Materials for organic electroluminescent devices

Abstract

The present invention relates to heterocyclic compounds of formula (1) as well as compositions and devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as host materials.

Description

[0001] The present invention describes heterocyclic derivatives substituted by at least one cyano group, and compositions and devices comprising these compounds, in particular organic light-emitting devices comprising these compounds as host materials.

[0002] In organic light-emitting devices (OLEDs), phosphorescent organometallic complexes are often used as light-emitting materials. Generally, in OLEDs, especially those exhibiting triplet emission (phosphorescence), there is still room for improvement, for example, in terms of efficiency, operating voltage, and lifetime. The performance of phosphorescent OLEDs depends not only on the triplet emitters used. Here, other materials used, such as host materials or charge transport materials, are also particularly important. Therefore, the improvement of these materials can also lead to the improvement of OLED performance.

[0003] OLEDs exhibiting singlet emission (fluorescence and / or thermally activated delayed fluorescence) also still have room for improvement in terms of efficiency, operating voltage, and lifetime. Similarly, here, the performance of fluorescent OLEDs depends not only on the singlet emitters but also on other materials used, such as host materials and charge transport materials. Therefore, the improvement of these materials can also lead to the improvement of OLED performance.

[0004] The emitter compound should be understood here to mean a compound that emits light during the operation of the electronic device. The host compound should be understood in this case to mean a compound that is present in a larger proportion than the emitter compound in the mixture. The terms matrix compound and host compound can be used synonymously. The host compound preferably does not emit light. Even if there are multiple different host compounds in the mixture of the light-emitting layer, their respective proportions are usually greater than that of the emitter compound, or if there are multiple emitter compounds in the mixture of the light-emitting layer, they are usually greater than the proportions of the various emitter compounds.

[0005] If there is a mixture of multiple compounds in the light-emitting layer, the emitter compound is usually a component present in a smaller amount, that is, in a smaller proportion than the other compounds present in the mixture of the light-emitting layer. In this case, the emitter compound is also referred to as a dopant.

[0006] Host materials for organic electronic devices are well known to those skilled in the art. When referring to host materials for phosphorescent emitters, the term "matrix material" is also often used in the prior art. This usage of the term also applies to the present invention. At the same time, a variety of host materials for fluorescent and phosphorescent electronic devices have been developed.

[0007] 6H - Benzimidazo[1,2 - a]benzimidazole (BimBim) is a common building block used in the synthesis and development of high - triplet - energy (T1) host materials for next - generation blue organic light - emitting diodes (OLEDs). It was first described in WO11160757A1 and WO12130709A1.

[0008] In the BimBim structure, there is no conjugation between the two benzene rings, which results in a large gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and thus a high excited - state energy. This is particularly advantageous for host materials in deep - blue OLEDs based on phosphorescence, hyper - phosphorescence, or hyper - fluorescence, because in this way, the luminescence of the emitter is less likely to be quenched by the host, and high efficiency can be achieved.

[0009] Generally, there is still a need to improve these materials used as host materials. The problem solved by the present invention is to provide compounds that are particularly suitable for use as host materials or as electron - transporting materials in phosphorescent or fluorescent OLEDs.

[0010] Another means of improving the performance data of electronic devices, especially organic electroluminescent devices, is to use a combination of two or more materials, especially two or more host materials.

[0011] However, in the case of using host materials or in the case of using mixtures of host materials, there is still a need for improvement, especially in terms of the efficiency, operating voltage, and / or lifetime of organic electronic devices.

[0012] Surprisingly, it has been found that the compounds described in more detail below and mixtures containing the compounds solve this problem and are particularly suitable for use in OLEDs. In particular, the OLEDs have a long lifetime, high efficiency, and low operating voltage. Therefore, these compounds, mixtures containing these compounds, and electronic devices containing these compounds, especially organic electroluminescent devices, are the object of the present invention.

[0013] Accordingly, the present invention provides a compound of the following formula (1):

[0014]

[0015] The symbols and notations used therein are as follows:

[0016] Ar 1 is a group of formula (Ar1),

[0017]

[0018] wherein

[0019] The dashed bond represents the bonding position to the nitrogen in formula (1);

[0020] Y is the same or different in each case and is CR Y or N, or the two groups Y together form a fused ring, provided that Y 1 connected is C when p = 1 and CR when p = 0 Y or N; and

[0021] provided that in the group of formula (Ar1), at most two Ys in each ring are N;

[0022] Y 1 is O, S, CR Y 2 or a single bond;

[0023] p is 0 or 1;

[0024] Q is C, Ge or Si;

[0025] X is the same or different in each case and is CR X or N, or the two groups X together form a fused ring, provided that X connected to N is C;

[0026] R 1 、R X 、R Y each occurrence of which, independently of one another, represents a group selected from the group consisting of: H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)2, S(═O)Ar, S(═O)2Ar, N(R)2, N(Ar)2, NO2, Si(R)3, B(OR)2, OSO2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of said groups being optionally substituted by one or more groups R, where in each case one or more non-adjacent CH2 groups may be replaced by RC═CR, C≡C, Si(R)2, Ge(R)2, Sn(R)2, C═O, C═S, C═Se, P(═O)(R), SO, SO2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, said aromatic or heteroaromatic ring system being optionally substituted by one or more groups R in each case, and an aryloxy group having 5 to 60 aromatic ring atoms, said aryloxy group being optionally substituted by one or more groups R;

[0027] where two groups R 1 、one group R 1 and one group R Y 、two groups R x 、two groups RY can together form an aliphatic, aromatic or heteroaromatic ring system, which ring system can be substituted by one or more groups R;

[0028] R, each occurrence being the same or different, represents H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)2, S(═O)Ar, S(═O)2Ar, N(R')2, N(Ar)2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which groups can be substituted by one or more groups R', where in each case one or more non-adjacent CH2 groups can be replaced by R'C═CR', C≡C, Si(R')2, Ge(R')2, Sn(R')2, C═O, C═S, C═Se, P(═O)(R'), SO, SO2, O, S or CONR' and where one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system can in each case be substituted by one or more groups R', or an aryloxy group having 5 to 60 aromatic ring atoms, which aryloxy group can be substituted by one or more groups R'; where two groups R can together form an aliphatic or aromatic ring system, which ring system can be substituted by one or more groups R';

[0029] Ar, each occurrence being the same or different, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system can in each case also be substituted by one or more groups R';

[0030] R', each occurrence being the same or different, represents H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH2 groups can be replaced by SO, SO2, O, S and where one or more H atoms can be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

[0031] Furthermore, the following definitions of chemical groups apply for the purposes of the present application:

[0032] An aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; a heteroaryl group in the sense of the present invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, with at least one being a heteroatom. The heteroatom is preferably selected from N, O, and S. This represents the basic definition. If other preferred options are indicated in the description of the present invention, for example, regarding the number of aromatic ring atoms or heteroatoms present, then these preferred options apply.

