Materials for electronic devices

Abstract

The invention relates to a compound of formula (I), to the use of a compound of formula (I) in an electronic device, to an electronic device containing at least one compound of formula (I), and to a method for producing a compound of formula (I).

Description

[0001] The present invention relates to aromatic amines having specific carbazolyl, dibenzofuranyl or dibenzothiophenyl groups on the amine nitrogen atom. The compounds are suitable for use in electronic devices.

[0002] Electronic devices in the context of the present application are understood to mean so-called organic electronic devices, which contain organic semiconductor materials as functional materials. More particularly, these are understood to mean OLEDs (organic electroluminescent devices). The term OLED is understood to mean an electronic device which has one or more layers containing organic compounds and which emits light when a voltage is applied. The general principles of the structure and function of OLEDs are known to those skilled in the art.

[0003] There is great interest in improving the performance data in electronic devices, especially in OLEDs. In these areas, no completely satisfactory solutions have been found so far. In addition, there is a need to use alternative compounds in electronic devices, especially in OLEDs.

[0004] The light-emitting layer and the layer with hole transport function have an important influence on the performance data of the electronic device. New compounds for these layers are constantly being sought, especially hole transport compounds and compounds that can be used as hole transport matrix materials, especially hole transport matrix materials for phosphorescent emitters in the light-emitting layer. For this purpose, compounds with high glass transition temperature, high stability and high hole conductivity are being sought in particular. The high stability of the compound is a prerequisite for achieving a long life of the electronic device. It is also being sought for compounds that cause improvements in the performance data of the device when used in the electronic device, especially high efficiency, long life and low operating voltage.

[0005] In the prior art, triarylamine compounds, in particular spirobifluorenamine and fluorenamine, are known as hole transport materials and hole transport matrix materials for electronic devices. However, there is still a need for alternative compounds for the uses mentioned and, fundamentally, also for improvements in the above-mentioned properties.

[0006] It has now been found that aromatic amines of the following formula have excellent suitability, in particular for use in electronic devices, which are characterized in that they have specific carbazolyl, dibenzofuranyl or dibenzothiophenyl groups on the amine nitrogen atom. They are particularly suitable for use in OLEDs and even more particularly for use therein as hole transport materials and as hole transport matrix materials, in particular for hole transport matrix materials for phosphorescent emitters. These compounds lead to high lifetimes, high efficiencies and low operating voltages of the devices. Also preferably, the compounds found have high glass transition temperatures, high stability, low sublimation temperatures, good solubility, good synthetic accessibility and high hole conductivity.

[0007] The present application thus provides a compound of formula (I),

[0008]

[0009] The variables that appear are as follows:

[0010] X is O, S or NR 2 ;

[0011] Z is the same or different in each case and is CR 3 or N;

[0012] Z 1 are in each case identical or different and are selected from CR 1 and CA;

[0013] Z 2 are in each case identical or different and are selected from CR 1 and CA;

[0014] Wherein in formula (I) is selected from Z 1 and Z 2 At least one of the groups is CA;

[0015] A is a group of the formula:

[0016]

[0017] The dashed bonds are the bonds to the carbon atoms of the CA units;

[0018] Ar 1 are identical or different in each case and are selected from: 4 Aromatic ring systems substituted with a radical and having 5 to 40 aromatic ring atoms and being replaced by R 4 A heteroaromatic ring system substituted with a group, wherein the two Ar in formula (A) 1 The groups may be bonded to each other via a bond or an E group;

[0019] E is identical or different in each case and is selected from: C(R 4 )2、-C(R 4 )2-C(R 4 )2-、-C(R 4 )=C(R 4 )-、C=O、Si(R 4 )2. NR 4 , O, S, S=O and SO2;

[0020] R 1 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 1 The groups may be connected to each other and may form an aromatic ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2;

[0021] R 2 is selected from a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl, alkenyl and alkynyl groups and the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 wherein one or more CH2 groups in the alkyl, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2;

[0022] R 3 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 1 The groups may be connected to each other and may form an aromatic ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2;

[0023] R 4 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 4 The groups may be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2;

[0024] R 5 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 6 、CN、Si(R 6 )3、N(R 6 )2、P(=O)(R 6 )2.OR 6 、S(=O)R 6 、S(=O)2R 6 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 5 The groups may be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 6 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -、-C≡C-、Si(R 6 )2. C=O, C=NR 6 、-C(=O)O-、-C(=O)NR 6 -、NR 6 、P(=O)(R 6 ), -O-, -S-, SO or SO2;

[0025] R 6 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more of R 6 The groups may be connected to each other and may form a ring; and the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more groups selected from F and CN;

[0026] Among them, when X=NR 2 In the case of 2 The group must be CA.

[0027] The following definitions are applicable to chemical groups used in this application. Unless any more specific definitions are given, they are applicable.

[0028] Aryl groups in the context of the present invention are understood to refer to single aromatic rings, i.e. benzene, or fused aromatic polycyclics such as naphthalene, phenanthrene or anthracene. The fused aromatic polycyclics in the context of the present application are composed of two or more single aromatic rings fused to each other. The fusion between the rings is understood to refer to the rings sharing at least one edge with each other. Aryl groups in the context of the present invention contain 6 to 40 aromatic ring atoms. In addition, aryl groups do not contain any heteroatoms as aromatic ring atoms, but only contain carbon atoms as aromatic ring atoms.

