Materials for electronic devices

Abstract

The present invention relates to compounds of formula (I) or formula (II), to processes for preparing compounds of this type, to electronic devices, in particular OLEDs, containing one or more of these compounds, and to the use of these compounds in electronic devices, in particular in OLEDs. # imgabs0 #

Description

[0001] The present application 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] In the context of the present application, an electronic device should be understood to mean a so-called organic electronic device comprising an organic semiconductor material as a functional material. More particularly, these should be understood to mean organic light-emitting diodes (OLEDs). The term OLED should be understood to mean an electronic device having one or more layers containing organic compounds and emitting light when a voltage is applied. The structure and general functional principle of OLEDs are known to those skilled in the art.

[0003] In electronic devices, especially OLEDs, there is great interest in improving the performance data. In these respects, no completely satisfactory solution has yet been found.

[0004] The light-emitting layer and the layer having a hole-transporting function have a great influence on the performance data of the electronic device. There is a continuing search for novel compounds for these layers, especially hole-transporting compounds and compounds which can be used as hole-transporting matrix materials in the light-emitting layer, especially for phosphorescent emitters. For this purpose, compounds having a high glass transition temperature, high stability and high hole conductivity are particularly sought. The high stability of the compound is a prerequisite for achieving a long lifetime of the electronic device. In addition, compounds are also sought which improve the performance data of the device when used in an electronic device, especially those which lead to high efficiency, long lifetime and low operating voltage.

[0005] In the prior art, triarylamine compounds, especially for example spirobifluoreneamine and fluoreneamine, are considered as hole-transporting materials and hole-transporting matrix materials for electronic devices. However, there is still room for improvement in the above properties.

[0006] It has now been found that aromatic amines of the following general formulae, which are characterized in that they have a specific aromatic or heteroaromatic ring system on the amine nitrogen atom, are very suitable for use in electronic devices. They are particularly suitable for use in OLEDs, and even more particularly as hole-transporting materials and as hole-transporting matrix materials, especially for phosphorescent emitters. The compounds lead to a high lifetime, high efficiency and low operating voltage of the device. More preferably, it has been found that the compounds have a high glass transition temperature, high stability, low sublimation temperature, good solubility, good synthetic accessibility and high hole conductivity.

[0007] Accordingly, the present application provides a compound of one of the following formulae:

[0008]

[0009] wherein:

[0010] W is the same or different in each case and is selected from O and S, preferably O;

[0011] Z is the same or different in each case and is selected from CR 1 and N, preferably CR 1 ;

[0012] i is 0 or 1, where when i = 0, the Y group is absent;

[0013] When i = 0, Z 1 is the same or different in each case and is selected from CR 1 and N;

[0014] When i = 1, Z 1 is C;

[0015] Y is the same or different in each case and is selected from a bond, C(R 1 )2, O and S;

[0016] Ar L is the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with R 2 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted with R 2 groups;

[0017] k is 0, 1, 2 or 3, where when k = 0, the Ar L group is absent, and the two groups bonded to Ar L in formula (I) and formula (II) are directly bonded to each other, where when k = 2, the two Ar L groups are chain-bonded in sequence, and where when k = 3, the three Ar L groups are chain-bonded in sequence;

[0018] Ar 1 is the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with R 4 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted with R 4 groups;

[0019] Ar 2 is the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with R 5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted with R 5 groups, where the aromatic or heteroaromatic ring system is connected to the V group and the nitrogen atom at the ortho position;

[0020] V is the same or different in each case and is selected from a bond, O, S, Si(R 5 )2 and C(R 5 )2;

[0021] R 1 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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; where two or more R 1 groups can be connected to each other and can form a ring; where the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each substituted by R 6 groups; and where one or more CH2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups can be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 (-), NR 6 , P(=O)(R 6 )-, -O-, -S-, SO or SO2;

[0022] R 2 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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; where two or more R2 The groups may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R 6 groups; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 ]-, NR 6 , P(=O)(R 6 )2, -O-, -S-, SO or SO2;

[0023] R 3 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 3 groups may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted by R 6 groups; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 ]-, NR 6 , P(=O)(R 6 )2, -O-, -S-, SO or SO2;

[0024] R 4 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6)3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 4 groups may be connected to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl, and alkynyl groups, and said aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl, and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 )、-O-、-S-、SO or SO2;

[0025] R 5 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 5 groups may be connected to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl, and alkynyl groups, and said aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl, and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6)2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2 is replaced;