[0033] The aryl group or heteroaryl group should be understood herein to refer to a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a fused (annelated) aromatic or heteroaromatic polycycle, such as naphthalene, phenanthrene, quinoline, or carbazole. A fused (annelated) aromatic or heteroaromatic polycycle in the sense of this application consists of two or more simple aromatic or heteroaromatic rings fused to each other.

[0034] An aryl or heteroaryl group (which in each case can be substituted by the above groups and can be linked to an aromatic or heteroaromatic ring system via any desired position) should be understood in particular to refer to a group derived from the following substances: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo - 5,6 - quinoline, benzo - 6,7 - quinoline, benzo - 7,8 - quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, azole, benzo azole, naphtho azole, anthra azole, phenanthro azole, iso azole, 1,2 - thiazole, 1,3 - thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, aza - carbazole, benzocarbazole, phenanthroline, 1,2,3 - triazole, 1,2,4 - triazole, benzotriazole, 1,2,3 - diazole, 1,2,4 - diazole, 1,2,5 - diazole, 1,3,4 - Oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0035] An aryloxy group as defined according to the invention is to be understood as meaning an aryl group as defined above, bonded via an oxygen atom. A similar definition applies to a heteroaryloxy group.

[0036] An aromatic ring system in the sense of the present invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms. A heteroaromatic ring system in the sense of the present invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, where at least one is a heteroatom. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the sense of the present invention is to be understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups, but in which, additionally, non-aromatic units (preferably less than 10% of the non-H atoms) such as sp 3 hybridized C, Si, N or O atoms, sp 2 hybridized C or N atoms or sp hybridized C atoms connect a plurality of aryl or heteroaryl groups. Thus, systems in which two or more aryl groups are connected, for example, by a straight-chain or cyclic alkyl, alkenyl or alkynyl group or by a silyl group, such as, for example, 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene and the like, are also to be understood as aromatic ring systems in the sense of the present invention. In addition, systems in which two or more aryl or heteroaryl groups are connected to one another via a single bond, such as, for example, biphenyl, terphenyl or diphenyltriazine and the like, are also understood as aromatic or heteroaromatic ring systems in the sense of the present invention.

[0037] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (the ring system may in each case also be substituted by the groups defined above and may be linked to the aromatic or heteroaromatic group via any desired position) is to be understood in particular as referring to groups derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, bibenzylidene, terphenyl, terbenzylidene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indeno[1,2-b]fluorene, triphenylene, isotriphenylene, spirotriphenylene, spiroisotriphenylene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaphenanthrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluoranthene ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-dioxazole, 1,2,4-dioxazole, 1,2,5-dioxazole, 1,3,4-dioxazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or combinations of these groups. oxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzo oxazole, naphtho oxazole, anthra oxazole, phenanthro oxazole, iso oxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaphenanthrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, oxazine, phenothiazine, fluoranthene ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- dioxazole, 1,2,4- dioxazole, 1,2,5- dioxazole, 1,3,4- dioxazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or combinations of these groups.

[0038] For the purposes of the present invention, a straight-chain alkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms (wherein individual H atoms or CH2 groups may additionally be substituted by the groups mentioned above under the definition of the groups) is preferably understood to mean the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to 40 carbon atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0039] For the purposes of the present application, the expression that two groups can form a ring with each other is intended to be understood as particularly meaning that the two groups are connected to each other by a chemical bond. This is illustrated by the following scheme:

[0040]

[0041] However, in addition, the above expression is also intended to be understood as meaning that in the case where one of the two groups represents hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following scheme:

[0042]

[0043] When two groups form a ring with each other, it is preferred that the two groups are adjacent groups. Adjacent groups in the sense of the present invention are groups bonded to atoms directly connected to each other or to the same atom.

[0044] According to a preferred embodiment, the compound of formula (1) is selected from the compounds of formula (1-1) to formula (1-4),

[0045]

[0046]

[0047] wherein the symbols have the definitions as above.

[0048] According to a preferred embodiment, the group Ar of formula (1) 1 is selected from the groups of formula (Ar1-1) to formula (Ar1-5),

[0049]

[0050]

[0051] wherein the symbols have the definitions as above.

[0052] According to a highly preferred embodiment, the compound of formula (1) is selected from the compounds of formula (1-1-1-1) to formula (1-4-5-4),

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Wherein the symbols have the definitions as above.

[0094] In a preferred embodiment of the present invention, Q is C and Ar 1 is a group of formula (Ar1-1) to formula (Ar1-4), or Q is Ge or Si and Ar 1 is a group of formula (Ar-4).

[0095] In a preferred embodiment of the present invention, X is the same or different each time it appears and represents CR X .

[0096] In a preferred embodiment of the present invention, X is the same or different each time it appears and represents CR X , and Y is the same or different each time it appears and represents CR Y . In this embodiment, X or Y is not N.

[0097] In a preferred embodiment of the present invention, Y is the same or different each time it appears and represents CR Y .

[0098] In a preferred embodiment, the compound is a compound according to one of formula (1-1-1-1) to formula (1-1-5-4) or formula (1-2-1-1) to formula (1-2-5-4).

[0099] Preferred embodiments of the compounds according to formula (1-1-1-1) to formula (1-4-5-4) are shown in the following table:

[0100]

[0101]

[0102] In a preferred embodiment, the compound contains no more than two of the following substituents R, and the substituent R is a group other than H, F, CN or D, preferably a group other than H or D.

[0103] In a preferred embodiment, the compound contains no more than two of the following substituents selected from R X and / or R Y , and the substituent is a group other than H, F, CN or D, preferably a group other than H or D.

[0104] In a preferred embodiment, the compound is a compound according to one of formulas (1-1-1-1) to (1-1-5-4) or formulas (1-2-1-1) to (1-2-5-4), preferably a compound according to one of formulas (1-1-1-1a) to (1-1-5-4a) or formulas (1-2-1-1a) to (1-2-5-4a).

[0105] Preferably, R 1 、R X 、R Y each occurrence independently represents H, D, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms, each of which may be substituted by one or more groups R, where in each case one or more non-adjacent CH2 groups may be replaced by RC═CR, C≡C, O or S and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18 aromatic ring atoms, the aromatic or heteroaromatic ring system in each case being substitutable by one or more groups R.

