Compounds for electronic devices

Abstract

The present invention relates to a compound of formula (I), to a method for producing a compound of formula (I), to the use of a compound of formula (I) in an electronic device, and to an electronic device containing a compound of formula (I). # imgabs0 #

Description

[0001] The present invention relates to aromatic amines having a specific aromatic or heteroaromatic ring system 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 yet been found.

[0004] The light-emitting layer and the layer with hole transport function have a great influence on the performance data of the electronic device. New compounds used in 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. In addition, in order to be able to manufacture electronic devices containing the compound by means of a vapor deposition method, a sufficiently low sublimation temperature is of interest and is preferred. In addition, a sufficiently high HOMO of the compound is also of interest and is preferred. It is also being sought to cause improvements in the performance data of the device when used in the electronic device, especially compounds of 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 room for improvement in the above-mentioned properties.

[0006] It has now been found that aromatic amines of the following formula have excellent suitability, in particular when used in electronic devices, which are characterized in that they have a specific aromatic or heteroaromatic ring system on the amine nitrogen atom. They are particularly suitable for use in OLEDs, and even more particularly suitable for use therein as hole transport materials and as hole transport matrix materials, in particular hole transport matrix materials for phosphorescent emitters. These compounds lead to long life, high efficiency and low operating voltage of the devices. Also preferably, the compounds found have a high glass transition temperature, high stability, low sublimation temperature, good solubility, good synthetic accessibility, a sufficiently high HOMO and high hole conductivity.

[0007] The present application provides an electronic device, which comprises an anode, a cathode, a light-emitting layer, and a layer comprising a compound of formula (I), wherein the layer comprising the compound of formula (I) is arranged between the anode and the light-emitting layer.

[0008]

[0009] The variables that appear are as follows:

[0010] G is a group of formula (G), which is bonded to the rest of formula (I) via an unoccupied position on the benzene ring, wherein the other unoccupied positions on the benzene ring are each represented by R 1 Group substitution;

[0011]

[0012] X 1 O or S;

[0013] X 2 C(R 2 )2 or Si(R 2 )2;

[0014] X 3 C(R 2 )2 or Si(R 2 )2;

[0015] Ar L having 6 to 40 aromatic ring atoms and being R 3 An aromatic ring system substituted with a radical or having 5 to 40 aromatic ring atoms and being replaced by R 3 Group-substituted heteroaromatic ring systems;

[0016] Ar 1 ,Ar 2 are the same or different and have 6 to 40 aromatic ring atoms and are replaced by R 4 An aromatic ring system substituted with a radical or having 5 to 25 aromatic ring atoms and being replaced by R 4 A heteroaromatic ring system substituted with a radical, wherein Ar 1 and Ar 2 may optionally be linked together via a bond or an E group;

[0017] E is 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 or SO2;

[0018] 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 radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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;

[0019] R 2 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 2The radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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;

[0020] 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 3 The radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 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 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 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 the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 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 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 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 the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 6 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -R 6 C=CR 6 -、-C≡C-、Si(R 6 )2. C=O, C=NR 6 、-C(=O)O-、-C(=O)NR 6 -、NR6 、P(=O)(R 6 ), -O-, -S-, SO or SO2;

[0023] R 6 are in each case identical or different 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; and the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN;

[0024] n is 0 or 1, wherein when n=0, the G group and the nitrogen atom in formula (I) are directly bonded to each other.

[0025] In formula (G), it is shown that the following formula

[0026]

[0027] The group bonded to the group

[0028]

[0029] It means that in the rest of the formula shown above, the following two labels are Key

[0030]

[0031] Each comes from a different carbon atom of the benzene ring on the right, and the two The two carbon atoms bound by the bond are adjacent to each other in the benzene ring. This makes X 1 is part of a five-membered ring. According to the present application, no further restrictions should be inferred from the above definition. In particular, it cannot be inferred from X in formula (G) 1 The fact that it is indicated as "downward" infers that only embodiments of the type of formula (G-1), (G-3) and (G-5) shown below are covered. In contrast, formula (G) of the present application covers groups represented by formulas (G-1) to (G-6) as shown below

[0032]

[0033] All six geometrically feasible binding variants of. This definition is also applicable to all subformulas of formula (G) and formula (I) as shown below. Thus, it is also obvious that formula (G) covers the following alternative embodiments:

[0034]

[0035]

[0036] The formulae are defined the same as above for formula (G). Among the alternative embodiments of the aforementioned formula (G), formula (G-1) is preferred.

[0037] The following definitions are applicable to chemical groups used in this application. Unless any more specific definitions are given, they are applicable.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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".

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In a preferred embodiment, X 1 is O.

[0050] In a preferred embodiment, X 2 and X 3 Each is C(R 2 )2.

[0051] In a particularly preferred embodiment, X 1 O, X 2 and X 3 Each is C(R 2 )2.