[0029] The heteroaryl group in the context of the present invention is understood to refer to a single heteroaromatic ring such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycyclic such as quinoline or carbazole. In the context of the present application, the fused heteroaromatic polycyclic is composed of two or more single aromatic or heteroaromatic rings fused to each other, wherein at least one of the aromatic and heteroaromatic rings is a heteroaromatic ring. The fusion between the rings is understood to refer to the rings sharing at least one edge with each other. The heteroaryl group in the context of the present invention contains 5 to 40 aromatic ring atoms, at least one of the aromatic ring atoms being a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O and S.

[0030] Aryl or heteroaryl radicals which may in each case be substituted by the abovementioned radicals are understood in particular to mean radicals derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, letrozole, perylene, terphenylene, fluoranthene, benzanthracene, triphenylene, 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, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazole [1,2-a] benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxadiazole, benzoxadiazole, naphthimidazole oxadiazole, anthraquinone oxadiazole, phenanthraquinone oxadiazole, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole oxadiazole, 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, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0031] The aromatic ring system in the context of the present invention is the following system: it does not have to contain only aryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl group. These non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups covered by this definition are tetralin, fluorene and spirobifluorene. In addition, the term "aromatic ring system" includes a system consisting of two or more aromatic ring systems connected to each other via a single bond, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3,5-diphenyl-1-phenyl. The aromatic ring system in the context of the present invention contains 6 to 40 carbon atoms in the ring system and does not contain heteroatoms. The definition of "aromatic ring system" does not include heteroaryl groups.

[0032] The heteroaromatic ring system meets the definition of the above-mentioned aromatic ring system, except that it must contain at least one heteroatom as a ring atom. As in the case of aromatic ring systems, heteroaromatic ring systems do not have to contain only aryl groups and heteroaryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl or heteroaryl group. Non-aromatic rings may contain only carbon atoms as ring atoms, or they may additionally contain one or more heteroatoms, wherein the heteroatoms are preferably selected from N, O and S. An example of such a heteroaromatic ring system is benzopyranyl. In addition, the term "heteroaromatic ring system" is understood to refer to a system consisting of two or more aromatic or heteroaromatic ring systems bonded to each other via a single bond, such as 4,6-diphenyl-2-triazine. The heteroaromatic ring system in the context of the present invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, wherein at least one ring atom is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.

[0033] Thus, the terms "heteroaromatic ring system" and "aromatic ring system" as defined in the present application differ from each other in that an aromatic ring system cannot have heteroatoms as ring atoms, whereas a heteroaromatic ring system must have at least one heteroatom as a ring atom. Such a heteroatom may be present as a ring atom of a non-aromatic heterocycle or as a ring atom of an aromatic heterocycle.

[0034] According to the above definition, any aryl group is encompassed by the term "aromatic ring system" and any heteroaryl group is encompassed by the term "heteroaromatic ring system".

[0035] An aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms is understood in particular to mean radicals derived from the radicals mentioned above under aryl radicals and heteroaryl radicals, as well as biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, indenocarbazole, or combinations of these radicals.

[0036] In the context of the present invention, straight-chain alkyl radicals having 1 to 20 carbon atoms, and branched or cyclic alkyl radicals having 3 to 20 carbon atoms, and alkenyl or alkynyl radicals having 2 to 40 carbon atoms, in which individual hydrogen atoms or CH2 groups may also be substituted by radicals mentioned in the above definitions of radicals, are preferably understood to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methyl butyl, 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 radical.

[0037] Alkoxy or thioalkyl radicals having 1 to 20 carbon atoms, in which individual hydrogen atoms or CH2 groups may also be substituted by radicals mentioned in the definitions of the above radicals, are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio wherein the group is selected from the group consisting of: an isopropylthio, an n-butylthio, an isobutylthio, a sec-butylthio, a tert-butylthio, an n-pentylthio, a sec-pentylthio, an n-hexylthio, a cyclohexylthio, an n-heptylthio, a cycloheptylthio, an n-octylthio, a cyclooctylthio, 2-ethylhexylthio, a trifluoromethylthio, a pentafluoroethylthio, a 2,2,2-trifluoroethylthio, an ethylenethio, a propylenethio, a butenylthio, a pentylthio, a cyclopentenylthio, a hexenylthio, a cyclohexenylthio, a heptylthio, a cycloheptylthio, an octylthio, a cyclooctylthio, an ethynylthio, a propynylthio, a butynylthio, a pentylthio, a hexynylthio, a heptylthio or an octynylthio.

[0038] In the context of the present application, the phrase that two or more groups together can form a ring is to be understood as meaning in particular that the two groups are connected to each other via a chemical bond. However, in addition, the above phrase is also to be understood as meaning that, if one of the two groups is hydrogen, the second group combines with the position to which the hydrogen atom is bonded, thereby forming a ring.

[0039] In a preferred embodiment, the compound of formula (I) is a monoamine, meaning that it contains exactly one amino group and no other amino groups.

[0040] X is preferably O or NR 2 , more preferably O. In an alternative, equally preferred embodiment, X is O or S, more preferably O.

[0041] Z is preferably CR 3 In another preferred embodiment, no more than 3 Z groups in formula (I) are N, more preferably no more than 2 Z groups in formula (I) are N, and most preferably no more than 1 Z group in formula (I) is N. It is also preferred that the Z groups that are N are not directly bonded to each other.

[0042] In a preferred embodiment, in formula (I), Z 1 and Z 2 In a particularly preferred embodiment, in formula (I), exactly one of the groups selected from Z 2 In an alternative preferred embodiment, in formula (I), at least one of the groups is CA. 1 At least one of the groups is CA.