[0106] More preferably, R 1 、R X 、R Y each occurrence independently represents H, D, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 carbon atoms, each of which may be substituted by one or more groups R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, the aromatic or heteroaromatic ring system in each case being substitutable by one or more groups R, where two groups R 1 and / or one group R 1 and one group R Y together may form an aliphatic, aromatic or heteroaromatic ring system, the ring system being substitutable by one or more groups R.

[0107] Particularly preferably, R 1 、R X 、R Yrepresents, each time it appears, the same or different, H, D, a straight-chain alkyl group having 1 to 10, preferably 1 to 6 C atoms or a branched or cyclic alkyl group having 3 to 10, preferably 3 to 6 C atoms, each of which groups may be substituted by one or more groups R, or an aromatic or heteroaromatic ring system having 5 to 18, preferably 6 to 12 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more groups R, where two groups R 1 and / or one group R 1 and one group R Y together may form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more groups R.

[0108] Very particularly preferably, R X 、R Y represent H or D.

[0109] In the case where R 1 、R X 、R Y represent an aromatic or heteroaromatic ring system, preferably they are the same or different in each case and are selected from the groups of the following formulas Ar-1 to Ar-83:

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] wherein R is as defined above, the dashed bond represents a bond to the corresponding carbon atom, furthermore:

[0117] Ar 3 is the same or different in each case and is a divalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms and which may in each case be substituted by one or more R groups;

[0118] A 1 is the same or different in each case and is NR, O, S or C(R)2;

[0119] n is 0 or 1, where n = 0 means that no A 1 group is bonded at this position, but rather an R group is bonded to the corresponding carbon atom;

[0120] m is 0 or 1, where m = 0 means that the Ar 3 group does not exist and the corresponding aromatic or heteroaromatic group is directly bonded to a carbon atom.

[0121] Particularly preferred Ar groups are the Ar-1, Ar-2, Ar-3, Ar-4, Ar-13 groups (where A 1 = O or S, m = 1 and Ar 3 = p-phenylene), Ar-13 (where m = 0 and A 1 = C(CH3)2 or C(C6H5)2), Ar-14 (where m = 0 and A 1 = C(CH3)2 or C(C6H5)2), Ar-15 (where A 1 = N-phenyl, m = 1 and Ar 3 = m-phenylene or p-phenylene), Ar-16 (where m = 0 and A 1 = O, S, C(CH3)2 or C(C6H5)2), Ar-43, Ar-45 and Ar-46, especially the following groups: Ar-1a, Ar-2a, Ar-3a, Ar-4a, Ar-13a (where A 1 = O or S), Ar-13b (where A 1 = C(CH3)2 or C(C6H5)2), Ar-14a (where A 1 = C(CH3)2 or C(C6H5)2), Ar-15a, Ar-15b, Ar-16a (where A 1 = O, S, C(CH3)2 or C(C6H5)2), Ar-43a, Ar-45a and Ar-46a,

[0122]

[0123]

[0124] where the symbols used have the definitions given above.

[0125] In a preferred embodiment, R 1 is the same or different each time it appears and represents a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably 5 to 18, more preferably 6 to 12 aromatic ring atoms, where the group or ring system can in each case be substituted by one or more groups R, where two groups R 1 together can form an aliphatic, aromatic or heteroaromatic ring system, which ring system can be substituted by one or more groups R.

[0126] In a preferred embodiment, R1 represents, identically or differently at each occurrence, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably 5 to 18, more preferably 6 to 12 aromatic ring atoms, said group or ring system being in each case optionally substituted by one or more groups R, where two groups R 1 together can form an aliphatic, aromatic or heteroaromatic ring system, said ring system being optionally substituted by one or more groups R, preferably two groups R 1 can form an aromatic or heteroaromatic ring system via at least one single bond.

[0127] In a preferred embodiment, R 1 is selected from the groups according to CR3, CR2CR3, Ar-1, Ar-2, Ar-3, Ar-4, preferably Ar-1 and CR3, where two R 1 can be connected via a single bond.

[0128] Preferably, in formulas (1-1-1-1) to (1-4-5-4), Q and two R 1 are selected as follows:

[0129]

[0130] According to a very preferred embodiment, the compounds of formula (1) are selected from the compounds of formula (1-1-1-1a) to formula (1-4-6-4a),

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178] Among formulas (1-1-1-1a) to (1-4-5-4a): p and q are the same or different and are each independently selected from 0, 1, 2, 3, and 4; and r and s are the same or different and are each independently selected from 0, 1, 2, 3, 4, and 5.

[0179] The following compounds are examples of the compound of formula (1):

[0180]

[0181]

[0182]

[0183]

[0184] Therefore, the present invention also provides a method for preparing the compound of the present invention, which is characterized by the following steps:

[0185] (1) Synthesize the basic skeleton of the compound of formula (1) containing a reactive leaving group or H replacing the Ar 1 group, and the reactive leaving group is preferably selected from boric acid, borate ester, Cl, Br, I, trifluoromethanesulfonate, tosylate, or mesylate;

[0186] (2) Introduce the Ar 1 group through a coupling reaction.

[0187] In addition, the present invention also provides a composition, which comprises a material selected from the compounds of formula (1) as defined above and a material selected from hole transport host materials, and the hole transport host materials are preferably selected from triazines, pyrimidines, quinazolines, quinoxalines and lactams or derivatives of these structures.

[0188] Preferred triazine, pyrimidine, quinazoline or quinoxaline derivatives that can be used as a mixture with the compounds of the present invention are compounds of the following formula (e-1), formula (e-2), formula (e-3) and formula (e-4):

[0189]

[0190] wherein R has the meaning given above. R is preferably the same or different in each case and is H or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms and which may be substituted by one or more R 1 groups.

[0191] Preferred are compounds of the following formula (e-1a) to formula (e-4a):

[0192]

[0193] wherein the symbols used have the definitions given above.

[0194] Particularly preferred are triazine derivatives of formula (e-1) or formula (e-1a) and quinoxaline derivatives of formula (e-4) or formula (e-4a), especially triazine derivatives of formula (e-1) or formula (e-1a).

[0195] In a preferred embodiment of the present invention, Ar in formula (e-1a), formula (e-2a), formula (e-3a) and formula (e-4a) is the same or different in each case and is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, especially 6 to 24 aromatic ring atoms, and which may be substituted by one or more R groups. Here, suitable aromatic or heteroaromatic ring systems Ar are the same as the embodiments described above for Ar, especially structures Ar-1 to Ar-83.

[0196] Examples of suitable triazine and pyrimidine compounds that can be used as matrix materials together with the compounds of the present invention are the compounds shown in the following table:

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218] Examples of suitable quinazoline and quinoxaline derivatives are the structures shown in the following table:

[0219]

[0220] Examples of suitable lactams are the structures shown in the following table:

[0221]

[0222] Other examples of suitable matrix materials that can be used with the compounds of the present invention are the compounds shown in the following table:

[0223]

[0224] Preferably, the composition comprises a first host material selected from compounds of formula (1) as defined above, a second host material selected from electron transport host materials, and a third compound selected from phosphorescent emitters, fluorescent emitters, and emitters exhibiting TADF (thermally activated delayed fluorescence).

