aromatic units of Ar or to a nitrogen atom via a carbon atom rather than via a nitrogen atom.

[0068] When n=1, the compounds of the present invention contain heteroaryl groups of the following formula, which are abbreviated as (Het-Ar) below:

[0069] When n=1, this group is present in the compound of the present invention, and when m=1, it is connected to Ar, or when m=0, it is connected to nitrogen. In the (Het-Ar) group, at least one Y group, preferably no more than three Y groups, is N, and the other Y groups are CR. 1 .

[0070] Preferred embodiments use groups of formulas (Het-Ar-1) to (Het-Ar-10).

[0071] The dashed bond represents a bond connected to Ar or, when m=0, a bond connected to nitrogen, and the symbols used have the definitions given above.

[0072] Groups of formulas (Het-Ar-1a) to (Het-Ar-10b) are particularly preferred.

[0073] The dashed bond represents a bond connected to Ar or, when m=0, a bond connected to nitrogen, and the symbols used have the definitions given above.

[0074] When (Het-Ar) is a (Het-Ar-1) or (Het-Ar-1a) group, the two R groups in this group 1 The substituents are preferably those having 5 to 24 aromatic ring atoms and can be replaced by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups, especially phenyl; o-biphenyl, m-biphenyl, or p-biphenyl; o-terphenyl, m-terphenyl, p-terphenyl, or branched terphenyl; o-tetraphenyl, m-tetraphenyl, p-tetraphenyl, or branched tetraphenyl; 1-fluorene, 2-fluorene, 3-fluorene, or 4-fluorene; 1-spirobifluorene, 2-spirobifluorene, 3-spirobifluorene, or 4-spirobifluorene; 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran, or 4-dibenzofuran; or 1-carbazole, 2-carbazole, 3-carbazole, or 4-carbazole.

[0075] When (Het-Ar) is a (Het-Ar-2) to (Het-Ar-10) group or a (Het-Ar-2a) to (Het-Ar-10a) group, the R in these groups 1 Preferably, they are the same or different in each case and are H, D, or have 5 to 24 aromatic ring atoms and can be converted by one or more R atoms. 2 Aromatic or heteroaromatic ring systems substituted with groups, especially H, or phenyl, o-biphenyl, meta-biphenyl or para-biphenyl, o-terphenyl, meta-terphenyl, para-terphenyl or branched terphenyl, or o-tetraphenyl, meta-tetraphenyl, para-tetraphenyl or branched tetraphenyl.

[0076] The above-described preferred embodiments can be freely combined with each other. In a particularly preferred embodiment of the invention, the above-described preferences occur simultaneously.

[0077] When the compound of formula (1) or formula (1A) and in preferred embodiments are used as a matrix material for a phosphorescent emitter or in a layer directly adjacent to the phosphorescent layer, it is also preferred that the compound does not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused together. Particularly preferred groups are R, R... 1 R 2 Ar does not contain any fused aryl or heteroaryl groups in which two or more six-membered rings are directly fused together, and the two adjacent X groups are not groups of formula (2A), (2B), (2C), (2D), (2E) or (2F).

[0078] When the compound of formula (1) or formula (1A) is a deuterated compound, when preparing the compound, if the undeuterated compound of one of formulas (1) and (1A) is selected to be prepared by reacting with a deuterated source, or if a deuterated starting compound of a mixture of deuterated starting compounds is selected for preparation, a mixture of deuterated products having the same parent chemical structure but different only in degree of deuteration and / or deuteration mode can be formed.

[0079] In the context of this invention, the expression “at least one compound of formula (1) or formula (1A)” is considered to cover such a mixture of deuterated compounds having the same parent chemical structure of formula (1) or formula (1A) or the parent structure of preferred embodiments, differing only in degree of deuteration and / or deuteration mode.

[0080] In one embodiment of the present invention, (D) a (D) b (D) c (D) d and (D) e Indicates no substitution.

[0081] In one embodiment of the present invention, (D) a (D) b (D) c (D) d and (D) e This indicates the maximum substitution.

[0082] In a preferred embodiment of at least one compound of formula (1) or formula (1A) as described above or as preferably described, the average degree of deuteration is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, more preferably 70 mol% to 90 mol%.

[0083] The corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR 2016041014, WO2017 / 122988, KR 202005282, KR 101978651 and WO 2018 / 110887, 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.

[0084] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms 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 deuterium atoms that is capable of releasing them under suitable conditions.

[0085] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D₂O, benzene-d₆, chloroform-d, acetonitrile-d₃, acetone-d₆, acetic acid-d₄, methanol-d₄, or toluene-d₈. Preferred deuterium sources are D₂O or a combination of D₂O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D₂O and fully deuterated organic solvents, with no limitation on the fully deuterated solvent. Particularly suitable fully deuterated solvents are benzene-d₆ and toluene-d₈. Particularly preferred deuterium sources are combinations of D₂O and toluene-d₈. The reaction is preferably carried out under heating, more preferably at a temperature between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0086] According to the embodiments detailed above, examples of preferred compounds of formula (1) or formula (1A) are the compounds detailed in Table 1 below.

[0087] Table 1:

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] The particularly preferred compounds of formula (1) or formula (1A) are compounds E1 to E45 in Table 2 below: Table 2:

[0109]

[0110]

[0111]

[0112]

[0113] The compounds of the present invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullman coupling, Hartwig-Buchwald coupling, etc.

[0114] In the following synthetic schemes, the compounds exhibit a few substituents to simplify the structure. This does not preclude the presence of any other desired substituents during the process. The methods shown for synthesizing the compounds of this invention should be considered exemplary. Those skilled in the art will be able to develop alternative synthetic routes within the scope of common knowledge in the art.

[0115] The basic structure of the compound of the present invention can be prepared via the route outlined in Scheme 1. Functionalization can be achieved according to Scheme 2.

[0116] Option 1:

[0117] Option 2: .

[0118] Synthesis typically begins with 4-bromospirobisfluorene as known in the literature (Organic Letters 2009, 11(12), 2607-2610) or with correspondingly substituted 4-bromospirobisfluorene. This is similar to the reaction of ortho-haloaminobenzenes in a CN coupling reaction, for example, under Pd or Cu catalysis, wherein the halogen is preferably Cl, Br, or I. In a completely similar manner, for example, naphthalene, fluorene, dibenzofuran, or dibenzothiophene derivatives can be used to obtain compounds containing groups of formula (2) or (3). Ring closure is achieved by intramolecular Pd-catalyzed coupling to obtain the corresponding carbazole derivatives.

[0119] The compound of formula (1A) can be synthesized in a completely similar manner from 4,4'-dibromospirodifluorene, which is known in the literature.

[0120] The compound of formula (1) with n=0 and m=1 is obtained by coupling reaction with a suitably functionalized aromatic or heteroaromatic compound, such as Hartwig-Buchwald coupling or Ullmann coupling, wherein the reactive group is preferably Cl, Br or I.