[0043] Ar 1 are preferably identical or different in each case and are selected from the group consisting of a group having 6 to 40 aromatic ring atoms and being replaced by R 4 Aromatic ring systems substituted with radicals.

[0044] Preferred Ar 1 The radicals are in each case identical or different and are selected from the monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenanthrene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, wherein each monovalent radical is replaced by R 4 Ar 1 The radicals are in each case identical or different and are selected from a combination of 2 to 4 radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenanthrene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, wherein each monovalent radical is replaced by R 4 Group substitution.

[0045] Ar 1The radicals are in each case identical or different and are selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzofuranyl, benzothienyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothienyl, and phenyl substituted by radicals selected from the group consisting of naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl and triazinyl, wherein each of these radicals is substituted by R 4 Group substitution.

[0046] Ar 1 Preference is given to groups which are identical or different in each case and are selected from the following formulae:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] wherein the dashed line represents the bond to the nitrogen atom and wherein the groups at the positions shown as unsubstituted may be replaced by R 4 The group is substituted and preferably has only H at the positions shown as unsubstituted.

[0065] In a preferred embodiment, the two Ar in formula (A) 1 The groups are not bonded via a bond or via an E group. In an alternative preferred embodiment, the two Ar in formula (A) 1 The groups are not bonded to each other, or are bonded to each other via a bond.

[0066] In a preferred embodiment, R 1 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3、N(R 5 ) 2, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 and wherein one or more CH2 groups in the alkyl group may be replaced by -C≡C-, -R 5 C=CR 5 -、Si(R 5 )2. C=O, C=NR 5 、-NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 More preferably, R 1 are identical or different in each case and are selected from: H, D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Even more preferably, R 1 are identical or different in each case and are selected from the group consisting of: H, D, a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Most preferably, R 1 are identical or different in each case and are selected from H and D, preferably from H.

[0067] In a preferred embodiment, R 2 is selected from a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 More preferably, R 2 is selected from an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Even more preferably, R 2 selected from a group consisting of a group having 6 to 40 aromatic ring atoms and being replaced by R 5 Aromatic ring systems substituted with radicals.

[0068] In a preferred embodiment, R 3 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3、N(R 5 ) 2, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 and wherein one or more CH2 groups in the alkyl group may be replaced by -C≡C-, -R 5 C=CR 5 -、Si(R 5 )2. C=O, C=NR 5 、-NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 More preferably, R 3 are identical or different in each case and are selected from: H, D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Even more preferably, R 3are identical or different in each case and are selected from the group consisting of: H, D, a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Most preferably, R 3 are identical or different in each case and are selected from H and D, preferably from H.

[0069] Preferably, R 4 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3、N(R 5 ) 2, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 and wherein one or more CH2 groups in the alkyl group may be replaced by -C≡C-, -R 5 C=CR 5 -、Si(R 5 )2. C=O, C=NR 5 、-NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 More preferably, R 4 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 Group substitution.

[0070] Preferably, R 5 are identical or different in each case and are selected from: H, D, F, CN, Si(R 6 )3、N(R 6 ) 2, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 6and wherein one or more CH2 groups in the alkyl group may be replaced by -C≡C-, -R 6 C=CR 6 -、Si(R 6 )2. C=O, C=NR 6 、-NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 More preferably, R 5 are identical or different in each case and are selected from: H, D, F, CN, straight-chain alkyl radicals having 1 to 20 carbon atoms, branched or cyclic alkyl radicals having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms.

[0071] Formula (I) preferably corresponds to one of the following formulae (IA) to (IC):

[0072]

[0073] The variables appearing therein are as defined above and preferably correspond to one of their preferred embodiments, and

[0074] Wherein, for formula (IA) and (IB), Z 1 and Z 2 At least one of the groups is CA, and

[0075] Wherein, for formula (IC), at least one Z 2 The group is CA. In formulas (IA) to (IC), R 1 Preferably, R is identical or different in each case and is H, D or phenyl, more preferably H.

[0076] Particularly preferred embodiments of formula (I) correspond to the following formulae (IA-1) to (IA-6), (IB-1) to (IB-6) and (IC-1) and (IC-2):

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] The variables occurring therein are as defined above and preferably correspond to one of their preferred embodiments.

[0083] Among the above formulae, formulae (IA-1), (IA-4), (IB-1), (IB-4), (IC-1) and (IC-2) are particularly preferred. Among them, formulae (IA-1), (IA-4), (IB-1) and (IB-4) are very particularly preferred. Among them, formulae (IA-1) and (IA-4) are most preferred.

[0084] In a preferred embodiment, formula (I) conforms to one of formulas (IA-1) to (IA-3), (IB-1) to (IB-3) and (IC-1), wherein formulas (IA-1), (IB-1) and (IC-1) are particularly preferred.

[0085] Particularly preferred embodiments of formula (I) also conform to the following formula:

[0086]

[0087]

[0088]

[0089]

[0090] The variables occurring therein are as defined above and preferably correspond to their above-described preferred embodiments.

[0091] In a preferred embodiment, the compound of formula (I) conforms to one of formulas (IA-1) to (IA-6), (IB-1) to (IB-6), (IC-1) or (IC-2), wherein the variables appear as follows:

[0092] -Ar 1 are identical or different and are selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, and phenyl substituted by a radical selected from the group consisting of naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl and triazinyl, wherein each of these radicals is substituted by R 4 Group substitution;

[0093] -R 1are identical or different in each case and are selected from: H, D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Group substitution; and

[0094] -R 2 is selected from: an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Group substitution; and

[0095] -R 3 are identical or different in each case and are selected from: H, D, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Group substitution; and

[0096] -R 4 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 Group substitution; and

[0097] -R 5 are identical or different in each case and are selected from: H, D, F, CN, straight-chain alkyl radicals having 1 to 20 carbon atoms, branched or cyclic alkyl radicals having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms.