[0225] According to a preferred embodiment, the third compound is selected from phosphorescent emitters. In the context of the present invention, phosphorescence should be understood to refer to luminescence from an excited state with a higher spin multiplicity, i.e., a spin state > 1, especially luminescence from an excited triplet state. In the context of the present application, all luminescent complexes having transition metals or lanthanide elements, especially all iridium, platinum, and copper complexes, should be considered phosphorescent emitters.

[0226] Suitable phosphorescent compounds ( = triplet emitters) are in particular compounds which emit light when appropriately excited, preferably in the visible region, and which 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 a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum.

[0227] Examples of such light emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 041769, WO 2019 / 020538, WO 2018 / 178001, WO 2019 / 115423, or WO 2019 / 158453. Generally, all phosphorescent complexes used for phosphorescent OLEDs according to the prior art and known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art will be able to use other phosphorescent complexes without creative effort.

[0228] Examples of phosphorescent dopants are shown below:

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] According to another preferred embodiment, the third compound is selected from emitters exhibiting thermally activated delayed fluorescence (TADF emitters) (e.g., H. Uoyama et al., Nature 2012, Vol. 492, 234). These emitters are organic materials in which the energy gap between the lowest triplet state T1 and the first excited singlet state S1 is small enough that the S1 state is thermally accessible from the T1 state. The TADF emitter is preferably an aromatic compound having both a donor substituent and an acceptor substituent, in which there is only a slight spatial overlap between the LUMO and the HOMO of the compound. It should be understood that the donor substituent and the acceptor substituent are known to those skilled in the art in principle. Suitable donor substituents are in particular diarylamino groups or diheteroarylamino groups and carbazole groups or carbazole derivatives, each of which is preferably bonded to the aromatic compound via N. These groups may also have further substitutions. Suitable acceptor substituents are in particular cyano groups, but also electron-deficient heteroaryl groups which may also have further substitutions, such as substituted or unsubstituted triazine groups.

[0245] The general technical knowledge of those skilled in the art includes knowledge of which materials are generally suitable as TADF compounds. The following references disclose by way of example materials that may be suitable as TADF compounds:

[0246] - Tanaka et al., Chemistry of Materials 25(18), 3766 (2013).

[0247] - Lee et al., Journal of Materials Chemistry C 1(30), 4599 (2013).

[0248] - Zhang et al., Nature Photonics advance online publication, 1(2014), doi:10.1038 / nphoton.2014.12.

[0249] - Serevicius et al., Physical Chemistry Chemical Physics 15(38), 15850(2013).

[0250] - Li et al., Advanced Materials 25(24), 3319(2013).

[0251] - Youn Lee et al., Applied Physics Letters 101(9), 093306(2012).

[0252] - Nishimoto et al., Materials Horizons 1, 264(2014), doi:10.1039 / C3MH00079F.

[0253] - Valchanov et al., Organic Electronics, 14(11), 2727(2013).

[0254] - Nasu et al., ChemComm, 49, 10385(2013).

[0255] In addition, the following patent applications disclose possible TADF compounds: WO 2013 / 154064, WO 2013 / 133359, WO 2013 / 161437, WO 2013 / 081088, WO 2013 / 081088, WO 2013 / 011954, JP 2013 / 116975, and US 2012 / 0241732.

[0256] In addition, those skilled in the art can infer the design principles of TADF compounds from these publications. For example, Valchanov et al. showed how the color of TADF compounds can be adjusted.

[0257] Examples of suitable molecules exhibiting TADF are the structures shown in the following table:

[0258]

[0259]

[0260] According to another preferred embodiment, the third compound is selected from fluorescent emitters. Preferred fluorescent emitters are aromatic anthrylamines, aromatic anthryldiamines, aromatic pyrenylamines, aromatic pyrenyldiamines, aromatic chrysenylamines or aromatic chrysenyldiamines. Aromatic anthrylamines are to be understood as compounds in which one diarylamino group is directly bonded to the anthracene group, preferably at the 9-position. Aromatic anthryldiamines are to be understood as compounds in which two diarylamino groups are directly bonded to the anthracene group, preferably at the 9,10-positions. Aromatic pyrenylamines, pyrenyldiamines, chrysenylamines and chrysenyldiamines are defined in a similar manner, where the diarylamino group is bonded to the pyrene preferably at the 1-position or at the 1,6-positions. Other preferred emitters are indeno[1,2-b]fluoreneamines or indeno[1,2-b]fluorenediamines, such as according to WO 2006 / 108497 or WO 2006 / 122630; benzoindeno[1,2-b]fluoreneamines or dibenzoindeno[1,2-b]fluorenediamines, such as according to WO 2008 / 006449; and dibenzoindeno[1,2-b]fluoreneamines or dibenzoindeno[1,2-b]fluorenediamines, such as according to WO 2007 / 140847; and indeno[1,2-b]fluorene derivatives containing fused aryl groups as disclosed in WO 2010 / 012328. Other preferred emitters are benzoanthracene derivatives as disclosed in WO 2015 / 158409, anthracene derivatives as disclosed in WO 2017 / 036573, fluorene dimers linked via heteroaryl groups as in WO 2016 / 150544 or phen azine derivatives as disclosed in WO 2017 / 028940 and WO 2017 / 028941. Also preferred are pyrenylarylamines as disclosed in WO 2012 / 048780 and WO 2013 / 185871. Also preferred are benzoindeno[1,2-b]fluoreneamines as disclosed in WO 2014 / 037077, benzo[1,2-b]fluoreneamines as disclosed in WO 2014 / 106522 and indeno[1,2-b]fluorene as disclosed in WO 2014 / 111269 or WO 2017 / 036574, WO 2018 / 007421. Also preferred are emitters containing dibenzofuran or indeno[1,2-b]dibenzofuran moieties as disclosed in WO 2018 / 095888, WO 2018 / 095940, WO2019 / 076789, WO 2019 / 170572 as well as WO 2020 / 043657, WO 2020 / 043646 and WO / 2020 / 043640. Also preferred are boron derivatives as disclosed in, for example, WO 2015 / 102118, CN108409769, CN107266484, WO2017195669, US2018069182 as well as WO 2020 / 208051, WO2021 / 058406 and WO 2021 / 094269.