[0121] Compounds of formula (1) with n=1 and m=0 are obtained by nucleophilic aromatic substitution reactions or by Pd-catalyzed coupling reactions with (Het-Ar) groups substituted with appropriate leaving groups, especially Cl or Br.

[0122] The compound of formula (1) with n=1 and m=1 is obtained by coupling with a bifunctionalized aromatic or heteroaromatic compound, such as Hartwig-Buchwald coupling or Ullman coupling, wherein the reactive groups are preferably bromine and iodine groups; subsequently, optionally after converting the halogen group to a boric acid derivative, a Pd-catalyzed coupling reaction is carried out, such as Suzuki coupling, Negishi coupling, Yamamoto coupling, Grinner cross coupling or Stieler coupling.

[0123] The present invention also provides a method for preparing compounds of formula (1) or formula (1A), the method comprising the following reaction steps: a) The basic skeleton of compound (1) or compound (1A), wherein the basic skeleton does not yet contain (Het-Ar) and / or Ar groups; and b) To make the basic framework from a) react in CC couplings such as Suzuki coupling, Negishi coupling, Yamamoto coupling, Griner cross coupling or Stieler coupling, or CN couplings such as Buchwald coupling or Ullman coupling.

[0124] Detailed reaction conditions are known from the prior art or described in the Examples section.

[0125] These methods, followed by purification if necessary, such as recrystallization or sublimation, can yield high purity, preferably exceeding 99% (via...). 1 Compounds of formula (1) or formula (1A) as determined by ¹H NMR and / or HPLC.

[0126] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms 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 deuterium atoms that is capable of releasing them under suitable conditions.

[0127] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D₂O, benzene-d₆, chloroform-d, acetonitrile-d₃, acetone-d₆, acetic acid-d₄, methanol-d₄, or toluene-d₈. Preferred deuterium sources are D₂O or a combination of D₂O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D₂O and fully deuterated organic solvents, with no limitation on the fully deuterated solvent. Particularly suitable fully deuterated solvents are benzene-d₆ and toluene-d₈. Particularly preferred deuterium sources are combinations of D₂O and toluene-d₈. The reaction is preferably carried out under heating, more preferably at a temperature between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0128] The following describes compounds (body material 2) of formulas (2A), (2B), (2C), (2D), (2E), and (2F) present in the devices of the present invention, and their preferred embodiments. Preferred embodiments of body materials 2 of formulas (2A), (2B), (2C), (2D), (2E), and (2F) are also applicable to mixtures and / or formulations of the present invention.

[0129] In the first preferred embodiment, the compounds of formulas (2A), (2B), (2C), (2D), (2E), and (2F) are deuterated compounds, i.e., R 6 R 7 and / or R8 At least one of the groups is a deuterium atom.

[0130] In this embodiment, the degree of deuteration of the compounds of formulas (2A), (2B), (2C), (2D), (2E) and (2F) is generally in the range of 1 mol% to 100 mol%, preferably in the range of 10 mol% to 100 mol%, more preferably in the range of 50 mol% to 95 mol%, and most preferably in the range of 70 mol% to 90 mol%.

[0131] In the second preferred embodiment, the compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) and formula (2F) are undeuterated compounds.

[0132] The compounds of formulas (2A), (2B), (2C), (2D), (2E), and (2F) have the following structures: Equation (2A), Equation (2B), Equation (2C), Equation (2D), Equation (2E), Equation (2F), The symbols and markings used are as follows: A 1 For C(R) 7 2. NR 7 , O or S; L represents bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (2D-1) or formula (2D-2) in each case.

[0133] X2 is the same or different in each case and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the position connected to equation (2D); U 1 U 2 When it appears, it is a key, O, S, C(R). 7 )2 or NR 7 ; R 6In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 5 to 60 ring atoms and in each case can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 The groups can also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring systems together; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being able to be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; here, two or more R groups are substituted. 7 The groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8In each case, the same or different and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; c, c1, and c2 are independently 0 or 1 in each case, and the sum of the labels is c + c1 + c2 = 1 in each case; d, d1, and d2 are independently 0 or 1 in each case, and the sum of the labels is d + d1 + d2 = 1 in each case; q, q1, and q2 are independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1 or 2; u1 and u2 are independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

[0134] Compounds of formula (2A) and formula (2E) are particularly preferred here.

[0135] The preferred compound of formula (2D) is the compound of formula (2D-A). Formula (2D-A), Where X2 is independently CH or CR in each case. 6 And Ar5, R 6 q, q1, q2 and v have the definitions given above or preferably given above.

[0136] The preferred compounds of formula (2E) are those of formulas (2E-1) to (2E-5). Equation (2E-1), Equation (2E-2), Equation (2E-3), Equation (2E-4), Equation (2E-5), Among them, Ar5, R 6 , s and u have the definitions given above or preferably given above.

[0137] In compounds of formula (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5), or (2F), when R 6 When the group is not D, s is preferably 0 or 1, or more preferably 0.

[0138] In compounds of formula (2A), (2B), or (2C), when R 6 When the group is not D, t is preferably 0 or 1, or more preferably 0.

[0139] In compounds of formula (2A), (2B), (2C), (2E), (2E-1), (2E-2), (2E-3), (2E-4), or (2E-5), when R 6 When the group is not D, u is preferably 0 or 1, or more preferably 0.

[0140] In compounds of formulas (2A), (2B), (2C), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5), or (2F), the sum of the designations s, t, and u preferably does not exceed 6, particularly preferably does not exceed 4, and more preferably does not exceed 2. When R 6 This is the preferred case when it is not D.

[0141] In the compounds of formula (2D) and formula (2D-A), c, c1, and c2 are independently 0 or 1 in each case, and the sum of the labels is c + c1 + c2 = 1 in each case. c2 is preferably defined as 1.

[0142] In compounds of formula (2D) and formula (2D-A), L is preferably a single bond or C(R) bond. 7 )2, where R 7 It has the definition given above; more preferably, L is a single bond.

[0143] In equation (2D-1), when R 6 When the group is not D, v is preferably 0 or 1.

[0144] In equation (2D-2), U 1 or U 2 When present, it is preferably a single bond or C(R) bond. 7 )2, where R 7 It has the definition given above; more preferably, U 1 or U 2 It appears as a single key.

[0145] In equation (2D-2), when R 6When the group is not D, q, q1, and q2 are preferably 0 or 1.

[0146] In a preferred embodiment of compounds of formulas (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5), and (2F) that can be combined with compounds of formula (1) or (1A) as described above or preferred compounds of formula (1) or (1A), R 6 In each case, the same or different and selected from: 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, wherein the alkyl group in each case may be one or more R 7 Group substitution, or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and in each case being substituted with one or more R groups. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0147] In a preferred embodiment of compounds of formulas (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5), and (2F) that can be combined with compounds of formula (1) or (1A) as described above or preferred compounds of formula (1) or (1A), R 6 In each case, they may be the same or different and are selected from: D, or have 6 to 30 ring atoms and can be selected from one or more R. 7 Aromatic or heteroaromatic ring systems with substituted groups.