[0098] Examples of preferred compounds of formula (I) are shown in the following table:

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] The compounds of formula (I) can be prepared by reactions known in organic synthetic chemistry.

[0108] Preferably, the synthesis is performed as shown in the following Scheme 1. Those skilled in the art will be able to modify and adapt the methods described herein within the scope of their ordinary knowledge in the art to obtain compounds similar to those shown herein.

[0109] Solution 1

[0110]

[0111] The variables present in the described scheme are as follows:

[0112] R is in each case identical or different and is H or an organic radical;

[0113] X is O, S or NR;

[0114] Y is a reactive group, preferably a halogen;

[0115] W is a reactive group, preferably a halogen;

[0116] Ar is identical or different in each case and is selected from aromatic and heteroaromatic groups.

[0117] The reactants in the method shown in Scheme 1 are commercially available or can be obtained by methods known from the literature. In the first step, these reactants are reacted at one of their reactive groups, the W group, by means of a Suzuki coupling, the reactive group being preferably the more reactive of the two W and Y groups in the Suzuki coupling reaction, thereby giving the corresponding intermediate in which a phenyl group is introduced instead of the W group. Preferably, the Suzuki coupling is achieved using a phenylboronic acid compound. Further preferably, the W group is Br.

[0118] In the second step, the compound formed in the first step is reacted with a secondary amine having two Ar groups as defined above via a Buchwald coupling reaction. This forms a compound of formula (I). The reactive Y group reacted here is preferably Cl.

[0119] The present application thus provides a method for preparing a compound of formula (I), characterized in that a compound containing a carbazole group, a dibenzofuran group or a dibenzothiophene group and a reactive Y group and a reactive W group first undergoes a Suzuki coupling reaction with a phenylboronic acid derivative, and then the resulting compound undergoes a Buchwald coupling reaction with a secondary amine. The reactive W group is converted in the Suzuki coupling, and the reactive Y group is converted in the Buchwald coupling. The reactive W group is preferably more reactive than the reactive Y group in the Suzuki coupling. More preferably, the reactive W group is Br and the reactive Y group is Cl.

[0120] The above-mentioned compounds according to the invention, in particular those substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters, can be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boric acid, boric esters, amines, alkenyl or alkynyl groups with terminal C-C double bonds or C-C triple bonds, oxirane, oxetane, groups participating in cycloadditions such as 1,3-dipolar cycloadditions such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0121] Therefore, the present invention also provides an oligomer, polymer or dendrimer, said oligomer, polymer or dendrimer comprising one or more compounds of formula (I), wherein one or more bonds to said polymer, oligomer or dendrimer may be located in the region of formula (I) where R 1 , R 2 , R 3 or R 4 At any desired position of substitution. According to the attachment of the compound of formula (I), said compound is part of a side chain or part of the main chain of an oligomer or polymer.

[0122] Further disclosures about oligomers, polymers or dendrimers can be found in WO 2020 / 109434 A1, page 49, line 26 to page 51, line 17. The disclosure content of these text passages is hereby fully incorporated into the present application by reference.

[0123] In order to process the compound of the present invention from the liquid phase, for example, by spin coating or by printing, a preparation of the compound of the present invention is required. These preparations may be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenketone, 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, phenethyl Ketone, alpha-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 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, or a mixture of these solvents.

[0124] The invention therefore also provides a preparation, in particular a solution, dispersion or emulsion, comprising at least one compound of formula (I) or at least one polymer, oligomer or dendrimer containing at least one unit of formula (I) and at least one solvent, preferably an organic solvent. The manner in which such solutions can be prepared is known to the person skilled in the art.

[0125] The compounds of formula (I) are suitable for use in electronic devices, in particular organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds of formula (I) can be used for different functions and layers. They are preferably used as hole-transporting materials in hole-transporting layers and / or as matrix materials in light-emitting layers, more preferably in combination with phosphorescent emitters.

[0126] Therefore, the present invention also provides the use of the compound of formula (I) in an electronic device. The electronic device is preferably selected from: organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and more preferably organic electroluminescent devices (OLEDs).

[0127] The present invention also provides an electronic device, comprising at least one compound of formula (I). The electronic device is preferably selected from the above devices.

[0128] Particularly preferred is an organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, characterized in that at least one organic layer comprising at least one compound of formula (I) is present in the device.Preferred is an organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, characterized in that at least one organic layer selected from the group consisting of a hole transport layer and an emitting layer in the device comprises at least one compound of formula (I).

[0129] The hole transport layer is understood here to mean all layers arranged between the anode and the light-emitting layer, preferably a hole injection layer, a hole transport layer and an electron blocking layer. The hole injection layer is understood here to mean a layer directly adjacent to the anode. The hole transport layer is understood here to mean a layer between the anode and the light-emitting layer but not directly adjacent to the anode and preferably not directly adjacent to the light-emitting layer. The electron blocking layer is understood here to mean a layer between the anode and the light-emitting layer and directly adjacent to the light-emitting layer. The electron blocking layer preferably has a high-energy LUMO, thereby preventing electrons from leaving the light-emitting layer.