[0052] Ar L Preferably selected from a group having 6 to 25 aromatic ring atoms and replaced by R 3 The aromatic ring system substituted by a group is more preferably selected from 3 substituted phenyl, biphenyl, naphthyl or fluorenyl, most preferably selected from R 3 A phenyl group substituted with a group.

[0053] Preferably, Ar L are in each case identical or different and are selected from the group consisting of:

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061] Therein, the dashed line represents a bond to the rest of the formula.

[0062] In a preferred embodiment, the index n=0. In an alternative preferred embodiment, the index n=1.

[0063] Ar 1 and Ar 2 are identical or different in each case and are selected from: 4 Aromatic ring systems substituted with a group, and having 5 to 25 aromatic ring atoms and being replaced by R 4 Group-substituted heteroaromatic ring systems.

[0064] Ar 1 and Ar 2 Preferably they are the same or different and are selected from the following formulae:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] 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 Ar-1 to Ar-276 groups shown also contain one or more R 4 Group.

[0083] Ar 1 and Ar 2 At least one of the groups is a radical having at least 12 aromatic ring atoms and is R 4 Aromatic ring systems substituted with radicals.

[0084] In a preferred embodiment, Ar 1 and Ar 2 are not bonded to each other via a bond or an E group.

[0085] R 1 are preferably identical or different in each case and are selected from: H, D, F, CN, Si(R5 )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 mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl group mentioned therein may be -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 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 Most preferably, R 1 For H.

[0086] R 2 are preferably identical or different in each case and are selected from: linear 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; wherein two or more R 2 The groups may be connected to one another and may form a ring; wherein the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl group mentioned therein may be -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 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms; wherein two or more R 2The groups may be connected to each other and may form a ring; the alkyl groups mentioned therein may each be replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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. Even more preferably, R 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms. Most preferably, R 2 It is methyl.

[0087] R 3 are preferably 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 mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl group mentioned therein may be -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 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.

[0088] R 4 are preferably identical or different in each case and are selected from: H, D, F, CN, Si(R 5 )3、N(R5 )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 mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl group mentioned therein may be -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, 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.

[0089] R 5 are preferably 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 mentioned are each replaced by R 6 and one or more CH2 groups in the alkyl group mentioned therein may be -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 5are identical or different in each case and are selected from: H, D, 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 6 Group substitution.

[0090] R 6 Preferably H.

[0091] Preferred embodiments of formulas (G-1) to (G-6) are shown below:

[0092]

[0093]

[0094]

[0095] The above formulae are each defined the same as the above formula (G). Among the above formulae, formulae (G-1-1) and (G-1-2) are particularly preferred, and formula (G-1-1) is very particularly preferred.

[0096] Preferred embodiments of formula (I) conform to the following formula:

[0097]

[0098]

[0099] The groups present therein are as defined above. Particularly preferably, X 2 and X 3 Here, each is C(R 2 ) 2. Even more preferably, X 1 is O.

[0100] Preferred embodiments of formula (I-1) to (I-4) conform to the following formula:

[0101]

[0102]

[0103] The groups present therein are as defined above. Particularly preferably, X 2 and X 3 Here, each is C(R 2 ) 2. Even more preferably, X 1 is O.

[0104] In a preferred embodiment, formula (I) complies with one of formula (I-1) and (I-3), especially formula (I-1). In a particularly preferred embodiment, formula (I) complies with one of formula (I-1-A) and (I-3-A), especially formula (I-1-A).

[0105] The preferred embodiment of formula (I-1) conforms to the following formula:

[0106]

[0107]

[0108] The variables occurring therein are as defined above and preferably correspond to the preferred embodiments thereof specified above. Among the formulae mentioned, formula (I-1-1) is particularly preferred.

[0109] Particularly preferred embodiments of formulae (I-1-1) to (I-1-4) are the following:

[0110]

[0111]

[0112] The variables occurring therein are as defined above and preferably correspond to the preferred embodiments thereof specified above. Among the formulae mentioned, formula (I-1-1-A) is particularly preferred.

[0113] The preferred embodiment of formula (I-2) conforms to the following formula:

[0114]

[0115]

[0116] The variables occurring therein are as defined above and preferably correspond to the preferred embodiments thereof specified above. Among the formulae, formulae (I-2-1), (I-2-3) and (I-2-4) are particularly preferred.

[0117] Particularly preferred embodiments of formulae (I-2-1) to (I-2-4) are the following:

[0118]

[0119]

[0120] The variables occurring therein are as defined above and preferably correspond to the preferred embodiments thereof specified above. Among the formulae mentioned, formula (I-2-1-A) is particularly preferred.

[0121] The preferred embodiment of formula (I-3) conforms to the following formula:

[0122]

[0123]

[0124] The variables present therein are as defined above and preferably correspond to their above-specified preferred embodiments.

[0125] Particularly preferred embodiments of formula (I-3-1) and (I-3-2) conform to the following formula:

[0126]

[0127]

[0128] The variables present therein are as defined above and preferably correspond to their above-specified preferred embodiments.