[0148] Preferably, Ar5 in the compounds of formulas (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5), and (2F) is selected from phenyl, biphenyl (especially ortho-biphenyl, meta-biphenyl, or para-biphenyl), terphenyl (especially ortho-terphenyl, meta-terphenyl, or para-terphenyl, or branched terphenyl), tetraphenyl (especially ortho-tetraphenyl, meta-tetraphenyl, or para-tetraphenyl or branched tetraphenyl), The following groups may be connected via a fluorene group at positions 1, 2, 3, or 4; a spirodifluorene group at positions 1, 2, 3, or 4; a naphthyl group (especially a naphthyl group at position 1 or 2); or a group derived from indole, benzofuran, benzothiophene, or carbazole at positions 1, 2, 3, or 4; a dibenzofuran group at positions 1, 2, 3, or 4; a dibenzothiophene group at positions 1, 2, 3, or 4; an indobenzocarbazole group; an indolecarbazole group; a pyridine group; a pyrazine group; a pyridazine group; a triazine group; a quinoline group; an isoquinoline group; a quinazoline group; a quinoxaline group; a phenanthrene group; or a triphenylene group, each of which may be associated with one or more R groups. 7 Group substitution. Ar5 is preferably unsubstituted.

[0149] When A in equation (2B), equation (2C), or equation (2F) 1 For NR 7 At that time, R connected to the nitrogen atom 7 The substituents are preferably composed of 5 to 24 aromatic ring atoms and may also be replaced by one or more R atoms. 8 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, the R... 7 The substituents may be the same or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, especially 6 to 18 aromatic ring atoms. R 7 The preferred embodiment is preferably an unsubstituted phenyl, biphenyl, terphenyl, and tetraphenyl, as well as a phenyl that can be substituted by one or more R 8 The substituents are derived from triazine, pyrimidine, and quinazoline groups.

[0150] When A in equation (2B), equation (2C), or equation (2F) 1 For C(R) 7 At )2, R bonded to this carbon atom 7 The substituents are preferably the same or different in each case and are straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, or having 5 to 24 aromatic ring atoms and may also be replaced by one or more R... 8 Aromatic or heteroaromatic ring systems with substituted groups. Most preferably, R 7 It is a methyl group or a phenyl group. In this case, R7 Groups can also form ring systems together, thereby producing spirocyclic systems.

[0151] In a preferred embodiment of the compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2D-A), formula (2E), formula (2E-1), formula (2E-2), formula (2E-3), formula (2E-4), formula (2E-5) and formula (2F), these compounds are partially or completely deuterated, more preferably completely deuterated.

[0152] The preparation of compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2D-A), formula (2E), formula (2E-1), formula (2E-2), formula (2E-3), formula (2E-4), formula (2E-5) and formula (2F) is generally known, and some of the compounds are commercially available.

[0153] Compounds of formula (2D) and formula (2D-A) are disclosed, for example, on pages 110 to 119 of WO 2021 / 180614 A1, and particularly as examples on pages 120 to 127. Their preparation is disclosed in synthetic examples on page 128 and on pages 214 to 218 of WO 2021 / 180614 A1.

[0154] The preparation of triarylamines of formula (2F) is known to those skilled in the art, and some compounds are commercially available.

[0155] If at least one other matrix material is a deuterated compound, then that at least one other matrix material may be a mixture of deuterated compounds with the same chemical basic structure but different degrees of deuteration. The descriptions relating to the production of deuterated mixtures and deuterated materials as described above for compounds of formula (1) or (1A) may also be adapted to this purpose with necessary modifications.

[0156] In a preferred embodiment of at least one other matrix material, it is a mixture of deuterated compounds of formula (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5) and / or (2F) as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably at least 70% to 100%.

[0157] Examples of suitable other matrix materials for combination with compounds of formula (1) or formula (1A) as described above or preferably described are the compounds described in Table 3 on pages 137-203 of WO 2019 / 229011 A1, which may also be partially or completely deuterated.

[0158] Examples of suitable other matrix materials for use in combination with compounds of formula (1) or (1A) as described above or preferred are the compounds described in Table 3 on pages 131 to 137 and Table 4 on pages 137 to 139 of WO 2021 / 180625 A1, which may also be partially or completely deuterated.

[0159] Examples of suitable other matrix materials for use in combination with compounds of formula (1) or (1A) as described above or preferred are compounds of formula (1) or (1A) as described above or preferred. Examples of other matrix materials are compounds described in KR 2023 / 0034896 A, compounds [2-1] to [2-110] on pages 42 to 47 or compounds [3-1] to [3-26] on pages 49 to 51.

[0160] For combinations with compounds of formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or preferably, particularly suitable compounds are compounds of formulas (2A), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), and / or (2E-5) as described above or preferably.

[0161] For combinations with compounds of formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or preferably, the compounds of formula (2A) are particularly suitable, wherein at least one Ar5 group is having 5 to 40 ring atoms and can be converted by one or more R 7 Group-substituted heteroaromatic ring systems, and / or compounds of formula (2D) or formula (2D-A), and / or compounds of formula (2E), formula (2E-1), formula (2E-2), formula (2E-3), formula (2E-4) or formula (2E-5).

[0162] For combinations with compounds of formulas (5), (6), (7), (8), (9), (10), (11), and (12) as described above or preferred, the most preferred compounds are those of formulas (2D) and (2D-A) or (2E), (2E-1), (2E-2), (2E-3), (2E-4), and (2E-5).

[0163] Other examples of preferred host materials of formulas (2A), (2B), (2C), (2D), (2D-A), (2E), (2E-1), (2E-2), (2E-3), (2E-4), (2E-5) and (2F) used in combination with compounds of formula (1) or (1A) as described above or more preferably are the structures in Tables 3 and 4 given below.

[0164] Table 3:

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] In Table 3 above, n represents the number of deuterium atoms in the corresponding compound and is either 0 or D1 to D2. 最大 Preferably, D1 to D 最大 When n=0, this means the compound has not been deuterated. n=D1 means that one hydrogen atom in the corresponding compound has been replaced by a deuterium atom. 最大 It is the maximum number of deuterium atoms that can exist in the corresponding compound. Maximum number D最大 It can vary depending on the compound. Depending on the compound, D 最大 The following values ​​can be used here: 20, 24, 26, 28, 30, 31, 32, 34, 35, 36, 37, 38 and 40.

[0182] The compounds of particularly preferred formulas (2A), (2B), (2C), (2D), (2E) and (2F) selected according to the present invention and preferably used in combination with at least one compound of formula (1) or formula (1A) in the electroluminescent device of the present invention are the compounds listed in Table 4 below.

[0183] Table 4:

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] In the device of the present invention, the host material of formula (1) or formula (1A) and its preferred embodiments or compounds E1 to E45 of Table 1 and Table 2 can be freely combined with the host material, the host material of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) and / or formula (2F) and its embodiments of Table 3 or compounds H1 to H56 of Table 4.