[0130] In addition to the cathode, anode and light-emitting layer, the electronic device may also contain other layers. These are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers and / or organic or inorganic p / n junctions in each case. However, it should be pointed out that not every one of these layers must be present, and the choice of layer always depends on the compounds used, in particular also on whether the device is a fluorescent electroluminescent device or a phosphorescent electroluminescent device.

[0131] The order of layers in the electronic device is preferably as follows:

[0132] -anode-

[0133] -Hole injection layer-

[0134] -Hole transport layer-

[0135] -Optional additional hole transport layer-

[0136] -Luminous layer-

[0137] -Optional hole blocking layer-

[0138] -Electron transport layer-

[0139] -Electron injection layer-

[0140] -cathode-.

[0141] At the same time, it should be pointed out again that not all of the layers mentioned are necessarily present and / or further layers may additionally be present.

[0142] The organic electroluminescent device of the present invention may contain two or more emitting layers. More preferably, these emitting layers generally have several luminescence maxima between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a variety of luminescent compounds that can emit fluorescence or phosphorescence and emit blue, green, yellow, orange or red light are used in the luminescent layer. A three-layer system is particularly preferred, i.e. a system with three emitting layers, wherein in each case one of the three layers shows blue luminescence, in each case one of the three layers shows green luminescence, and in each case one of the three layers shows orange or red luminescence. The compound of the present invention is preferably present in a hole transport layer or in a luminescent layer. It should be noted that, in order to produce white light, it may also be suitable to use a single luminescent compound that emits light in a wide wavelength range, compared to a variety of luminescent compounds that emit colors.

[0143] The compound of formula (I) is preferably used as hole transport material. The emitting layer may be a fluorescent emitting layer, or the emitting layer may be a phosphorescent emitting layer. The emitting layer is preferably a blue fluorescent layer or a green phosphorescent layer.

[0144] When the device comprising a compound of the formula (I) comprises a phosphorescent emitting layer, it is preferred that this layer comprises two or more, preferably exactly two, different matrix materials (mixed-matrix system). Preferred embodiments of the mixed-matrix system are described in further detail below.

[0145] If the compound of formula (I) is used as hole transport material in a hole transport layer, hole injection layer or electron blocking layer, the compound can be used as pure material, ie in a proportion of 100%, in the hole transport layer, or it can be used in combination with one or more further compounds.

[0146] In a preferred embodiment, the hole transport layer comprising the compound of formula (I) further comprises one or more additional hole transport compounds. These additional hole transport compounds are preferably selected from triarylamine compounds, more preferably from monotriarylamine compounds. They are most preferably selected from the preferred embodiments of the hole transport materials further specified below. In the preferred embodiment described, the compound of formula (I) and one or more additional hole transport compounds are preferably each present in a ratio of at least 10%, more preferably each present in a ratio of at least 20%.

[0147] In a preferred embodiment, the hole-transporting layer comprising the compound of formula (I) additionally comprises one or more p-dopants. The p-dopants used according to the invention are preferably those organic electron acceptor compounds which are able to oxidize one or more other compounds in the mixture.

[0148] Particularly preferred p-type dopants are the following substances: quinone dimethane compounds; azaindenofluorenediones; azaperidobenzonaphthalene; azaterphenylidene; I2; metal halides, preferably transition metal halides; metal oxides, preferably metal oxides containing at least one transition metal or a metal of the third main group; and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as a binding site. The dopants are also preferably transition metal oxides, preferably oxides of rhenium, molybdenum and tungsten, more preferably Re2O7, MoO3, WO3 and ReO3. Also preferred are complexes of bismuth in the (III) oxidation state, more particularly bismuth (III) complexes with electron-deficient ligands, more particularly bismuth (III) complexes with carboxylic acid anion ligands.

[0149] The p-type dopant is preferably substantially uniformly distributed in the p-type doped layer. This can be achieved, for example, by co-evaporation of the p-type dopant and the hole transport material matrix. The p-type dopant is preferably present in the p-type doped layer in a proportion of 1% to 10%.

[0150] Preferred p-type dopants are also the compounds explicitly described on pages 86-87 of the published specification WO 2021 / 156323 A1.

[0151] In a preferred embodiment, a hole injection layer is present in the device in accordance with one of the following embodiments: a) the hole injection layer comprises a triarylamine and a p-type dopant; or b) the hole injection layer comprises a single electron-deficient material (electron acceptor). In a preferred embodiment of embodiment a), the triarylamine is a monotriarylamine, in particular one of the preferred triarylamine derivatives further mentioned below. In a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755.

[0152] The compound of formula (I) may be present in the hole injection layer, the hole transport layer and / or the electron blocking layer of the device. When the compound is present in the hole injection layer or the hole transport layer, the compound is preferably p-type doped, meaning that the compound is in the layer in a mixed form with a p-type dopant as described above.

[0153] The compound of formula (I) is preferably present in the electron blocking layer. In this case, the compound is preferably not p-doped. Also preferably, in this case, the compound is preferably in the form of a single compound in the layer without addition of further compounds.

[0154] In an alternative preferred embodiment, the compound of formula (I) is used as a matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds, in an emitting layer. The phosphorescent compounds are preferably selected from red phosphorescent compounds and green phosphorescent compounds.

[0155] In this case, the proportion of the matrix material in the light-emitting layer is between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5% by volume, and more preferably between 85.0% and 97.0% by volume.

[0156] Accordingly, the proportion of the luminescent compound is between 0.1% by volume and 50.0% by volume, preferably between 0.5% by volume and 20.0% by volume, and more preferably between 3.0% by volume and 15.0% by volume.