[0129] The preferred embodiment of formula (I-4) conforms to the following formula:

[0130]

[0131]

[0132] The variables occurring therein are as defined above and preferably correspond to the preferred embodiments thereof specified above. Among the formulae, formulae (I-4-1), (I-4-2) and (I-4-4) are particularly preferred. Formula (I-4-1) is very particularly preferred.

[0133] In an alternative preferred embodiment, formula (I) conforms to formula (I-4-3).

[0134] Preferred embodiments of formula (I-4-1) to (I-4-4) conform to the following formula:

[0135]

[0136]

[0137] The variables appearing therein are as defined above and preferably correspond to the preferred embodiments specified above. Among the formulae, formulae (I-4-1-A), (I-4-2-A) and (I-4-4-A) are particularly preferred; formula (I-4-1-A) is very particularly preferred.

[0138] In an alternative preferred embodiment, formula (I) conforms to formula (I-4-3-A).

[0139] In a preferred embodiment, formula (I) corresponds to one of the formulae (I-1-1), (I-1-2), (I-1-3), (I-1-4), (I-3-1), (I-3-2), (I-4-1), (I-4-2) and (I-4-4). Among the formulae mentioned, preferred embodiments of the formulae (I-1-1-A), (I-1-2-A), (I-1-3-A), (I-1-4-A), (I-3-1-A), (I-3-2-A), (I-4-1-A), (I-4-2-A) and (I-4-4-A) are preferred in each case.

[0140] In an alternative preferred embodiment, formula (I) conforms to one of formulas (I-2-1) and (I-2-2), in particular conforms to formulas (I-2-1-A) and (I-2-2-A).

[0141] In a preferred embodiment, formula (I) corresponds to one of the formulae (I-1-1), (I-1-2), (I-1-3), (I-1-4), (I-3-1), (I-3-2). Among the mentioned formulae, preferred embodiments of the formulae (I-1-1-A), (I-1-2-A), (I-1-3-A), (I-1-4-A), (I-3-1-A), (I-3-2-A) are preferred in each case.

[0142] In a preferred embodiment, formula (I) conforms to one of formulas (I-4-1), (I-4-2) and (I-4-4), preferably conforms to formula (I-4-1), especially conforms to formula (I-4-1-A), (I-4-2-A) and (I-4-4-A), preferably conforms to formula (I-4-1-A), and at least one of conditions a) and b) may be applicable:

[0143] a) R 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms; wherein two or more R 2 The groups may be connected to each other and may form a ring; the alkyl groups mentioned therein may each be replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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;

[0144] b) Mark n as 1.

[0145] In a preferred embodiment, both condition a) and condition b) are applicable.

[0146] In an alternative preferred embodiment, formula (I) conforms to formula (I-4-3), in particular to formula (I-4-3-A), wherein at least one of conditions a) and b) exists:

[0147] a) R 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms; wherein two or more R 2 The groups may be connected to each other and may form a ring; the alkyl groups mentioned therein may each be replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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;

[0148] b) Mark n as 1.

[0149] In a preferred embodiment, both conditions a) and b) exist. Such compounds are particularly suitable for use in a hole transport layer, which is also referred to as a "common layer" in the terminology of those skilled in the art and is not directly adjacent to the light-emitting layer, but is adjacent to another hole transport layer on the anode side, which in turn is adjacent to the light-emitting layer on the anode side.

[0150] In a preferred embodiment of formula (I), the following definitions of the variables are present in combination:

[0151] G is a group of formula (G), which is bonded to the rest of formula (I) via an unoccupied position on the benzene ring, wherein the other unoccupied positions on the benzene ring are each represented by R 1 Group substitution;

[0152] X 1 O or S;

[0153] X 2C(R 2 )2;

[0154] X 3 C(R 2 )2;

[0155] Ar L is selected from phenyl, biphenyl, naphthyl and fluorenyl, each of which is replaced by R 3 Group substitution;

[0156] Ar 1 ,Ar 2 are the same or different and have 6 to 40 aromatic ring atoms and are replaced by R 4 An aromatic ring system substituted with a radical or having 5 to 25 aromatic ring atoms and being replaced by R 4 Group-substituted heteroaromatic ring systems;

[0157] R 1 are identical or different in each case and are selected from: H, D, 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;

[0158] R 2 are identical or different in each case and are selected from: straight-chain alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms;

[0159] R 3 are identical or different in each case and are selected from: H, D, 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;

[0160] R 4 are identical or different in each case and are selected from: H, D, 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;

[0161] R 5are identical or different in each case and are selected from: H, D, 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 6 group substituted, and wherein R 6 The group is H;

[0162] n is 0 or 1.

[0163] The present application also relates to compounds of formula (I) as defined above, wherein, unlike the above definition, R 2 as follows:

[0164] R 2 are the same or different and are selected from: a linear alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; wherein two or more R 2 The groups may be connected to each other and may form a ring; wherein the alkyl groups mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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; preferably, R 2 are the same or different and are selected from: a linear alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; more preferably, R 2 It is methyl.