[0261] According to another preferred embodiment, the composition comprises a first host material selected from compounds of formula (1) as defined above, a second host material selected from hole-transporting host materials, a third compound selected from phosphorescent emitters and emitters exhibiting TADF (thermally activated delayed fluorescence), and a fourth compound selected from phosphorescent emitters and fluorescent emitters.

[0262] In other layers of the organic electroluminescent device of the present invention, any materials commonly used according to the prior art can be used. Therefore, those skilled in the art can combine any materials known for use in organic electroluminescent devices with the compound of formula (1) or the compounds of the above preferred embodiments without creative work.

[0263] The composition may also comprise other organic or inorganic compounds also used in electronic devices, such as other emitters or other host materials.

[0264] The compound of formula (1) or the composition comprising the compound of formula (1) can be processed by vapor deposition or from solution. If the composition is applied from solution, the formulation of the composition of the present invention is required to comprise at least one other solvent. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents are preferably used.

[0265] Therefore, the present invention also provides a formulation comprising the compound of formula (1) or a composition comprising the compound of formula (1) and at least one solvent.

[0266] Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, decalin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, di alkane, phenyltolyl ether, especially 3-phenyltolyl ether, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane, or mixtures of these solvents.

[0267] The present invention also provides the use of the compound of formula (1) or a composition comprising the compound of formula (1) in an organic electronic device, preferably in a light-emitting layer and / or in an electron-transporting layer.

[0268] The organic electronic device is preferably selected from an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic electroluminescent device, an organic solar cell (OSC), an organic optical detector, and an organic photoreceptor, and particularly preferably an organic electroluminescent device.

[0269] Very particularly preferred organic electroluminescent devices containing at least one compound of formula (1) as described above or as preferred are an organic light-emitting transistor (OLET), an organic field quenching device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser), and an organic light-emitting diode (OLED); particularly preferably OLEC and OLED, and most preferably OLED.

[0270] Preferably, the compound of formula (1) as described above or as preferred is used in a layer having an electron-transporting function in an electronic device. The layer is preferably an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL), and / or a light-emitting layer (EML), more preferably ETL, EIL, and / or EML. Most preferably, the compound of formula (1) or the composition is used as a host material in combination with an electron-transporting host material in the EML.

[0271] Accordingly, the present invention also provides an organic electronic device, which is particularly selected from one of the above-mentioned electronic devices and comprises the compound of formula (1) as described above or as preferred or a composition comprising the compound of formula (1), preferably in a light-emitting layer (EML), in an electron transport layer (ETL), in an electron injection layer (EIL), and / or in a hole blocking layer (HBL), very preferably in EML, EIL, and / or ETL, and most preferably in EML, and comprises the compound of formula (1) as described above or as preferred or a composition comprising the compound of formula (1).

[0272] In a particularly preferred embodiment of the present invention, the electronic device is an organic electroluminescent device containing the compound of formula (1) or a composition comprising the compound of formula (1) in a light-emitting layer (EML), and most preferably an organic light-emitting diode (OLED).

[0273] In a particularly preferred embodiment of the present invention, the organic light-emitting device thus comprises an anode, a cathode, and at least one organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of formula (1) as described above or a composition comprising a compound of formula (1).

[0274] Based on the overall composition of the luminescent material and the host material, the light-emitting layer in the device of the present invention as described above preferably contains a host material in the range of 99.9 vol% to 1 vol%, more preferably in the range of 99 vol% to 10 vol%, particularly preferably in the range of 98 vol% to 40 vol%, very particularly preferably in the range of 97 vol% to 50 vol%. The host material comprises at least one compound of formula (1) or a first host material comprising at least one compound selected from formula (1) and a second host material selected from the electron-transporting host materials as described above. Accordingly, based on the overall composition of the light-emitting layer comprising the luminescent material and the host material, the light-emitting layer in the device of the present invention preferably contains a luminescent material in the range of 0.1 vol% to 99 vol%, more preferably in the range of 1 vol% to 90 vol%, more preferably in the range of 2 vol% to 40 vol%, and most preferably in the range of 3 vol% to 20 vol%. If the compound is processed from a solution, the corresponding amounts in weight% are preferably used instead of the amounts in vol% described above.

[0275] The light-emitting layer in the device of the present invention as described above preferably contains a host material of formula (1), preferably in combination with a host material selected from electron-transporting host materials, in a volume percentage ratio between 3:1 and 1:3, preferably between 1:2.5 and 1:1, more preferably between 1:2 and 1:1. If the compound is processed from a solution, the corresponding ratio in weight% is preferably used instead of the ratio in vol% described above.

[0276] In addition to the cathode, anode, and the layer comprising the composition of the present invention, the electronic device may further comprise other layers. These layers are each selected from, for example, one or more hole injection layers, hole transport layers, hole blocking layers, light-emitting layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers (IDMC 2003, Taiwan, China; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n junctions. However, it should be noted that not every one of these layers necessarily needs to be present.

[0277] The preferred order of the layers in the organic electroluminescent device is as follows:

[0278] Anode / Hole injection layer / Hole transport layer / Light-emitting layer / Electron transport layer / Electron injection layer / Cathode.

[0279] The layer order is the preferred order.

[0280] At the same time, it should be pointed out again that not all of the mentioned layers need to be present and / or other layers may also be present.

[0281] The organic electroluminescent device of the present invention may contain two or more light-emitting layers. According to the present invention, at least one of the light-emitting layers contains at least one compound of formula (1) as described above and a composition containing the compound of formula (1). More preferably, in this case, these light-emitting layers generally have a plurality of emission peaks between 380 nm and 750 nm, so that the overall result is white light emission; in other words, a variety of light-emitting compounds that can emit fluorescence or phosphorescence and emit blue light or yellow light or orange light or red light are used in the light-emitting layer. Particularly preferred is a three-layer system, that is, a system having three light-emitting layers, wherein the three layers emit light of blue, green, and orange or red light (for the basic structure, see, for example, WO 2005 / 011013). It should be noted that in order to generate white light, it may also be suitable to use a luminescent compound that emits light in a wide wavelength range alone instead of a variety of luminescent compounds that emit colored light.

[0282] Suitable charge transport materials for use in the hole injection layer or hole transport layer or electron blocking layer or electron transport layer of the organic electroluminescent device of the present invention are, for example, the compounds disclosed by Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0283] The material for the electron transport layer can be any material used as an electron transport material in the electron transport layer according to the prior art. 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, phosphadiazole derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0284] Preferred hole transport materials are especially materials that can be used in a hole transport layer, a hole injection layer or an electron blocking layer, such as indeno[1,2-b]fluorene amine derivatives (e.g., according to WO 06 / 122630 or WO 06 / 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g., according to WO 01 / 049806), amine derivatives having a fused aromatic system (e.g., according to US 5,061,569), amine derivatives disclosed in WO 95 / 09147, monobenzylindeno[1,2-b]fluorene amine (e.g., according to WO08 / 006449), dibenzylindeno[1,2-b]fluorene amine (e.g., according to WO 07 / 140847), spirobifluorene amine (e.g., according to WO 2012 / 034627 or EP 12000929.5 which has not been published yet), fluorene amine (e.g., according to WO 2014 / 015937, WO 2014 / 015938 and WO 2014 / 015935), spirodibenzopyran amine (e.g., according to WO 2013 / 083216) and dihydroacridine derivatives (e.g., according to WO 2012 / 150001).