[0157] The light-emitting layer of the organic electroluminescent device may also comprise a system containing a variety of matrix materials (mixed matrix system) and / or a variety of light-emitting compounds. Also in this case, the light-emitting compounds are generally those compounds with a smaller proportion in the system, and the matrix materials are those compounds with a larger proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be less than the proportion of a single light-emitting compound.

[0158] The compound of formula (I) is preferably used as a component of a mixed matrix system, preferably for a phosphorescent emitter. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other material is a material with electron transport properties. It is also preferred that one of the materials is selected from compounds with a large energy difference between HOMO and LUMO (wide bandgap materials). The compound of formula (I) in the mixed matrix system is preferably a matrix material with hole transport properties. Accordingly, when the compound of formula (I) is used as a matrix material for a phosphorescent emitter in the light-emitting layer of an OLED, a second matrix compound with electron transport properties is present in the light-emitting layer. The two different matrix materials can be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1:1.

[0159] In a preferred embodiment, in the case of mixed-matrix systems, two or more matrix materials present in the mixed-matrix system are used as a mixture and applied by evaporation, at least one of which preferably corresponds to one of the formula (I).

[0160] However, the desired electron-transport properties and hole-transport properties of the mixed-matrix components can also be predominantly or completely combined in a single mixed-matrix component, in which case the further mixed-matrix component or components fulfil further functions.

[0161] The following material classes are preferably used in the above-mentioned layers of the device:

[0162] Phosphorescent emitters:

[0163] The term "phosphorescent emitting compound" generally includes compounds in which light emission is achieved via a spin-forbidden transition, such as a transition from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0164] Suitable phosphorescent emitters are, in particular, compounds which emit light when suitably excited, preferably in the visible region, and which further comprise at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. As phosphorescent emitters, preference is given to using compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper.

[0165] In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

[0166] In general, all phosphorescent complexes which are used in phosphorescent OLEDs according to the prior art and which are known to the person skilled in the art in the field of organic electroluminescent devices are suitable for use in the devices according to the invention. Further examples of suitable phosphorescent emitters are shown in the following table:

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173] Fluorescent luminescent body:

[0174] Preferred fluorescent luminescent compounds are selected from arylamines. In the context of the present invention, arylamines or aromatic amines are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic leucine or aromatic leucine diamines. Aromatic anthracene amines refer to compounds in which the diarylamino group is directly bonded to the anthracene group, preferably in the 9-position. Aromatic anthracene diamines refer to compounds in which two diarylamino groups are directly bonded to the anthracene group, preferably in the 9,10-position. Aromatic pyrene amines, pyrene diamines, leucine and leucine diamines are similarly defined, wherein the diarylamino group is preferably bonded to pyrene in the 1-position or 1,6-position. Also preferred luminescent compounds are the following substances: indenofluoreneamine or indenofluorenediamine, benzoindenofluoreneamine or benzoindenofluorenediamine, and dibenzoindenofluoreneamine or dibenzoindenofluorenediamine, and indenofluorene derivatives with fused aryl groups. Also preferred are pyrene arylamines. Also preferred are benzoindenofluoreneamine, benzofluoreneamine, extended benzoindenofluorene, phenoxazine, and fluorene derivatives connected to furan units or thiophene units.

[0175] Matrix materials for fluorescent emitters:

[0176] Preferred matrix materials for fluorescent emitters are selected from the following classes of substances: oligoarylene compounds (e.g. 2,2',7,7'-tetraphenylspirobifluorene), in particular oligoarylene compounds containing fused aromatic groups; oligoarylene vinylidene compounds; polypodal metal complexes; hole-conducting compounds; electron-conducting compounds, in particular ketones, phosphine oxides and sulfoxides; atropisomers; boronic acid derivatives; or benzanthracene. Particularly preferred matrix materials are selected from the following classes: oligoarylene compounds, which contain naphthalene, anthracene, benzanthracene and / or pyrene, or atropisomers of these compounds; oligoarylene vinylidene compounds; ketones; phosphine oxides; and sulfoxides. Very particularly preferred matrix materials are selected from the following classes: oligoarylene compounds, which contain anthracene, benzanthracene, triphenylene and / or pyrene, or atropisomers of these compounds. Oligoarylene compounds in the context of the present invention should be taken to mean compounds in which at least three aryl or arylene groups are bonded to one another.

[0177] Matrix materials for phosphorescent emitters:

[0178] Preferred matrix materials for phosphorescent emitters are, in addition to the compounds of formula (I), the following substances: aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones; triarylamines; carbazole derivatives such as CBP (N,N-dicarbazolylbiphenyl) or carbazole derivatives; indolocarbazole derivatives; indenocarbazole derivatives; azacarbazole derivatives; bipolar matrix materials; silanes; borazol or boric esters; triazine derivatives; zinc complexes; siladiazacyclopenta or siladiazacyclopenta derivatives; phosphodiazacyclopenta derivatives; bridged carbazole derivatives; terphenylidene derivatives; or lactams.

[0179] Electron transport materials:

[0180] Suitable electron-transporting materials are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art.

[0181] 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, lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, phosphodiazoline derivatives and phosphine oxide derivatives.

[0182] Preferred electron transport materials and electron injection materials are also the compounds explicitly shown on pages 73 to 75 of WO 2020 / 109434 A1.