[0165] All other physical definitions mentioned above in connection with formula (I) are also considered to be preferred here. 2 The compounds of the formula (I) having this definition can generally be used in electronic devices, in particular in OLEDs, without being subject to the abovementioned mandatory use in a layer between anode and light-emitting layer.

[0166] The following compounds are preferred embodiments of the compounds of formula (I):

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180] The compounds of formula (I) can be prepared by the synthetic method described below. A person skilled in the art will be able to modify it within the scope of his knowledge in the art to prepare other compounds according to the present application that are not directly comparable to the method shown below.

[0181] The compounds of formula (I) can be prepared by different synthetic routes as described in detail below.

[0182] In the first variant (Scheme 1), in the Suzuki reaction (a), a benzene derivative having two carboxylate groups, a dibenzofuran or dibenzothiophene group and a halogen atom as substituents is coupled with a benzene derivative having an amino group and boronic acid as substituents. Thereafter, in the Grignard reaction (b), a metal organic group, preferably a magnesium organic group, is added to the carbonyl group of the carboxylate group. This forms a tertiary alcohol group on the benzene ring. These are cyclized in another step under acidic conditions to form an indenofluorenyl structure (c).

[0183]

[0184] X is O or S, Ar L and n and Ar 1 and Ar 2 As defined above. Hal is Cl, Br or I, preferably Cl. R is an organic group.

[0185] In a second variant (Scheme 2), steps a) to c) are carried out as described above in Scheme 1, except that in step a) a halogen-substituted phenyl group is used instead of an amine-substituted phenyl group. Subsequently, in step d), with Ar 1 Ar 2 N-Ar L -B(OR)2 group undergoes Suzuki coupling reaction or reacts with Ar 1 Ar 2 The NH group undergoes a Buchwald coupling reaction (d).

[0186]

[0187] X is O or S, Ar L and n and Ar 1 and Ar 2 As defined above. Hal is Cl, Br or I, preferably Cl. R is an organic group.

[0188] In a third variant (Scheme 3), steps a) to c) are carried out as shown in Scheme 1 above, except that in step a) an unsubstituted phenyl group is used instead of an amine-substituted phenyl group. After step c), borylation (d) is carried out, followed by reaction with compound Ar 1 Ar 2 N-Ar L -Hal performed Suzuki coupling (e).

[0189]

[0190] X、Ar L and n and Ar 1 and Ar 2 As defined above. Hal is Cl, Br or I, preferably Cl. R is an organic group.

[0191] In order to prepare compounds corresponding to the preferred embodiments of formula (I), according to one of the formulae (I-3), (I-3-A), (I-3-1), (I-3-2), (I-3-1-A) and (I-3-2-A), in which the amino group is bonded to the middle benzene ring of the indenofluorene, the process for the synthesis is preferably in accordance with substitution variant 4 (Scheme 4). This starts from a fluorenyl derivative having two halogen atoms on one benzene ring. This is similar to the compound Ar 1 Ar 2 N-Ar L -B(OR)2 or Ar 1 Ar 2NH undergoes Suzuki reaction or Buchwald reaction (step a), and then introduces a boronic acid group. Thereafter, in step b), a Suzuki reaction is carried out on the boronic acid group with a dibenzothiophene or dibenzofuran derivative having a carboxylate group. To the latter, a metal organic group is added, such as steps b) and c) of schemes 1 to 3, and an acid-catalyzed ring closure reaction is carried out, wherein a compound of formula (I) is obtained (step c) and step d)).

[0192]

[0193] X、Ar L and n and Ar 1 and Ar 2 As defined above. Hal is Cl, Br or I, preferably Cl. R is an organic group.

[0194] Those skilled in the art will be able to use the above method to obtain compounds of (I). They will also adjust, modify and optimize the method to the extent required within the scope of their known technical knowledge to prepare compounds of formula (I). The compounds shown above may each be substituted with an organic group at the position where they are shown as unsubstituted.

[0195] The present application therefore provides a process for preparing a compound of formula (I), characterized in that there is a sequence of at least one process step a) followed by a process step b), wherein process step a) comprises the following reaction, wherein the carboxylate group bound to the biphenyl unit in the ortho position of the bond between the two phenyl rings of the biphenyl unit is converted into a tertiary alcohol group by adding a metal organic group, preferably a Grignard reagent, and wherein process step b) comprises the following reaction, wherein the tertiary alcohol group obtained in process step a) undergoes a ring-closing reaction under acidic conditions, in particular an acidic ion exchange resin such as Amberlyst-15, thereby forming a fluorenyl unit from the biphenyl unit.

[0196] The process preferably comprises a further step selected from Suzuki coupling, Buchwald coupling and borylation.

[0197] The compounds of the above formula (I), 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.

[0198] 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.

[0199] 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.

[0200] 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 needed. 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.

[0201] 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.

[0202] The use of the compound of formula (I) according to the present application is described below:

[0203] 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.