[0285] Preferred cathodes for electronic devices are metals, metal alloys or multilayer structures having a low work function, said metal alloys or multilayer structures comprising a plurality of metals, such as alkaline earth metals, alkali metals, main group metals or lanthanide elements (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or an alkaline earth metal and silver, such as an alloy comprising magnesium and silver. In the case of a multilayer structure, in addition to the metals mentioned, other metals having a relatively high work function, such as Ag or Al, can be used, in which case a combination of metals, such as Ca / Ag, Mg / Ag or Ba / Ag, is usually used. It is also preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials that can be used for this purpose are alkali metal fluorides or alkaline earth metal fluorides, but can also be the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinolate (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0286] Preferred anodes are materials having a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. First, metals having a high redox potential are suitable for this purpose, such as Ag, Pt or Au. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO x 、Al / PtO x) can also be preferred. For some applications, at least one electrode must be transparent or partially transparent in order to be able to irradiate the organic material (organic solar cell) or emit light (OLED, O-laser). The preferred anode material here is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, especially conductive doped polymers. In addition, the anode can also consist of two or more layers, for example, an inner ITO layer and an outer metal oxide layer, and the metal oxide is preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0287] The organic electronic device is appropriately (depending on the application) structured during production, contact connections are provided, and finally sealed, because the lifetime of the device according to the invention is shortened in the presence of water and / or air.

[0288] In another preferred embodiment, the organic electronic device comprising the composition according to the invention is characterized in that one or more organic layers comprising the composition according to the invention are coated by a sublimation method. In this case, the material is applied by vapor deposition in a vacuum sublimation system at an initial pressure below 10 -5 mbar, preferably below 10 -6 mbar. However, in this case, the initial pressure can even be lower, for example, below 10 -7 mbar.

[0289] Also preferred is an organic electroluminescent device, which is characterized in that one or more layers are coated by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, the material is applied at a pressure between 10 -5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is directly applied through a nozzle and thus structured (for example, M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0290] Also preferred is an organic electroluminescent device, which is characterized in that one or more organic layers comprising the composition according to the invention are produced 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 LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds of the components of the composition according to the invention are required. High solubility can be achieved by suitable substitution of the corresponding compounds. The advantage of processing from a solution is that the layer comprising the composition according to the invention can be applied in a very simple and inexpensive manner. This technique is particularly suitable for mass production of organic electronic devices.

[0291] In addition, hybrid methods are also feasible, where, for example, one or more layers are applied from solution and one or more additional layers are applied by vapor deposition.

[0292] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0293] Accordingly, the present invention also provides a method for producing an organic electronic device comprising the inventive composition as described above or as preferably described, characterized in that at least one organic layer comprising the inventive composition is applied by vapor deposition, in particular by sublimation and / or by OVPD (organic vapor phase deposition) method and / or by sublimation with a carrier gas, or from solution, in particular by spin coating or by printing method.

[0294] When producing an organic electronic device by means of vapor deposition, in principle there are two methods to apply or deposit by vapor deposition an organic layer comprising the inventive composition and which can comprise a plurality of different components onto any substrate. First, the materials used can each be initially loaded in a material source and finally evaporated from different material sources ("co-evaporation"). Second, the various materials can be premixed (premix system), the mixture can be initially loaded in a single material source and finally evaporated therefrom ("premix evaporation"). In this way, vapor deposition of a layer with a uniform distribution of components can be achieved in a simple and rapid manner without the need to precisely drive a plurality of material sources.

[0295] Accordingly, the present invention also provides a method characterized in that at least one compound of formula (1) as described above or as preferably described and the composition comprising the compound of formula (1) as described above or as preferably described are deposited from at least two material sources, optionally together with other materials as described above or as preferably described, sequentially or simultaneously from the gas phase and form an organic layer.

[0296] Accordingly, the present invention also provides a method characterized in that the inventive composition as described above or as preferably described is used as a material source for a vapor deposition bulk system and optionally forms an organic layer together with other materials.

[0297] The present invention also provides a method for producing an organic electronic device comprising the inventive composition as described above or as preferably described, characterized in that the inventive formulation as described above is used to apply the organic layer.

[0298] It should be noted that the scope of the present invention covers variations of the embodiments described herein. Any feature disclosed in the present invention can be exchanged for an alternative feature serving the same purpose or an equivalent or similar purpose, unless explicitly excluded. Therefore, any feature disclosed in the present invention should be regarded as an instance of a general series or an equivalent or similar feature, unless otherwise specified.

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

[0300] The technical teachings disclosed in the present invention can be extracted and combined with other embodiments. The present invention is illustrated in more detail by the following examples, without intending to limit the present invention thereby.

[0301] Synthesis Examples

[0302]

[0303] 5-(9H-carbazol-3-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (CAS: 1537905-39-7) was synthesized in a manner similar to WO2014009317A1.

[0304] Example 1:

[0305] 5-(9-(9,9'-Spirobi[fluorene]-4-yl)-9H-carbazol-3-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole

[0306]

[0307] 5-Fluoro-9,9'-spirobi[fluorene] (25.12 g; 72.80 mmol; 1.00 equivalent), 5-(9H-carbazol-3-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (34.07 g; 87.36 mmol; 1.20 equivalents) and cesium carbonate (47.92 g; 145.60 mmol; 2.00 equivalents) were added to 800 ml of dimethylacetamide and stirred under nitrogen for 30 minutes. Thereafter, it was heated to 150 °C for 48 hours. After cooling to room temperature, the solvent was distilled off and the residue was dissolved in dichloromethane and water. The aqueous phase was extracted twice with dichloromethane. After combining the organic phases, the mixture was washed with brine and dried over sodium sulfate. After evaporating the solvent, the crude product was purified by chromatography to obtain 49 g of the final product (yield 98%).