[0183] Hole transport materials:

[0184] In addition to the compounds of the formula (I), further compounds preferably used in the hole-transporting layer of the OLED according to the invention are indenofluoreneamine derivatives, amine derivatives, hexaazatriphenylidene derivatives, amine derivatives with condensed aromatic systems, monobenzoindenofluoreneamines, dibenzoindenofluoreneamines, spirodifluoreneamines, fluoreneamines, spirodibenzopyranamines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthryldiarylamines, spirotribenzocycloheptatrienolone, spirobifluorenes with metaphenylenediamine groups, spirobiacridines, xanthenediarylamines and 9,10-dihydroanthracenylspiro compounds with diarylamino groups.

[0185] Preferred hole-transporting compounds are also the compounds explicitly described on pages 76 to 80 of WO 2020 / 109434 A1.

[0186] The preferred cathode of the electronic device is a metal with a low work function, a metal alloy or a multilayer structure comprising various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In addition, it is suitable to be an alloy consisting of an alkali metal or alkaline earth metal and silver, such as an alloy consisting of magnesium and silver. In the case of a multilayer structure, in addition to the metals mentioned, other metals such as Ag or Al with a relatively high work function can also be used, in which case a combination of the metals is generally used, such as Ca / Ag, Mg / Ag or Ba / Ag. It is also preferred to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal fluorides or alkaline earth metal fluorides, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinoline (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0187] Preferred anodes are materials 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 a high redox potential are suitable, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x ). For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to illuminate the organic material (organic solar cells) or to couple out the light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0188] In a preferred embodiment, the electronic device is characterized in that one or more layers are applied by sublimation. In this case, the material is sublimated in a vacuum system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The initial pressure can be applied by vapor deposition at an initial pressure of 10 mbar. However, in this case, the initial pressure can also be even lower, for example less than 10 -7 millibar.

[0189] Likewise preferred is an electronic component, characterized in that one or more layers are applied by an OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. In this case, the material is deposited at 10 -5The material is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet) method, in which the material is applied directly through a nozzle and thereby structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0190] In addition, an electronic device is preferred, characterized in that one or more layers are produced from a solution, for example by spin coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble compounds of formula (I) are required. High solubility can be achieved by suitable substitution of the compounds.

[0191] It is also preferred that the electronic device of the invention is produced by applying one or more layers from solution and by applying one or more layers by sublimation methods.

[0192] After the layers have been applied, the component is structured, contact connections are provided and finally sealed, depending on the intended use, in order to exclude the damaging effects of water and air.

[0193] According to the invention, electronic devices comprising one or more compounds of the formula (I) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications. Example

[0194] A) Synthesis Examples

[0195] 3-Chloro-5-phenyl-8-oxatricyclo[7.4.0.0 2,7 Synthesis of Tridecane-1(9),2,4,6,10,12-Hexaene 1a

[0196]

[0197] 8.1 g (66.5 mmol) of phenylboronic acid, 18.7 g (66.5 mmol) of 5-bromo-3-chloro-8-oxatricyclo[7.4.0.0 2,7 ]13 carbon-1(9),2,4,6,10,12-hexaene, 1.2 g (2 mmol) of bis(triphenylphosphine)Pd(II) chloride and 23 g (167 mmol) of potassium carbonate are suspended in 520 ml of acetonitrile and 220 ml of methanol. The reaction mixture is heated to boiling overnight under a protective atmosphere. It is then filtered with suction, washed with MeOH, washed with water and washed again with MeOH. The residue is purified by crystallization with MeOH. Yield: 14.8 g (80% of theory), purity according to GC-MS>99%.

[0198] The following compounds were prepared in a similar manner:

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] N,N-bis({[1,1'-biphenyl]-4-yl})-5-phenyl-8-oxatricyclo[7.4.0.0 2,7 Synthesis of Tridecyl-1(13),2,4,6,9,11-hexaenyl-3-amine 2a

[0205]

[0206] N-{[1,1'-biphenyl]-4-yl}[1,1'-biphenyl]-4-amine (24 g, 75 mmol), 3-chloro-5-phenyl-8-oxatricyclo[7.4.0.0 2,7 ] Tridecane-1(9),2,4,6,10,12-hexaene (20.9 g, 75 mmol) and sodium tert-butoxide (14.7 g, 150 mmol) were dissolved in 350 ml of toluene. The solution was degassed and saturated with N2. Tri-tert-butylphosphine (7.5 ml; 7.5 mmol, 1 M in xylene) and 3.4 g (3.8 mmol) of Pd2(dba)3 were then added. The reaction mixture was heated to boiling overnight under a protective atmosphere. The mixture was cooled and partitioned between toluene and water, the organic phase was washed three times with water, dried over Na2SO4 and concentrated by rotary evaporation. After filtering the crude product through silica gel with toluene, the remaining residue was recrystallized from toluene and finally sublimed under high vacuum; the purity was 99.9%. The yield was 21.1 g (50% of theory).

[0207] The following compounds were prepared in a similar manner:

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] B) Device Examples

[0215] The compounds according to the present application can be used in OLEDs having the following structure:

[0216] Substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / luminescent layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. A glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm forms the substrate on which the OLED is applied.

[0217] The exact structure of the OLED is shown below. The "HTM" materials used in the HIL and HTL are fluorene derivatives. The p-type dopant used is NDP-9 from Novaled AG, Dresden.