[0204] 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).

[0205] 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.

[0206] 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).

[0207] 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.

[0208] 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.

[0209] The order of layers in the electronic device is preferably as follows:

[0210] -anode-

[0211] -Hole injection layer-

[0212] -Hole transport layer-

[0213] -Optional additional hole transport layer-

[0214] -Luminous layer-

[0215] -Optional hole blocking layer-

[0216] -Electron transport layer-

[0217] -Electron injection layer-

[0218] -cathode-.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] If the compound of the 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.

[0224] 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%.

[0225] 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.

[0226] Particularly preferred p-type dopants are the following substances: quinone dimethane compounds; azaindenofluorenediones; azaperibenzonaphthalene; azaterphenylidene; I2; metal halides, preferably transition metal halides; metal oxides, preferably metal oxides containing at least one transition metal or a metal from 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 bonding 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.

[0227] 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%.

[0228] Preferred p-type dopants are also the compounds explicitly described on pages 86-87 of the published specification WO 2021 / 156323 A1.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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, and most preferably 1:4 to 1:1.

[0237] 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 formula (I).

[0238] 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 components fulfil further functions.

[0239] The following material classes are preferably used in the above-mentioned layers of the device:

[0240] Phosphorescent emitters:

[0241] 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.

[0242] 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.

[0243] In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

[0244] 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:

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] Fluorescent luminescent body:

[0251] 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.

[0252] Matrix materials for fluorescent emitters:

[0253] 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.

[0254] Matrix materials for phosphorescent emitters:

[0255] 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.

[0256] Electron transport materials:

[0257] 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.

[0258] 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.

[0259] Preferred electron transport materials and electron injection materials are also the compounds explicitly shown on pages 73 to 75 of WO 2020 / 109434 A1.

[0260] Hole transport materials:

[0261] 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.

[0262] Preferred hole-transporting compounds are also the compounds explicitly described on pages 76 to 80 of WO 2020 / 109434 A1.

[0263] The following compounds HT-1 to HT-21 are particularly suitable for use in layers having a hole-transport function in OLEDs. This applies not only to the OLEDs defined and claimed in the present application, but also to OLEDs in general:

[0264]

[0265]

[0266]

[0267] Compounds HT-1 to HT-21 can generally be used in any hole transport layer of an OLED. The term "hole transport layer" herein refers to any layer of an OLED between the anode and the light-emitting layer. The term "OLED" is not particularly limited and applies to all OLEDs, especially OLED structures commonly used in the present application.

[0268] Compounds HT-1 to HT-21 can be prepared by the methods disclosed in the application texts listed in the above table under compounds HT-1 to HT-21, respectively. The teachings related to the use of the compounds and the methods for preparing the compounds in the above-mentioned application texts are hereby expressly incorporated into the present disclosure by reference. Compounds HT-1 to HT-21 have excellent properties, especially excellent lifetime and efficiency when used in OLEDs. This is especially true when they are used in the hole transport layer of OLEDs.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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).

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] The electronic device according to the present application comprises an anode, a cathode, a light-emitting layer and a layer containing a compound of formula (I), wherein the layer containing the compound of formula (I) is between the anode and the light-emitting layer, and the electronic device preferably has one or more of the preferred features mentioned above in connection with the electronic device containing the compound of formula (I).

[0278] In particular, with respect to the electronic device according to the present invention containing the compound of formula (I), it is preferably an OLED. More particularly, with respect to the device, it is preferred that it has a blue fluorescent light-emitting layer and the compound of formula (I) is in a hole transport layer, the hole transport layer is adjacent to another layer on the anode side, the other layer is adjacent to the light-emitting layer on the anode side. Alternatively, with respect to the device, it is preferred that it has a blue fluorescent or green phosphorescent light-emitting layer and the compound of formula (I) is in a hole transport layer, the hole transport layer is adjacent to the light-emitting layer on the anode side. Example

[0279] A) Synthesis Examples

[0280] Synthesis of Int-1a

[0281]

[0282] 15.4 g (35 mmol) of SM-1, 19.3 g (37 mmol) of BE-1 and 16.0 g (70 mmol) of potassium phosphate monohydrate were formed into an initial charge in 450 ml of THF / water (2:1). Subsequently, 883 mg (1.0 mmol) of XPhos palladacycle Gen. 3 were added and the mixture was stirred at 60°C. After the conversion was complete, the reaction mixture was cooled to room temperature and extracted twice with THF, dried over sodium sulfate, filtered and concentrated on a rotary evaporator. The residue was filtered through AlOx (heptane / toluene) and then concentrated. After crystallization from ethyl acetate and isopropanol, the product was isolated in solid form with an HPLC purity of >96%.

[0283] Yield: 20.9 g (27 mmol; 77%).

[0284] The following compounds can be prepared similarly:

[0285]

[0286]

[0287]

[0288] The borylation in the above-specified reaction is carried out analogously to the case of compound EG1 in WO 2019 / 170572.