[0193] For the devices of the present invention, a mixture of a compound of formula (1) or formula (1A) with a host material of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) and / or formula (2F) is particularly preferred, obtained by combining compounds E1 to E45 with compounds H1 to H56, as shown in Table 5 below. For example, the first mixture M1 is a combination of compounds E1 and H1.

[0194] Table 5:

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] In the mixture of the present invention or in the light-emitting layer of the device of the present invention, the concentration of the main material 1 of formula (1) or formula (1A) as described above or preferably as described above is generally in the range of 5 wt% to 90 wt%, preferably in the range of 10 wt% to 85 wt%, more preferably in the range of 20 wt% to 85 wt%, even more preferably in the range of 30 wt% to 80 wt%, very particularly preferably in the range of 20 wt% to 60 wt%, and most preferably in the range of 30 wt% to 50 wt%.

[0208] In the mixture of the present invention or in the organic layer or light-emitting layer of the device of the present invention, the concentration of the main material 2 of formula (2A), (2B), (2C), (2D), (2E) or (2F) as described above or preferably, is in the range of 10 wt% to 95 wt% based on the total mixture or the total composition of the organic layer or light-emitting layer, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0209] The present invention also relates to a mixture, which, in addition to containing the aforementioned main material 1 and main material 2 corresponding to formula (1) or formula (1A) and formula (2A), (2B), (2C), (2D), (2E) and (2F) respectively, particularly mixtures M1 to M1728, also contains at least one other compound and / or solvent.

[0210] The present invention also relates to a mixture comprising, in addition to the aforementioned main material 1 and main material 2 corresponding to formula (1) or formula (1A) and formula (2A), (2B), (2C), (2D), (2E) and (2F) as described above or preferably, particularly mixtures M1 to M1728, at least one other compound selected from the following materials: matrix material, phosphorescent emitter, fluorescent emitter and / or emitter exhibiting TADF (thermally activated delayed fluorescence).

[0211] For processing the mixtures of the present invention by liquid phase, for example by spin coating or printing, a formulation of the mixtures of the present invention is required. These formulations may be, for example, solutions, dispersions, or emulsions. The solvent used may preferably be a mixture of two or more solvents. Suitable and preferred solvents include, for example: toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol Cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenethyl ether, 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, 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.

[0212] When the mixture of the compound of formula (1) or formula (1A) as described above with the compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F) of the present invention is used as a matrix material or a synonymous host material in the luminescent layer, it is preferred to use it in combination with other compounds, for example, in combination with other matrix materials, as a combination of three host materials.

[0213] In the light-emitting layer of the device of the present invention, the total concentration of all the main materials is generally in the range of 10 wt% to 95 wt% based on the overall composition of the light-emitting layer, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0214] Suitable matrix materials and light emitters that can be used in the mixtures or organic layers of the present invention are described below.

[0215] Those skilled in the art will readily consider the various materials known in the prior art to select suitable materials for the aforementioned layers in organic electroluminescent devices. Here, those skilled in the art will reflect the chemical and physical properties of the materials in a conventional manner, as they know that materials in organic electroluminescent devices interact with each other. This involves, for example, orbital energy levels (HOMO, LUMO) or other triplet and singlet energy levels, as well as other material properties.

[0216] Suitable matrix materials that can be used in combination with the compounds of this invention include: aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, bicarbazoles, indoloxacarbazole derivatives, indoxacarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridged carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. Other phosphorescent emitters with shorter emission wavelengths than the actual emitters can also exist as co-hosts in the mixture, or compounds that do not participate in charge transport to a significant extent, such as wide-bandgap compounds.

[0217] In this document, wide bandgap material refers to the material disclosed in US 7,294,849, characterized by a bandgap of at least 3.5 eV, where bandgap refers to the gap between the HOMO and LUMO energy levels of the material.

[0218] The present invention also relates to a mixture, which, in addition to containing the main material of the above-described or preferably described formula (1) or formula (1A) and formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), particularly mixtures M1 to M1728, also contains at least one phosphorescent luminescent material.

[0219] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the light-emitting layer comprises, in addition to the host material of the above formula (1) or formula (1A) and formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), particularly material combinations M1 to M1728, at least one phosphorescent material.

[0220] The term "phosphorescent luminescent material" generally encompasses compounds that emit light through spin-forbidden transitions from excited states with higher spin multiplicity, i.e., spin states > 1, such as compounds that emit light through transitions from triplet states or states with higher spin quantum numbers, such as quintet states. This preferably refers to transitions from triplet states.

[0221] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds that emit light when properly excited, preferably in the visible light region; and that also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially containing a metal having such an atomic number. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, particularly compounds containing iridium or platinum. In the context of this invention, all luminescent compounds containing the metals mentioned above are considered phosphorescent emitters.

[0222] Generally, any phosphorescent complex known to those skilled in the art for use in phosphorescent OLEDs and organic electroluminescent devices is suitable.

[0223] The preferred phosphorescent emitters according to the present invention conform to formula (I), formula (II), formula (III), formula (IV) or formula (V). Formula (I)

[0224] Equation (II)

[0225] Equation (III)

[0226] Formula (IV)

[0227] Formula (V)

[0228] The symbols used for these equations (I), (II), (III), (IV), and (V) are defined as follows: R1 is either H or D. R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms that may be partially or fully substituted with deuterium.

[0229] According to the present invention, the preferred phosphorescent emitter conforms to formula (VI), formula (VII) or formula (VIII). Formula (VI)

[0230] Equation (VII)

[0231] Formula (VIII)

[0232] The symbols used in these equations (VI), (VII), and (VIII) are defined as follows: R1 is either H or D. R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms that may be partially or fully substituted with deuterium.

[0233] According to the preferred phosphorescent emitter formula (IX) of the present invention, Formula (IX) The symbols and notations used in this equation (IX) are defined as follows: When n+m is 3, n is 1 or 2, and m is 2 or 1. X is the same or different in each case and is N or CR. R may be the same or different in each case and is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 7 carbon atoms, which may be partially or completely substituted with deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may be partially or completely substituted with deuterium.

[0234] Therefore, the present invention also provides an organic electroluminescent device as described above or as preferably described, characterized in that the light-emitting layer, in addition to comprising the host material 1 and the host material 2, also comprises at least one phosphorescent material conforming to formula (IX) as described above.

[0235] In the light emitter of formula (IX), n is preferably 1, and m is preferably 2.

[0236] In the luminescent body of formula (IX), preferably one X is selected from N and the other X is CR, or all X are the same or different in each case and are CR.

[0237] In the light emitter of formula (IX), at least one R is preferably different from H. In the light emitter of formula (IX), preferably two Rs are different from H and have one of the other definitions given above for the light emitter of formula (IX).

[0238] Preferred examples of phosphorescent luminescent materials are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO 2019 / 007867 A1. These luminescent materials are incorporated herein by reference.

[0239] Table 6 below lists particularly preferred examples of phosphorescent luminescent materials.

[0240] Table 6:

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] In the mixtures of the present invention or in the light-emitting layer of the device of the present invention, it is preferable to combine any mixture selected from the sum of mixtures M1 to M1728 with compounds of formulas (I) to (IX) or compounds from Table 6.