[0218] The compounds according to the present application can advantageously be used in the EBL of green phosphorescent OLEDs, as is shown below by way of example for compounds HTM-1 to HTM-3:

[0219]

[0220] For the parameters of lifetime and external quantum efficiency, very good results are given, as shown below:

[0221]

[0222]

[0223]

Claims

1. A compound of formula (I), The variables that appear are as follows: X is O, S or NR 2 ; Z is the same or different in each case and is CR 3 or N; Z 1 are in each case identical or different and are selected from CR 1 and CA; Z 2 are in each case identical or different and are selected from CR 1 and CA; Wherein in formula (I) is selected from Z 1 and Z 2 At least one of the groups is CA; A is a group of the formula: The dashed bonds are the bonds to the carbon atoms of the CA units; Ar 1 are identical or different in each case and are selected from: 4 Aromatic ring systems substituted with a radical and having 5 to 40 aromatic ring atoms and being replaced by R 4 A heteroaromatic ring system substituted with a group, wherein the two Ar in formula (A) 1 The groups may be bonded to each other via a bond or an E group; E is identical or different in each case and is selected from: C(R 4 )2、-C(R 4 )2-C(R 4 )2-、-C(R 4 )=C(R 4 )-、C=O、Si(R 4 )2. NR 4 , O, S, S=O and SO2; R 1 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 1 The groups may be connected to each other and may form an aromatic ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2; R 2 is selected from a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl, alkenyl and alkynyl groups and the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 wherein one or more CH2 groups in the alkyl, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2; R 3 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 1 The groups may be connected to each other and may form an aromatic ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2; R 4 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 5 、CN、Si(R 5 )3、N(R 5 )2、P(=O)(R 5 )2.OR 5 、S(=O)R 5 、S(=O)2R 5 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 4 The groups may be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 5 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 5 C=CR 5 -、-C≡C-、Si(R 5 )2. C=O, C=NR 5 、-C(=O)O-、-C(=O)NR 5 -、NR 5 、P(=O)(R 5 ), -O-, -S-, SO or SO2; R 5 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, C(═O)R 6 、CN、Si(R 6 )3、N(R 6 )2、P(=O)(R 6 )2.OR 6 、S(=O)R 6 、S(=O)2R 6 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more of R 5 The groups may be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each R 6 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -、-C≡C-、Si(R 6 )2. C=O, C=NR 6 、-C(=O)O-、-C(=O)NR 6 -、NR 6 、P(=O)(R 6 ), -O-, -S-, SO or SO2; R 6 are identical or different in each case and are selected from: H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more of R 6 The groups may be connected to each other and may form a ring; and the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more groups selected from F and CN; in, At X=NR 2 In the case of 2 The group must be CA.

2. The compound according to claim 1, characterized in that The compound is a monoamine.

3. The compound according to claim 1 or 2, characterized in that Z is CR 3 .

4. Compounds according to one or more of claims 1 to 3, characterized in that Ar 1 in each case identical or different and selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, and phenyl substituted by radicals selected from the group consisting of naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl and triazinyl, wherein each of these radicals is substituted by R 4 Group substitution.

5. Compound according to one or more of claims 1 to 4, characterized in that The following rules apply in combination: -R 1 are identical or different in each case and are selected from the group consisting of: H, D, a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Group substitution; -R 2 selected from a group consisting of a group having 6 to 40 aromatic ring atoms and being replaced by R 5 Group-substituted aromatic ring systems; -R 3 are identical or different in each case and are selected from the group consisting of: H, D, a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system are each replaced by R 5 Group substitution; -R 4 are identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each replaced by R 5 Group substitution; -R 5 are identical or different in each case and are selected from: H, D, F, CN, straight-chain alkyl radicals having 1 to 20 carbon atoms, branched or cyclic alkyl radicals having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms.

6. Compounds according to one or more of claims 1 to 5, characterized in that The compound of formula (I) conforms to one of formulas (IA-1) to (IA-6), (IB-1) to (IB-6), and (IC-1) and (IC-2): The variables present therein are defined according to one or more of claims 1 to 5.

7. The compound according to claim 6, characterized in that The compound conforms to one of formulas (IA-1), (IA-4), (IB-1), (IB-4), (IC-1) and (IC-2).

8. The compound according to claim 6, characterized in that The compound conforms to one of formulas (IA-1) to (IA-3), (IB-1) to (IB-3) and (IC-1).

9. A process for preparing a compound according to one or more of claims 1 to 8, characterized in that A compound containing a carbazole group, a dibenzofuran group or a dibenzothiophene group and a reactive Y group and a reactive W group first undergoes a Suzuki coupling reaction with a phenylboronic acid derivative, and then the resulting compound undergoes a Buchwald coupling reaction with a secondary amine, wherein the reactive W group is converted in the Suzuki coupling and the reactive Y group is converted in the Buchwald coupling.

10. An oligomer, polymer or dendrimer comprising one or more compounds according to one or more of claims 1 to 8, wherein one or more bonds to the polymer, oligomer or dendrimer may be located in the formula 1 , R 2 , R 3 or R 4 Substitute at any desired position.

11. A preparation comprising at least one compound according to one or more of claims 1 to 8 or at least one polymer, oligomer or dendrimer according to claim 10 and at least one solvent. 12 . An electronic device comprising at least one compound according to one or more of claims 1 to 8 or at least one polymer, oligomer or dendrimer according to claim 10 .

13. The electronic device according to claim 12, characterized in that The electronic device is an organic electroluminescent device and comprises an anode, a cathode and at least one light-emitting layer and is characterized in that the compound is present in a hole-transporting layer or in a light-emitting layer of the device.

14. Use of compounds according to one or more of claims 1 to 8 in electronic devices.

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