[0289] Synthesis of Int-2a

[0290]

[0291] To the initial charge of 13.5 g (55 mmol) of cerium chloride (III), add 20.2 g (27 mmol) of Int-1a dissolved in 300 ml of THF, and stir the mixture at room temperature for one hour. The reaction mixture is cooled to 0 ° C, and at this temperature, 51.4 ml (154 mmol) of methylmagnesium chloride (solution in 3 M THF) is added dropwise and the mixture is stirred at this temperature for 45 minutes. Subsequently, the reaction mixture is stirred at room temperature for another two hours, and after conversion is completed, saturated aqueous ammonium chloride solution is carefully added. The suspension is expanded with 200 ml of water, and extracted three times with 200 ml of THF. The organic phase merged with sodium sulfate drying is filtered and concentrated to obtain the product in solid form.

[0292] Yield: 20.4 g (27 mmol; 100%).

[0293] The following compounds can be prepared similarly:

[0294]

[0295]

[0296] Synthesis of compound 1a

[0297]

[0298] To a solution of 20.2 g (27 mmol) of Int-2a in 500 ml of THF was added 3.7 g (38 mmol) of Amberlyst-15. The reaction mixture was stirred at 100 °C overnight until the conversion was complete, then filtered and concentrated on a rotary evaporator. The residue was extracted twice hot with toluene on AlOx and then crystallized repeatedly from toluene / heptane until HPLC purity >99.9%. Zone sublimation (10 -6 bar, 340° C.), the product was obtained in solid form.

[0299] Yield: 10.1 g (14 mmol; 53%).

[0300] The following compounds can be prepared similarly:

[0301]

[0302]

[0303] Int-3b-a and Int-3b-b formed as an isomeric mixture that could be separated by chromatography.

[0304] Synthesis of 2a

[0305]

[0306] 11.1 g (26 mmol) of Int-3a, 8.85 g (25 mmol) of 9,9-dimethylfluorenyl-2-(4-benzyl)amine, 3.5 g (37 mmol) of sodium tert-butoxide and 616 mg (0.73 mmol) of XPhos Pd Gen3 were suspended in 400 ml of toluene and stirred at 100 °C for 16 hours. After the conversion was complete, the reaction mixture was cooled to room temperature, filtered through alumina and washed with toluene. After removal of the solvent, the crude product was dissolved in 1:1 toluene / heptane and filtered through silica gel. Further purification was performed by repeated crystallization from heptane / toluene until the HPLC purity was >99.9%. Finally, two sublimations (310 °C, 10 -6 The product was obtained as a solid.

[0307] Yield: 7.5 g (10 mmol; 39%).

[0308] The following compounds can be prepared similarly:

[0309]

[0310]

[0311] Synthesis of Int-4

[0312]

[0313] 16.2 g (40 mmol) of Int-3d was suspended in 600 ml of THF and cooled to -45°C, 31 ml (43 mmol) of sec-BuLi (1.4 M solution in cyclohexane) was slowly added dropwise, and after the addition was completed, the mixture was stirred at -20°C for one hour. Subsequently, the reaction mixture was cooled to -35°C and 17.8 ml (80 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane was added dropwise, and the mixture was stirred at -20°C for 30 minutes. The reaction mixture was allowed to come to room temperature overnight. 50 ml of saturated aqueous ammonium chloride solution was gradually added to the reaction mixture, and the organic phase was expanded with ethyl acetate. The organic phase was washed twice with 200 ml of water, filtered and dried over sodium sulfate. The solvent was removed on a rotary evaporator to obtain the product in solid form.

[0314] Yield: 17.5 g (33.4 mmol; 84%).

[0315] Synthesis of 3a

[0316]

[0317] 12.1 g (23 mmol) of Int-4, 11.0 g (23 mmol) of bis(biphenyl-4-yl)(4-bromophenyl)amine (CAS 499128-71-1) and 8.8 g (23 mmol) of potassium phosphate monohydrate were suspended in 250 ml of THF / water (4:1). After addition of 483 mg (0.57 mmol) of XPhos palladacycle Gen3, the reaction mixture was stirred at 60 °C overnight until the conversion was complete. The reaction mixture was left to cool to room temperature, the precipitated solid was filtered off and washed with water, isopropanol and finally heptane. The residue was extracted four times hot with toluene on AlOx and crystallized from it until HPLC purity >99.9%. Zone sublimation (10 -6 bar, 360° C.), the product was obtained in solid form.

[0318] The following compounds can be prepared similarly:

[0319]

[0320] B) Device Examples

[0321] 1) General OLED manufacturing methods and OLED characterization

[0322] A glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm forms the substrate to which the OLED is applied.

[0323] An OLED essentially has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL1) / optional second hole transport layer (HTL2) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL1) / optional second electron transport layer (ETL2) / electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The exact structure of an OLED can be found in the table below. The materials required for the manufacture of an OLED are shown in the table below.