[0247] The light-emitting layer of the organic electroluminescent device of the present invention, which contains at least one phosphorescent light-emitting element, is preferably an infrared light-emitting layer, or a yellow, orange, red, green, or blue light-emitting layer, or an ultraviolet light-emitting layer, more preferably a yellow or green light-emitting layer, and most preferably a green light-emitting layer.

[0248] Here, a yellow emitting layer refers to a layer with a photoluminescence peak value in the range of 540 nm to 570 nm. An orange emitting layer refers to a layer with a photoluminescence peak value in the range of 570 nm to 600 nm. A red emitting layer refers to a layer with a photoluminescence peak value in the range of 600 nm to 750 nm. A green emitting layer refers to a layer with a photoluminescence peak value in the range of 490 nm to 540 nm. A blue emitting layer refers to a layer with a photoluminescence peak value in the range of 440 nm to 490 nm. Here, the photoluminescence peak value of the layer is determined by measuring the photoluminescence spectrum of a layer with a thickness of 50 nm at room temperature, wherein the layer comprises: the present invention combination of a host material 1 of formula (1) or formula (1A) and a host material 2 composed of at least one of formulas (2A), (2B), (2C), (2D), (2E) and (2F), and a corresponding emitting body.

[0249] The photoluminescence spectrum of the layer is recorded, for example, using a commercial photoluminescence spectrometer.

[0250] Typically at room temperature, 10 -5 The photoluminescence spectrum of the selected luminescent material is measured in a molar amount of oxygen-free solution. A suitable solvent is any solvent in which the selected luminescent material is dissolved at the mentioned concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, but dichloromethane may also be used. The spectra are measured using a commercial photoluminescence spectrometer. The triplet energy T1, in eV, is determined from the photoluminescence spectrum of the luminescent material. First, the peak value Plmax (in nm) of the photoluminescence spectrum is determined. Then, the peak value Plmax (in nm) is converted to eV using: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / PLmax (in nm).

[0251] Therefore, the preferred phosphorescent emitter is a yellow phosphorescent emitter, preferably those of formulas (I) to (IX) or those from Table 6, with a triplet energy T1 preferably of about 2.3 eV to about 2.1 eV.

[0252] Therefore, the preferred phosphorescent emitter is a green phosphorescent emitter, preferably those of formulas (I) to (IX) or those from Table 6, with a triplet energy T1 preferably of about 2.5 eV to about 2.3 eV.

[0253] Therefore, the particularly preferred phosphorescent emitter is a green phosphorescent emitter, preferably those of formulas (I) to (IX) as described above or those from Table 6, with a triplet energy T1 preferably of about 2.5 eV to about 2.3 eV.

[0254] Phosphorescent emitters that satisfy the energy level conditions specified above and are selected as the hTMM of formula (2) are preferred, especially those of formulas (I) to (IX) as described above or those from Table 6: The calculated HOMO of the luminescent material is ≤0.35 eV, preferably ≤0.23 eV, and more preferably ≤0.15 eV.

[0255] The fluorescent light emitter may also be present in the light-emitting layer of the device of the present invention or in the mixture of the present invention.

[0256] Preferred fluorescent compounds are selected from arylamines, wherein 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. Preferred examples of these compounds are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. An aromatic anthraceneamine is a compound in which a diaryl amino group is directly bonded to an anthracene group, preferably directly bonded at the 9 position. An aromatic anthracene diamine is a compound in which two diaryl amino groups are directly bonded to an anthracene group, preferably directly bonded at the 9th or 10th position. Aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are similarly defined, wherein the diaryl amino groups are preferably bonded to pyrene at the 1st or 1,6th position. Other preferred luminescent compounds are indene-fluoreneamine or indene-fluorene diamine, benzo[a]indene-fluoreneamine or benzo[a]indene-fluorene diamine, and dibenzo[a]indene-fluoreneamine or dibenzo[a]indene-fluorene diamine, as well as indene-fluorene derivatives having fused aryl groups. Pyrene arylamines are also preferred. Benzo[a]indene-fluoreneamine, benzo[a]fluoreneamine, extended benzo[a]indene, phenazine, and fluorene derivatives linked to furan or thiophene units are also preferred. The luminescent devices or mixtures of the present invention may further comprise materials exhibiting TADF (thermally activated delayed fluorescence).

[0257] In another preferred embodiment of the invention, at least one light-emitting layer of the organic electroluminescent device may have three or four different matrix materials, preferably three different matrix materials. These corresponding hybrid matrix systems may consist of the matrix materials described in host material 1 and host material 2, but in addition to host material 1 or host material 2, they may also include, for example, a wide-bandgap material, a bipolar host material, an electron transport material (ETM), or a hole transport material (HTM) as a third or fourth matrix material.

[0258] Preferably, the mixed matrix system is optimized for a light emitter of one of formulas (I) to (IX) or for a light emitter from Table 6.

[0259] In one embodiment of the invention, the mixture contains no other components, i.e., functional materials, besides the host material of formula (1) or formula (1A) as described above or preferably, and the host material of formulas (2A), (2B), (2C), (2D), (2E), or (2F). These are material mixtures used as is for the manufacture of the light-emitting layer. These mixtures, also called premixed systems, are the sole material source used as the host material for the light-emitting layer in vapor deposition and maintain a constant mixing ratio during vapor deposition. In this way, vapor deposition of a layer with uniformly distributed components can be achieved simply and quickly without the need for precise control of multiple material sources.

[0260] In an alternative embodiment of the invention, the mixture, in addition to comprising the body material 1 of formula (1) or (1A) as described above or preferably, and the body material 2 of formula (2A), (2B), (2C), (2D), (2E), or (2F), also comprises the phosphorescent luminescent material as described above. In vapor deposition, this mixture can also be used as the sole material source when the mixing ratio is appropriate.

[0261] Preferred is a premixed system consisting of two matrix materials, namely a compound of formula (1) or formula (1A) and a compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F).

[0262] The components or ingredients of the organic layer of the device of the present invention can thus be obtained by vapor deposition or solution processing. In the case of solution processing, the host materials 1 and 2 as described above or preferably, optionally in combination with the phosphorescent emitter as described above or preferably, are provided in a formulation containing at least one solvent. Suitable formulations have been described above.

[0263] According to preferred embodiments and luminescent compounds, the luminescent layer in the device of the present invention preferably contains a matrix material with an overall composition based on the luminescent material and matrix material of 99.9 vol% to 1 vol%, more preferably 99 vol% to 10 vol%, particularly preferably 98 vol% to 60 vol%, and very particularly preferably 97 vol% to 80 vol%, said matrix material being composed of at least one compound of formula (1) or formula (1A) according to preferred embodiments and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E), or formula (2F). Accordingly, the luminescent layer in the device of the present invention preferably contains a luminescent material with an overall composition based on the luminescent material and matrix material of 0.1 vol% to 99 vol%, more preferably 1 vol% to 90 vol%, more preferably 2 vol% to 40 vol%, and most preferably 3 vol% to 20 vol%. If the compound is processed by solution, it is preferable to use an amount in weight % rather than the amount in volume % as specified above.