[0026] R 6 is the same or different in each case and is selected from H, D, F, Cl, Br, I, C(=O)R 7 , CN, Si(R 7 )3, N(R 7 )2, P(=O)(R 7 )2, OR 7 , S(=O)R 7 , S(=O)2R 7 , a straight-chain 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 R 6 groups may be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring system and heteroaromatic ring system mentioned are each substituted by an R 7 group; and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R 7 C=CR 7 -, -C≡C-, Si(R 7 )2, C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 )-, -O-, -S-, SO or SO2 is replaced;

[0027] R 7 is the same or different in each case and is selected from H, D, F, Cl, Br, I, CN, an alkyl or alkoxy group having 1 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 R 7 groups may be connected to each other and may form a ring; and wherein the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring system and heteroaromatic ring system mentioned may be substituted by one or more groups selected from F and CN.

[0028] The representation shown in the ring is understood to mean R 3 group is bonded to each of the four free positions on said ring, where R 3 groups may be the same or different in each case.

[0029] For similar representations, such as the corresponding definitions apply, where R 1 group is bonded to the ring in question and has four or five free positions for bonding to said group, which may be the same or different in each case.

[0030] The following definitions apply to the chemical groups used in this application. They apply unless any more specific definition is given.

[0031] In the context of the present invention, an aryl group is understood to mean a simple aromatic ring, i.e., benzene, or a fused aromatic polycycle, such as naphthalene, phenanthrene or anthracene. In the context of this application, a fused aromatic polycycle consists of two or more simple aromatic rings fused to each other. The fusion between the rings is understood herein to mean that the rings share at least one edge with each other. In the context of the present invention, an aryl group contains 6 to 40 aromatic ring atoms. In addition, an aryl group does not contain any heteroatoms as aromatic ring atoms, but only contains carbon atoms as aromatic ring atoms.

[0032] In the context of the present invention, a heteroaryl group is understood to mean a simple heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. In the context of this application, a fused heteroaromatic polycycle consists of two or more simple aromatic or heteroaromatic rings fused to each other, where at least one of the aromatic and heteroaromatic rings is a heteroaromatic ring. The fusion between the rings is understood herein to mean that the rings share at least one edge with each other. In the context of the present invention, a heteroaryl group contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S.

[0033] An aryl or heteroaryl group each optionally substituted by the above groups is particularly understood to mean a group derived from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, terphenyl, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, benzimidazo[1,2-a]benzimidazole, naphthimidazole, phenanthrimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinimidazole, azole, benzo azole, naphtho azole, anthra azole, phenanthro azole, iso azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzo[c]carbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- diazole, 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.

[0034] In the context of the present invention, an aromatic ring system is a system that does not necessarily 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 tetrahydronaphthalene, fluorene and spirobifluorene. In addition, the term "aromatic ring system" includes systems composed of two or more aromatic ring systems connected to each other by single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3,5-diphenyl-1-phenyl. In the context of the present invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system and no heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0035] A heteroaromatic ring system conforms to the above definition of an aromatic ring system, but it must contain at least one heteroatom as a ring atom. As in the case of an aromatic ring system, a heteroaromatic ring system does not necessarily 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. The non-aromatic rings may contain only carbon atoms as ring atoms, or they may additionally contain one or more heteroatoms, where 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" should be understood to mean a system composed of two or more aromatic or heteroaromatic ring systems bonded to each other by single bonds, such as 4,6-diphenyl-2-triazinyl. In the context of the present invention, a heteroaromatic ring system contains 5 to 40 ring atoms selected from carbon and heteroatoms, where at least one of the ring atoms is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.

[0036] Thus, as defined in the present application, the terms "heteroaromatic ring system" and "aromatic ring system" differ from each other in that an aromatic ring system cannot have a heteroatom as a ring atom, while a heteroaromatic ring system must have at least one heteroatom as a ring atom. The heteroatom can be present as a ring atom of a non-aromatic heterocycle or as a ring atom of an aromatic heterocycle.

[0037] According to the above definitions, the term "aromatic ring system" encompasses any aryl group, and the term "heteroaromatic ring system" encompasses any heteroaryl group.

[0038] An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms should in particular be understood to refer to groups derived from the groups mentioned above under aryl groups and heteroaryl groups, and groups derived from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indeno[1,2-b]fluorene, triphenylene, isotriphenylene, spirotriphenylene, spiroisotriphenylene, indeno[2,1-b]carbazole or combinations of these groups.