[0324] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer consists of the following materials: at least one matrix material (host material); and a luminescent dopant (luminophore) added to the matrix material in a specific volume ratio by co-evaporation. Details given in the form of, for example, H:SEB (95%:5%) mean here that material H is present in the layer in a volume ratio of 95% and SEB is present in the layer in a ratio of 5%. In a similar manner, the electron transport layer and the hole injection layer also consist of a mixture of two materials. The structures of the materials used in OLED are shown in the table below. ETM-2, used as an electron transport material in OLED Example 11, is a spirobifluorenyl-triazine derivative. EBM-2, used as a material for the electron blocking layer in OLED Example 11, is a triarylamino-substituted spirobifluorene.

[0325] OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum is determined, the external quantum efficiency (EQE, measured in %) is calculated as a function of the luminous density from the current-voltage-luminous density characteristic assuming Lambertian luminescence characteristics, and the lifetime is determined. The parameter EQE @ 10 mA / cm² refers to the external quantum efficiency obtained at 10 mA / cm². The lifetime LT is defined as the time after which the luminous density has fallen to a certain fraction of the starting luminous density during operation at a constant current density. The LT90 figure here means that the reported lifetime corresponds to the time after which the luminous density has fallen to 90% of its starting value. Figure @ 60 mA / cm 2Here, the lifetime in question is at 60 mA / cm 2 Measured below.

[0326] 2) Use in the electron blocking layer of blue fluorescent OLED:

[0327] An OLED with the following structure was manufactured:

[0328]

[0329] OLEDs 1-3 show that the compounds of the invention have excellent suitability as materials in OLEDs. As hole transport materials in this configuration, the OLEDs show very good performance and achieve very high external quantum efficiencies, as well as low operating voltages and very good lifetimes:

[0330]

[0331] 3) Use in hole transport layer and electron blocking layer of green phosphorescent OLED:

[0332] An OLED with the following structure was fabricated:

[0333]

[0334] OLED 4-7 shows that the compounds of the present invention have excellent applicability as materials for electron blocking layers of green phosphorescent OLEDs. OLEDs show very good performance as hole transport materials or electron blocking materials, and achieve low operating voltages, good external quantum efficiencies and excellent lifetimes:

[0335]

[0336] 3) Use in the hole transport layer of blue fluorescent OLED

[0337] An OLED with the following structure was fabricated:

[0338]

[0339] OLED 8-10 shows that the compounds of the present invention have excellent applicability as hole transport materials for blue fluorescent OLEDs. OLEDs show very good performance as hole transport materials and achieve low operating voltages, good external quantum efficiencies and excellent lifetimes:

[0340]

[0341] In addition, the following blue fluorescent OLEDs were fabricated:

[0342]

[0343] OLED 11 shows that the compounds of the present invention have excellent suitability as hole transport materials for blue fluorescent OLEDs. The OLEDs show very good performance as hole transport materials and achieve low operating voltages, good external quantum efficiencies and excellent lifetimes:

[0344]

[0345]

[0346]

Claims

1. An electronic device comprising an anode, a cathode, a light-emitting layer and a layer comprising a compound of formula (I), wherein the layer comprising the compound of formula (I) is arranged between the anode and the light-emitting layer, The variables that appear are as follows: G is a group of formula (G), which is bonded to the rest of formula (I) via an unoccupied position on the benzene ring, wherein the other unoccupied positions on the benzene ring are each represented by R 1 Group substitution; X 1 O or S; X 2 C(R 2 )2 or Si(R 2 )2; X 3 C(R 2 )2 or Si(R 2 )2; Ar L having 6 to 40 aromatic ring atoms and being R 3 An aromatic ring system substituted with a radical or having 5 to 40 aromatic ring atoms and being replaced by R 3 Group-substituted heteroaromatic ring systems; Ar 1 ,Ar 2 are the same or different and have 6 to 40 aromatic ring atoms and are replaced by R 4 An aromatic ring system substituted with a radical or having 5 to 25 aromatic ring atoms and being replaced by R 4 A heteroaromatic ring system substituted with a radical, wherein Ar 1 and Ar 2 may optionally be linked together via a bond or an E group; E is 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 or 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 radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 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 2 The radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 3 The radicals may be linked to one another and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl radicals mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 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 the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 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 the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned are each replaced by R 6 and one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned therein may be substituted with -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 in each case identical or different 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; and the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; n is 0 or 1, where When n=0, the G group and the nitrogen atom in formula (I) are directly bonded to each other.

2. The electronic device according to claim 1, characterized in that Formula (I) conforms to one of formulas (I-1-1), (I-1-2), (I-1-3), (I-1-4), (I-3-1), (I-3-2), wherein the variables appearing therein are as defined in claim 1, and wherein the other unoccupied positions on the phenyl ring are each replaced by R 1 The group substitution, in this case, R 1 The group is preferably H.

3. The electronic device according to claim 1, characterized in that Formula (I) conforms to one of formulas (I-4-1), (I-4-2) and (I-4-4), in particular conforms to formula (I-4-1), wherein the variables appearing therein are as defined in claim 1, and wherein the other unoccupied positions on the phenyl ring are each replaced by R 1 The group substitution, in this case, R 1 The group is preferably H.