[0264] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), wherein the hole injection material and the hole transport material belong to the arylamine class.

[0265] Preferred hole injection materials and / or hole transport materials are shown in the table below. The materials in this table may also be partially or completely deuterated.

[0266] Table: The following compounds can also be partially or completely deuterated.

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] The preferred layer order in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0277] This layer order is a preferred order. It should also be noted again that not all mentioned layers are required, and / or other layers may exist.

[0278] The material used for the electron transport layer can be any material that serves as the electron transport material in the electron transport layer according to existing technology. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphazacyclopentane derivatives, and phosphine oxide derivatives.

[0279] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, wherein the electron injection material and / or electron transport material is selected from compounds of formula (1) or formula (1A) as described above or as preferably described.

[0280] Suitable cathodes for the devices of the present invention are metals with low work function, metal alloys composed of various metals, or multilayer structures, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, such as Ag or Al, can also be used. In this case, combinations of said metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal fluorides or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Lithium quinoline (LiQ) can also be used for this purpose. The layer thickness is preferably between 0.5 nm and 5 nm.

[0281] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, for this purpose, metals with high redox potentials are suitable, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are also preferred. x Al / PtO x ).

[0282] For some applications, at least one of the electrodes must be transparent or partially transparent to allow for the illumination of organic materials (organic solar cells) or the coupling of output light (OLEDs, O-lasers). The preferred anode material is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0283] Since the presence of water and / or air can shorten the lifespan of the device of the present invention, the organic electroluminescent device of the present invention is appropriately structured, has contact connections set, and is finally sealed during the manufacturing process (depending on the application).

[0284] The manufacture of the device of the present invention is not limited herein. One or more organic layers, including a light-emitting layer, can be coated by sublimation. In this case, by sublimation in a vacuum sublimation system at less than 10 -5 millibars, preferably less than 10 -6 Material is applied via vapor deposition at an initial pressure of millibars. However, in this case, even lower pressures, such as less than 10, are used. -7 An initial pressure of millibars is also feasible.

[0285] The organic electroluminescent device of the present invention is preferably characterized in that one or more layers are coated by OVPD (organic vapor deposition) or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied under a pressure between millibar and 1 bar. A special case of this method is OVJP (organic vapor phase inkjet printing), in which the material is applied directly through a nozzle, thereby structuring (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0286] The organic electroluminescent device of the present invention is further preferably characterized by producing one or more organic layers comprising the composition of the present invention from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (photoinduced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble host materials 1 and 2 and a phosphorescent emitter are required. The advantage of solution processing is, for example, that the luminescent layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the large-scale production of organic electroluminescent devices.

[0287] Furthermore, a hybrid approach is feasible, for example, in which one or more layers are applied by a solution and one or more other layers are applied by vapor deposition.

[0288] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0289] Therefore, the present invention also provides a method for manufacturing an organic electroluminescent device as described above or as preferably described in the present invention, characterized by applying an organic layer, preferably a light-emitting layer, by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by sublimation with the aid of a carrier gas, or by solution, especially by spin coating or by printing.

[0290] In the case of fabrication using vapor deposition, there are, in principle, two methods to apply or vapor deposit the organic layer, preferably the luminescent layer, of the present invention onto any substrate or prior layer. First, the materials used are initially packaged individually in material sources and can ultimately be evaporated from different material sources (“co-evaporation”). Second, the various materials can be premixed (premixed system), the mixture initially packaged in a single material source and ultimately evaporated from there (“premixed evaporation”). In this way, vapor deposition of a luminescent layer with uniformly distributed components can be achieved simply and quickly without the need for precisely driving multiple material sources.

[0291] The following processes are feasible: A method for manufacturing the organic electronic device of the present invention as described above or as preferably described, characterized in that an organic layer, preferably a light-emitting layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by carrier gas sublimation, or by solution, especially by spin coating or by printing.

[0292] A method for manufacturing an organic electronic device of the present invention as described above or as preferably described, characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (1) or formula (1A) and at least one compound of formula (2), formula (2B), formula (2C), formula (2D), formula (2E) and formula (2F), together with any other material forming the light-emitting layer, are sequentially or simultaneously deposited from at least two material sources by vapor deposition.

[0293] A method for manufacturing the device of the present invention, characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (1) or formula (1A), together with at least one compound of formula (2), formula (2B), formula (2C), formula (2D), formula (2E) and formula (2F) as a premix, is sequentially or simultaneously deposited by vapor deposition with a light-emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0294] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, has one or more of the following surprising advantages: 1. A mixture or preferred embodiment of a compound of formula (1) or formula (1A) described above and below with a compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), particularly as a matrix material, for electronic devices, particularly organic electroluminescent devices, exhibits very good lifetime, especially at low emitter concentrations.

[0295] 2. Electronic devices, particularly organic electroluminescent devices, that use compounds of formula (1) or (1A) as described above and below, or mixtures of compounds of formula (2A), (2B), (2C), (2D), (2E), or (2F), or preferred embodiments thereof, as matrix materials exhibit excellent efficiency. In this case, the compounds of formula (1) or (1A) of the present invention as described above and below, or mixtures of compounds of formula (2A), (2B), (2C), (2D), (2E), or (2F), or preferred embodiments thereof, result in low operating voltages when used in electronic devices.

[0296] 3. The compounds of formula (1) or formula (1A) described above and below, or mixtures or preferred embodiments of compounds of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F), have excellent glass film formation.

[0297] These advantages were not accompanied by an unusually severe deterioration in other electronic properties.

[0298] It should be noted that variations of the embodiments described in this invention are covered by the scope of this invention. Unless expressly excluded, any feature disclosed in this invention may be exchanged for an alternative feature having the same or equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered an example of a general series or an equivalent or similar feature.

[0299] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true for preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (and not in combination).

[0300] The technical teachings disclosed in this invention can be refined and combined with other examples.

[0301] The invention is illustrated in more detail by means of the following embodiments, but is not intended to limit the invention.

[0302] Example

[0303] Synthesis example

[0304] Unless otherwise specified, the following syntheses are carried out in dry solvents under an inert gas atmosphere. The compounds can be prepared by synthetic methods known to those skilled in the art.

[0305] Example 1

[0306] Example 1a: [[ID=X14]]Spiro[9 H -fluorene-9,7'(12' H )-indeno[1,2- a carbazole]-12'-[2-(4,6-diphenyl-1,3,5-triazin-2-yl)]

[0307] Under a protective atmosphere, 4.2 g of NaH in 60% mineral oil (0.106 mmol) was dissolved in 300 mL of dimethylformamide. 43 g (0.106 mol) of spiro[9H-fluorene-9,7'(1'H)-indeno[1,2-a]carbazole] was dissolved in 250 mL of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3,5]-triazine (34.5 g, 0.122 mol) in 200 mL of THF was added dropwise. The reaction mixture was then stirred at room temperature for 12 hours. After this time, the reaction mixture was poured onto ice. After warming to room temperature, the precipitated solid was filtered off and washed with ethanol and heptane. The residue was extracted with hot toluene, recrystallized from toluene / n-heptane, and finally sublimed under high vacuum; purity 99.9%. The yield was 28.4 g (44.5 mmol; 42%).