[0308] In the same manner, by changing the starting materials, the following molecules can be synthesized:

[0309]

[0310] 4-Fluoro-9,9-dimethyl-9H-fluorene (CAS: 2420524-96-3) is synthesized according to the following reaction sequence:

[0311]

[0312] a) Suzuki reaction: Methyl 2-bromobenzoate 99% (50.0 g; 230 mmol; 1.0 equiv), 2-fluorophenylboronic acid (32.3 g; 230 mmol; 1.0 equiv), and K2CO3 (63.6 g; 460 mmol; 2.0 equiv) were suspended in acetonitrile (750 ml) and ethanol (500 ml) under argon. Dichlorobis(triphenylphosphine)Pd(II) (3.2 g; 4.6 mmol; 0.02 equiv) was added, and the reaction mixture was heated at reflux for 20 h. After cooling to room temperature, the mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over Na2SO4 and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography to give methyl 2'-fluoro-[1,1'-biphenyl]-2-carboxylate as a colorless oil (47 g, 87%).

[0313] b) Grignard reaction: Cerium(III) chloride (5.6 g; 22.6 mmol; 1.05 equiv) was heated to 80 °C for 1 h under argon. After cooling to room temperature, methyl 2'-fluoro-[1,1'-biphenyl]-2-carboxylate (5.0 g; 21.5 mmol; 1.0 equiv) and THF (165 ml) were added. The reaction mixture was cooled to 2 °C, and a 3.0 M THF solution of methylmagnesium chloride (21.5 ml; 64 mmol; 3.0 equiv) was added dropwise. Stirring was continued overnight at room temperature. The mixture was poured into aqueous ammonia and extracted with ethyl acetate. The combined organic layers were dried over Na2SO4 and the solvent was removed in vacuo. Crude 2-{2'-fluoro-[1,1'-biphenyl]-2-yl}propan-2-ol was obtained as a yellow oil (6.5 g).

[0314] c) Condensation: 2-{2'-Fluoro-[1,1'-biphenyl]-2-yl}propan-2-ol (43.7 g; 185 mmol; 1.0 equiv) and Amberlyst 15 (17.8 g; 185 mmol; 1.0 equiv) were dissolved in toluene (1.5 l), and the reaction mixture was stirred under reflux for 48 h. After cooling to room temperature, the macroporous resin was filtered off and the solvent was removed in vacuo. The crude product was dissolved in heptane and filtered through silica, and the solvent was removed in vacuo. Colorless crystalline 4-fluoro-9,9-dimethyl-9H-fluorene (35.5 g, 89%) was obtained.

[0315] Example 3:

[0316] 5-(9-(Triphenylsilylbenzene-3-yl)-9H-carbazol-3-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole

[0317]

[0318] 3-(Bromophenyl)triphenylsilane (32.3 g; 77.3 mmol; 1.10 equiv), 5-(9H-carbazol-3-yl)-5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (19.4 g; 50.6 mmol; 0.72 equiv), K3PO4 (46.2 g; 211 mmol; 3.0 equiv) and CuI (4.0 g; 21.1 mmol; 0.30 equiv) were added to 1,4-d ane (500 ml) and trans-1,2-diaminocyclohexane (DACH) (85 ml; 703 mmol; 10.00 equiv), and the suspension was degassed under argon. Then it was heated to 100 °C for 2 days. After cooling to room temperature, the reaction mixture was poured into 500 ml of ammonia water (25%) and stirred for an additional 2 h. The product was extracted with toluene. The volume of the solution was reduced, the resulting precipitate was collected and washed with methanol. The crude product was recrystallized from toluene to give 27 g (36 mmol, 52%) of the product as a white solid.

[0319] In the same manner, by changing the starting materials, the following molecules can be synthesized:

[0320]

[0321]

[0322] Fabrication of OLED

[0323] Fabrication of Vapor-Processed OLED Devices

[0324] The OLED device is fabricated according to WO 04 / 058911, with the film thickness and layer sequence adjusted. The following Examples V1, E1, and E2 show the data of the OLED device.

[0325] The glass plate with structured ITO (50 nm, indium tin oxide) is pretreated with oxygen plasma and then with argon plasma. The pretreated glass plate forms the substrate on which the OLED device is fabricated.

[0326] The OLED device in principle has the following layer structure:

[0327] - Substrate,

[0328] - ITO (50 nm),

[0329] - Hole injection layer (HIL),

[0330] - Hole transport layer (HTL),

[0331] - Electron blocking layer (EBL),

[0332] - Emitting layer (EML),

[0333] - Hole blocking layer (HBL),

[0334] - Electron transport layer (ETL),

[0335] - Electron injection layer (EIL),

[0336] - Cathode.

[0337] The cathode is formed by an aluminum layer 100 nm thick. The detailed stack sequence is shown in Table A. The materials used for OLED fabrication are shown in Table B.

[0338] All materials are applied by hot vapor deposition in a vacuum chamber. The emitting layer always consists of at least one host material and one phosphorescent material here. By co-evaporation, the phosphorescent material is mixed with one or more host materials in a certain volume ratio. Expressions such as HH:EH:D (42%:43%:15%) here mean that material HH is present in the layer at a volume ratio of 42%, material EH is present in the layer at a volume ratio of 43%, and material D is present in the layer at a volume ratio of 15%. Similarly, the electron transport layer and the hole injection layer can also be composed of a mixture of two or more materials.

[0339] The OLED device is characterized by standard methods. For this purpose, the electroluminescence spectrum is determined, and the external quantum efficiency (EQE, measured in %) is determined according to the current / voltage / luminance density characteristic curve (IUL characteristic curve) assuming Lambertian emission characteristics. At 1000 cd / m 2The electroluminescence (EL) spectrum is recorded at a luminous density, and then the CIE 1931 x and y coordinates are calculated from the EL spectrum. U is defined as the voltage required for a current density of 10 mA / cm 2 The current density of. The parameter EQE represents the external quantum efficiency at a current density of 10 mA / cm 2 The current density of. The lifetime LT90 is defined as the time after which, during operation at a constant current density of 5 mA / cm 2 The luminous density drops from the initial luminous density to 90% of the initial luminous density.

[0340] The device data of each OLED device are summarized as shown in Tables A and C. Example V1 represents a comparative example according to the state of the art. Examples E1 and E2 show the data of the OLED devices of the present invention using an Ir complex as the light emitter. Examples E3, E4, and E5 show the data of the OLED devices of the present invention using a Pt complex as the light emitter.

[0341] In the next section, a plurality of embodiments will be described in more detail to show the advantages of the OLED devices of the present invention.

[0342] Using the compound of the present invention as a host material in a fluorescent OLED

[0343] The compound of the present invention is particularly suitable as a host (matrix) when mixed with an electron-conducting host material and a phosphorescent emitter to form the light-emitting layer of a phosphorescent blue OLED device. Representative examples use HH1, HH2, and HH3 as host materials. In addition, in Examples E1 to E5 given in Tables A and C, the host compounds HH1, HH2, and HH3 can be exchanged for compound HH4.