4. The electronic device according to claim 1, characterized in that Formula (I) conforms to formula (I-4-3), wherein the variables appearing therein are as defined in claim 1, and wherein the other unoccupied positions on the phenyl ring are each replaced by R 1 The group substitution, in this case, R 1 The group is preferably H, and At least one of conditions a) and b) exists: a) R 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms; wherein two or more R 2 The groups may be connected to each other and may form a ring; the alkyl groups mentioned therein may each be replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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; b) Mark n as 1.

5. The electronic device according to any one of claims 1 to 4, characterized in that Ar L is selected from phenyl, biphenyl, naphthyl and fluorenyl, each of which is replaced by R 3 Group substitution, Ar L Preferably selected from 3 A phenyl group substituted with a group.

6. Electronic device according to one or more of claims 1 to 5, characterized in that Ar 1 and Ar 2 At least one of the groups is a radical having at least 12 aromatic ring atoms and is R 4 Aromatic ring systems substituted with radicals.

7. Electronic device according to one or more of claims 1 to 6, characterized in that R 2 are identical or different in each case and are selected from: straight-chain alkyl radicals having 1 to 20 carbon atoms and branched or cyclic alkyl radicals having 3 to 20 carbon atoms.

8. Electronic device according to one or more of claims 1 to 7, characterized in that The following combinations of definitions of variables exist: G is a group of formula (G), which is bonded to the rest of formula (I) via an unoccupied position on the benzene ring, wherein the other unoccupied positions on the benzene ring are each represented by R 1 Group substitution; X 1 O or S; X 2 C(R 2 )2; X 3 C(R 2 )2; Ar L is selected from phenyl, biphenyl, naphthyl and fluorenyl, each of which is replaced by R 3 Group substitution; Ar 1 ,Ar 2 are the same or different and are: having 6 to 40 aromatic ring atoms and being R 4 An aromatic ring system substituted with a radical or having 5 to 25 aromatic ring atoms and being replaced by R 4 Group-substituted heteroaromatic ring systems; R 1 are identical or different in each case and are selected from: H, D, 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 2 are identical or different in each case and are selected from: linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms; R 3 are identical or different in each case and are selected from: H, D, 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 4 are identical or different in each case and are selected from: H, D, 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, 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 6 group substituted, and wherein R 6 The group is H; n is 0 or 1.

9. The electronic device according to one or more of claims 1 to 8, characterized in that In the compounds of formula (I), the G group is selected from one of the following formulae: wherein the G group is bonded to the rest of the formula (I) via an unoccupied position on the benzene ring, wherein the other unoccupied positions on the benzene ring are each 1 The formula (G-1) to (G-6) are preferably substituted with a group, and among them, the formula (G-1) and (G-2) are preferred, and the formula (G-1) is particularly preferred.

10. Electronic device according to one or more of claims 1 to 9, characterized in that The layer comprising the compound of formula (I) is selected from a hole injection layer, a hole transport layer and an electron blocking layer.

11. A compound of formula (I), The variables G, X 1 , X 2 , X 3 ,Ar L ,Ar 1 ,Ar 2 , E, R 1 , R 3 , R 4 , R 5 , R 6 and n is defined according to one or more of claims 1, 5, 6, 7, 8 and 9, and in addition: R 2 are the same or different and are selected from: a linear alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; wherein two or more R 2 The groups may be connected to each other and may form a ring; wherein the alkyl groups mentioned are each replaced by R 5 and one or more CH2 groups in the alkyl groups mentioned therein 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; preferably, R 2 are the same or different and are selected from: a linear alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms; more preferably, R 2 It is methyl.

12. A method for preparing the compound according to claim 11, characterized in that There is a sequence of at least one process step a) followed by a process step b), wherein process step a) comprises a reaction in which the carboxylate groups bound to the biphenyl units in the ortho position to the bond between the two phenyl rings of the biphenyl units are converted into tertiary alcohol groups by adding a metal organic radical, preferably a Grignard reagent, and wherein process step b) comprises a reaction in which the tertiary alcohol groups obtained in process step a) are subjected to a ring-closing reaction under acidic conditions, in particular an acidic ion exchange resin such as Amberlyst-15, to form fluorenyl units from the biphenyl units.

13. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 11, wherein one or more bonds to the polymer, oligomer or dendrimer are located in the region of formula (I) where R 1 , R 2 , R 3 or R 4 Substitute at any desired position.

14. A preparation comprising at least one compound according to claim 11 or at least one polymer, oligomer or dendrimer according to claim 13 and at least one solvent.

15. An electronic device, especially an organic electroluminescent device, comprising at least one compound according to claim 11 or at least one polymer, oligomer or dendrimer according to claim 13.

16. Use of the compound according to claim 11 in electronic devices, especially organic electroluminescent devices.

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