[0308] The following compounds were prepared in a similar manner:

[0309] Example 2

[0310] Example 2a: 5,8-dihydro-5-phenyl-8-(2-bitetraphenyl)indolo[2,3- c carbazole-d 26

[0311] 21.3 g (38.4 mmol; 1.00 equivalence) of 5,8-dihydro-5-phenyl-8-(2-triphenylimidazolium)indolo[2,3-c]carbazole was suspended in 520 mL (120 equivalence) toluene-d8 [CAS 2037-26-5]. While cooling, 12.28 mL (6.00 equivalence) trifluoromethanesulfonic acid was added to the mixture. The reaction mixture was stirred at room temperature for 6 hours. Then, 96 mL (130 equivalence) deuterated water [CAS 7789-20-0] was added dropwise at 0 °C. The mixture was neutralized with potassium sulfate solution, extracted with toluene, washed with physiological saline, and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. After purification by chromatography, 17 g (29 mmol, 76% of the theoretical value) of the above product, a mixture of H / D isotopic isomer fractions and H / D isotopic fractions, was obtained. This product was then subjected to high vacuum (p = 5 × 10⁻⁶). -7 Sublimation at 1000 mg / dL (99.9% purity).

[0312] The following products can be obtained in a similar manner:

[0313] OLED production

[0314] Data for each OLED are presented in the following Comparative Examples V1 to V11 and Invention Examples E1 to E7 (see Tables 7 and 8).

[0315] Examples E1 to E7 show the data for the OLED of the present invention. In Table 7, the substrate used for the OLED is a glass plate coated with a structured ITO (indium tin oxide) with a thickness of 50 nm.

[0316] The exact structure of an OLED is given in Table 7. The materials required for OLED manufacturing, if not described above, are shown in Table 9.

[0317] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (which is also the host material) and a luminescent dopant (emitter), which is added to the matrix material by co-evaporation in a specific volume ratio. Detailed information reported in the form of eV1:hV5:TEG2 (32%:60%:8%) 40 nm indicates that in this case, material eV1, as host material 1, exists at a volume ratio of 32%, compound hV5, as host material 2, at a ratio of 60%, and TEG2 at a ratio of 8% in a 40 nm thick layer. Similarly, the hole injection layer (HIL) and electron transport layer (ETL) can also be composed of a mixture of the two materials.

[0318] OLEDs are characterized in a standard manner. For this purpose, electroluminescence spectra and current-voltage-luminescence density characteristics (IUL characteristics) are measured; these are used to calculate EQE. The calculations are performed under the assumption of Lambertian light emission characteristics. The electroluminescence spectrum is at 1000 cd / m². 2 The luminescence density was measured. The parameter U10 in Table 8 represents 10 mA / cm². 2 The voltage required for the current density. EQE10 refers to 10 mA / cm². 2 The external quantum efficiency at the current density.

[0319] Lifetime LT is defined as the time taken in mA / cm². 2 During operation with a constant current density j0, the luminous density changes from the initial luminous density L0 (unit: cd / m²). 2 The value decreases to a certain proportion L1 (unit: cd / m³). 2 The time after L1 / L0 = 90% in Table 8 refers to the time (in hours) after the luminescent density reported in the LT column drops to 90% of its initial value (L0).

[0320] Use of the mixture of the present invention in OLEDs

[0321] The compounds or material combinations of the present invention can be used in the light-emitting layer of phosphorescent green OLEDs.

[0322] Data for each OLED is summarized in Table 8. Examples V1 to V11 are comparative examples according to the prior art; Examples E1 to E7 show data for the OLEDs of the present invention. The embodiments of the present invention show significant advantages, particularly in terms of device lifetime.

[0323] Table 7: Structure of OLED

[0324]

[0325]

[0326] Table 8:

[0327]

[0328] Table 9: Materials Used When Not Specified Above

[0329]

[0330]

[0331]

Claims

1. An organic electronic device comprising an anode, a cathode, and at least one organic layer, said organic layer comprising at least one compound of formula (1) or formula (1A) and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E), or formula (2F). The symbols and markings used are as follows: Y is the same or different in each case and is CR. 1 Or N, provided that at least one Y group is N; X is the same or different in every case and is CR. 1 Or N; or two adjacent X's are S, O, or NR. 1 Thus forming a five-membered ring; or two adjacent X groups are groups of the following formula (2), formula (3) or formula (4), Where ^ represents the corresponding adjacent X group in formula (1) or formula (1A); V is the same or different in each case and is C(R) 1 2. NR 1 O, S, BR 1 Si(R) 1 )2 or C=O; Z is the same or different in each case and is CR. 1 Or N; Ar may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R may be the same or different in each case and is selected from: H, D, F, Cl, Br, I, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 The atoms are either C≡C or O, and one or more of the hydrogen atoms may be replaced by D or F, or the atom has 6 to 60 aromatic ring atoms and may be replaced by one or more R atoms. 2 Aromatic ring systems with substituted groups; here, two adjacent substituents R can also form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be substituted by one or more R groups. 2 Group substitution; R 1 In each case, they may be the same or different and are selected from: H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 2 )2,C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3,Si(R 2 3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 C≡C, Si(R) 2 2. C=O, C=S, C=NR 2 P(=O)(R) 2 SO, SO2, NR 2 O, S or CONR 2 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and each of the aromatic or heteroaromatic ring systems may be replaced by one or more R atoms. 2 Group substitution, having 5 to 60 aromatic ring atoms and being substituted by one or more R groups 2 A group-substituted aryloxy or heteroaryloxy group; here, two adjacent R groups 1 The substituents may optionally form monocyclic or polycyclic aliphatic, aromatic, or heterocyclic ring systems, which may be formed by one or more R groups. 2 Group substitution; Ar 1 In each case, the same or different, and for those having 5 to 30 aromatic ring atoms and being capable of being separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; here, two Ar atoms bonded to the same nitrogen or phosphorus atom. 1 The group can also be formed by a single bond or by means of N(R) 2 ), C(R 2 2. Bridge bases of O or S are connected to each other; R 2 In each case, the same or different and selected from: H, D, F, CN, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein two or more adjacent R 2 Substituents can together form monocyclic or polycyclic aliphatic ring systems; m and n are the same or different in each case and are 0 or 1, provided that m+n≥1; p is the same or different in each case and is 0, 1, 2, 3 or 4; q is 0, 1, or 2; Equation (2A) Equation (2B) Equation (2C) Equation (2D) Equation (2E) Equation (2F) The symbols and markings used are as follows: A 1 For C(R) 7 2. NR 7 , O or S; L represents bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (2D-1) or formula (2D-2) in each case. X2 is the same or different in each case and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the position connected to equation (2D); U 1 U 2 When it appears, it is a key, O, S, C(R). 7 )2 or NR 7 ; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 5 to 60 ring atoms and in each case can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 The groups can also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring systems together; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being able to be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; here, two or more R groups are substituted. 7 The groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8 In each case, the same or different and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; c, c1, and c2 are independently 0 or 1 in each case, and the sum of the labels is c + c1 + c2 = 1 in each case; d, d1, and d2 are independently 0 or 1 in each case, and the sum of the labels is d + d1 + d2 = 1 in each case; q, q1, and q2 are independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1 or 2; u1 and u2 are independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

2. The organic electronic device according to claim 1, wherein the compound of formula (1) or formula (1A) is a deuterated compound.