[0344] The comparative compound of the state of the art is represented by StA (structure see Table B). Compared with the state of the art, excellent device data are obtained by using the compound of the present invention as a host (matrix) in a phosphorescent blue OLED device, especially in terms of the lifetime LT90. This technical advantage is clear when comparing Examples E1 and E2 in Table A with V1. Here, the host compounds HH1 and HH2 of the present invention in E1 and E2 can also be exchanged for the compound HH4 of the present invention.

[0345] Excellent device data are obtained by using the compound of the present invention as a host (matrix) in a phosphorescent blue OLED device incorporating a Pt complex as the light emitter, especially in terms of the lifetime LT90. This is clear in Examples E3 and E4 in Table C, where HTM2 is selected from fluorenamine compounds. In addition, the host compounds HH2 and HH3 of the present invention in E3 and E4 can also be exchanged for the compound HH4 of the present invention.

[0346] Furthermore, excellent device data were obtained when using the compound of the present invention as an electron blocking material in the EBL of a phosphorescent blue OLED, especially in terms of the lifetime LT90 and the operating voltage U. This is clear when comparing Examples E5 and E4 in Table C, where HTM2 is selected from fluorenamine compounds. Here, the host compound HH3 of the present invention in E4 and E5 can also be exchanged with the compound HH4 of the present invention.

[0347] Table A: Device stack and performance data of vapor-processed OLEDs with Ir complexes as emitters

[0348]

[0349] Table B: Structural formulas of vapor-processed OLED materials

[0350]

[0351]

[0352] Table C: Device stack and performance data of vapor-processed OLEDs with Pt complexes as emitters

[0353]

Claims

1. A compound of formula (1), wherein the symbols and notations used are as follows: Ar 1 is a group of formula (Ar1), wherein the dashed bond represents the bonding position to the nitrogen in formula (1); Y is the same or different in each case and is CR Y or N, or the two groups Y together form a fused ring, provided that Y 1 linked to Y is C when p = 1 and CR when p = 0 Y or N; and provided that in the group of formula (Ar1), at most two Ys in each ring are N; Y 1 is O, S, CR Y 2 or a single bond; p is 0 or 1; Q is C, Ge or Si; X is the same or different in each case and is CR X or N, or two groups X together form a fused ring, provided that X attached to N is C; R 1 、R X 、R Y each, when occurring each time, independently represents a group selected from the group consisting of: H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar)2, S(═O)Ar, S(═O)2Ar, N(R)2, N(Ar)2, NO2, Si(R)3, B(OR)2, OSO2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which groups may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH2 groups may be replaced by RC═CR, C≡C, Si(R)2, Ge(R)2, Sn(R)2, C═O, C═S, C═Se, P(═O)(R), SO, SO2, O, S or CONR and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more groups R, and an aryloxy group having 5 to 60 aromatic ring atoms, which aryloxy group may be substituted by one or more groups R; Two of the groups R 1 , one group R 1 and one group R Y , two groups R x , two groups R Y may together form an aliphatic, aromatic or heteroaromatic ring system, which aliphatic, aromatic or heteroaromatic ring system may be substituted by one or more groups R; R, each occurrence being the same or different, represents H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, N(R')2, N(Ar)2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of said groups being optionally substituted by one or more groups R', wherein in each case one or more non-adjacent CH2 groups can be replaced by R'C=CR', C≡C, Si(R')2, Ge(R')2, Sn(R')2, C=O, C=S, C=Se, P(=O)(R'), SO, SO2, O, S or CONR' and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, said aromatic or heteroaromatic ring system being optionally substituted by one or more groups R' in each case, or an aryloxy group having 5 to 60 aromatic ring atoms, said aryloxy group being optionally substituted by one or more groups R'; where two groups R can together form an aliphatic or aromatic ring system, said aliphatic or aromatic ring system being optionally substituted by one or more groups R'; Ar, each occurrence being the same or different, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, said aromatic or heteroaromatic ring system being further optionally substituted by one or more groups R' in each case; R', each occurrence being the same or different, represents H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH2 groups can be replaced by SO, SO2, O, S and wherein one or more H atoms can be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

2. The compound according to claim 1, wherein The compound is selected from the compounds of formula (1-1) to formula (1-4), wherein the symbols have the definitions given in claim 1.

3. The compound according to claim 1 or 2, characterized in that Group Ar 1 selected from the groups of formula (Ar1-1) to formula (Ar1-5), wherein the symbols have the definitions given in claim 1.

4. A compound according to one or more of the preceding claims, characterized in that The compound of formula (1) is selected from the compounds of formula (1-1-1-1) to formula (1-4-5-4), wherein the symbols have the definitions given in claim 1.

5. A compound according to one or more of the preceding claims, characterized in that Q is C and Ar 1 is a group of formula (Ar1-1) to formula (Ar1-4) as defined in claim 3, or Q is Ge or Si and Ar 1 is a group of formula (Ar-4) as defined in claim 3.

6. A compound according to one or more of the preceding claims, characterized in that The compound contains no more than two of the following substituents R, said substituent R being a group other than H, F, CN or D.

7. A compound according to one or more of the preceding claims, characterized in that The compound contains no more than two of the following substituents selected from R X and / or R Y wherein the substituents are not H, F, CN or D.

8. A compound according to one or more of the preceding claims, characterized in that X and Y are not N.

9. A compound according to one or more of the preceding claims, characterized in that The compound is a compound according to one of Formula (1-1-1-1) to Formula (1-1-5-4) or Formula (1-2-1-1) to Formula (1-2-5-4).

10. A method for preparing a compound according to one or more of claims 1 to 9, It is characterized by the following steps: (1) The basic skeleton of the compound of formula (1) containing a reactive leaving group or H replacing the Ar 1 group; (2) Introduce the said Ar through a coupling reaction 1 group.

11. A preparation, the preparation comprising at least one compound according to one or more of claims 1 to 9 and at least one solvent.

12. Use of the compound according to one or more of claims 1 to 9 in an electronic device.

13. An electronic device, the electronic device comprising at least one compound according to one or more of claims 1 to 9.

14. The electronic device according to claim 13, wherein the electronic device is an organic electroluminescent device The compound according to one or more of claims 1 to 9 is combined with at least one phosphorescent emitter for use in a light-emitting layer.

15. The electronic device according to claim 14, wherein The light-emitting layer contains other materials comprising at least one compound selected from Formula (e-1), Formula (e-2), Formula (e-3), and Formula (e-4). wherein R is the same or different in each case and is H or an aromatic or heteroaromatic ring system having from 6 to 30 aromatic ring atoms and which may be substituted by one or more R 1 groups.

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