3. The organic electronic device according to claim 2, wherein in the compound of formula (1) or formula (1A), at least one of the R groups of the spirodifluorene group and / or the R group of the 6-membered ring formed by the X group. 1 One of the groups is a deuterium atom.

4. The organic electronic device according to claim 2 or 3, wherein in the compound of formula (1) or formula (1A), the aromatic or heteroaromatic ring system Ar and / or the R of the 6-membered ring formed by the Y group 1 At least one of the groups is a deuterium atom.

5. The organic electronic device according to one or more of claims 2 to 4, wherein the degree of deuteration of the compound of formula (1) or formula (1A) is in the range of 1 mol% to 100 mol%, preferably in the range of 10 mol% to 100 mol%.

6. The organic electronic device according to claim 1, wherein the compound of formula (1) or formula (1A) is an undeuterated compound.

7. The organic electronic device according to one or more of claims 1 to 6, wherein the electronic device is selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic electroluminescent devices, organic solar cells (OSC), organic optical detectors, and organic photosensors.

8. The organic electronic device according to one or more of claims 1 to 7, wherein the electronic device is an electroluminescent device.

9. The organic electronic device according to claim 8, wherein the organic electronic device is selected from organic light-emitting transistors (OLET), organic field quenching devices (OFQD), organic light-emitting electrochemical cells (OLEC), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

10. The organic electronic device according to one or more of claims 1 to 9, wherein the organic layer comprises at least one light-emitting layer, the light-emitting layer comprising at least one compound of formula (1) or formula (1A) and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E) or formula (2F).

11. The organic electronic device of claim 10, wherein the light-emitting layer contains at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

12. The organic electronic device according to claim 10 or 11, wherein the light-emitting layer comprises a phosphorescent material.

13. The organic electronic device according to one or more of claims 1 to 12, wherein the organic layer comprises, in addition to the 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 a charge generation layer.

14. A method for producing an organic electronic device according to one or more of claims 1 to 13, characterized in that... The organic layer is applied by vapor deposition or from solution.

15. An organic electronic device comprising an anode, a cathode, and at least one organic layer, said organic layer comprising at least one compound of formula (1) or formula (1A) and at least one compound of formula (2A), formula (2B), formula (2C), formula (2D), formula (2E), or formula (2F). The symbols and markings used are as follows: Y is the same or different in each case and is CR. 1 Or N, provided that at least one Y group is N; X is the same or different in every case and is CR. 1 Or N; or two adjacent X's are S, O, or NR. 1 Thus forming a five-membered ring; or two adjacent X groups are groups of the following formula (2), formula (3) or formula (4), Where ^ represents the corresponding adjacent X group in formula (1) or formula (1A); V is the same or different in each case and is C(R) 1 2. NR 1 O, S, BR 1 Si(R) 1 )2 or C=O; Z is the same or different in each case and is CR. 1 Or N; Ar may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be substituted by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R may be the same or different in each case and is selected from: H, D, F, Cl, Br, I, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 The atoms are either C≡C or O, and one or more of the hydrogen atoms may be replaced by D or F, or the atom has 6 to 60 aromatic ring atoms and may be replaced by one or more R atoms. 2 Aromatic ring systems with substituted groups; here, two adjacent substituents R can also form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be substituted by one or more R groups. 2 Group substitution; R 1 In each case, they may be the same or different and are selected from: H, D, F, Cl, Br, I, CN, NO2, N (Ar) 1 )2,N(R 2 )2,C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3,Si(R 2 3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 C≡C, Si(R) 2 2. C=O, C=S, C=NR 2 P(=O)(R) 2 SO, SO2, NR 2 O, S or CONR 2 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and each of the aromatic or heteroaromatic ring systems may be replaced by one or more R atoms. 2 Group substitution, having 5 to 60 aromatic ring atoms and being substituted by one or more R groups 2 A group-substituted aryloxy or heteroaryloxy group; here, two adjacent R groups 1 The substituents may optionally form monocyclic or polycyclic aliphatic, aromatic, or heterocyclic ring systems, which may be formed by one or more R groups. 2 Group substitution; Ar 1 In each case, the same or different, and for those having 5 to 30 aromatic ring atoms and being capable of being separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; here, two Ar atoms bonded to the same nitrogen or phosphorus atom. 1 The group can also be formed by a single bond or by means of N(R) 2 ), C(R 2 2. Bridge bases of O or S are connected to each other; R 2 In each case, the same or different and selected from: H, D, F, CN, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, wherein two or more adjacent R 2 Substituents can together form monocyclic or polycyclic aliphatic ring systems; m and n are the same or different in each case and are 0 or 1, provided that m+n≥1; p is the same or different in each case and is 0, 1, 2, 3 or 4; q is 0, 1, or 2; Equation (2A) Equation (2B) Equation (2C) Equation (2D) Equation (2E) Equation (2F) The symbols and markings used are as follows: A 1 For C(R) 7 2. NR 7 , O or S; L represents bond, O, S, C(R) 7 )2 or NR 7 ; A is independently a group of formula (2D-1) or formula (2D-2) in each case. X2 is the same or different in each case and is CH, CR 6 Or N, where no more than two symbols X2 can be N; Indicates the position connected to equation (2D); U 1 U 2 When it appears, it is a key, O, S, C(R). 7 )2 or NR 7 ; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 5 to 60 ring atoms and in each case can be replaced by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; here, two R groups... 6 The groups can also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring systems together; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being able to be one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; here, two or more R groups are substituted. 7 The groups can also form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems together, but R 7 The group preferably does not form any such ring system; R 8 In each case, the same or different and are H, D, F, or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; c, c1, and c2 are independently 0 or 1 in each case, and the sum of the labels is c + c1 + c2 = 1 in each case; d, d1, and d2 are independently 0 or 1 in each case, and the sum of the labels is d + d1 + d2 = 1 in each case; q, q1, and q2 are independently 0, 1, 2, 3, or 4 in each case; s is the same or different in each case and is 0, 1, 2, 3 or 4; t is the same or different in each case and is 0, 1, 2 or 3; u is the same or different in each case and is 0, 1 or 2; u1 and u2 are independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v can be 0, 1, 2, or 3.

16. The mixture according to claim 15, wherein the mixture contains other compounds and / or solvents.

17. The mixture of claim 16, wherein the other compound is selected from matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

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