[0039] In the context of the present invention, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and an alkenyl or alkynyl group having 2 to 40 carbon atoms, in which individual hydrogen atoms or CH2 groups can also be replaced by the groups mentioned above in the group definitions, should preferably be understood to refer to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl groups.

[0040] An alkoxy or thioalkyl group having 1 to 20 carbon atoms, wherein individual hydrogen atoms or CH2 groups may also be substituted by the groups mentioned above in the definition of the group, is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0041] In the context of the present application, the phrase two or more groups together may form a ring should be understood to mean in particular that two groups are connected to each other by a chemical bond. However, in addition, the above phrase should also be understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded, thereby forming a ring.

[0042] In a preferred embodiment, Z is CR 1 . In an alternative preferred embodiment, Z is the same or different in each case and is selected from CR 1 and N, where no more than one Z group ring is N.

[0043] The label i is 0 or 1, where when i = 0, the Y group is absent and the Z 1 groups are the same or different in each case and are selected from CR 1 and N. Preferably, when i = 0, Z 1 is CR 1 .

[0044] If i = 1, then the Y group is present and is the same or different in each case and is selected from a bond, C(R 1 )2, O or S, preferably a bond or C(R 1 )2, more preferably a bond.

[0045] In a particularly preferred configuration, i = 1 and Y is a bond. In this configuration, a spirobifluorene skeleton is formed. When i = 0 and Z 1 is CR 1is also superior to other embodiments where i = 1. However, the configuration where i = 1 and Y is a bond is superior to the embodiment where i = 0 and Z 1 is CR 1 .

[0046] In a preferred embodiment, W is O in each case.

[0047] Ar L is the same or different in each case and is selected from aromatic ring systems having 6 to 25 aromatic ring atoms and substituted with R 2 groups and heteroaromatic ring systems having 5 to 25 aromatic ring atoms and substituted with R 2 groups; more preferably the same or different in each case and selected from phenyl, biphenyl, naphthyl and fluorenyl each substituted with R 2 groups; most preferably selected from phenyl substituted with R 2 groups.

[0048] Preferably, Ar L is the same or different in each case and is selected from groups of the following formulas:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] where the dashed line represents a bond connecting to the rest of the formulas, and where the formulas Ar L -1, formula Ar L -2 and formula Ar L -3 are particularly preferred.

[0055] It is also possible that Ar L is the same or different in each case and is selected from phenyl, biphenyl, naphthyl and fluorenyl each substituted with R 2 groups, preferably phenyl and biphenyl, more preferably phenyl.

[0056] Ar 1 is the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with R 4 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted with R 4 groups. Preferably, Ar 1Identical or different in each case and selected from aromatic ring systems having 6 to 25 aromatic ring atoms and substituted by R 4 groups and heteroaromatic ring systems having 5 to 25 aromatic ring atoms and substituted by R 4 groups.

[0057] Preferred Ar 1 groups are identical or different in each case and selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene (especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene), benzofluorene, spirobifluorene, indeno[1,2-b]fluorene, indeno[2,1-a]carbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, wherein each of said monovalent groups is substituted by R 4 groups. Ar 1 groups are also preferably identical or different in each case and selected from combinations of 2 to 4 groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene (especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene), benzofluorene, spirobifluorene, indeno[1,2-b]fluorene, indeno[2,1-a]carbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, wherein each of said monovalent groups is substituted by R 4 groups. More preferably, Ar 1 groups are identical or different in each case and selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, fluorene, benzofluorene, spirobifluorene, more preferably derived from biphenyl, terphenyl, fluorene, spirobifluorene, wherein each of said monovalent groups is substituted by R 4 groups.

[0058] Ar 1 is preferably identical or different in each case and selected from groups of the following formulas:

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] wherein the dashed line represents a bond connected to a nitrogen atom, and wherein the group may be substituted by an R 4 group at the position shown as unsubstituted, preferably only H at the position shown as unsubstituted. Among the above groups, preferably Ar 1 -1 to Ar 1 -106 and Ar 1 -139 to Ar 1 -271 groups, particularly preferably Ar 1 -2 to Ar 1 -106 and Ar 1 -139 to Ar 1 -271 groups. Very particularly preferably one or two Ar 1 groups, preferably two Ar 1 groups are each independently selected from Ar 1 -2, Ar 1 -5, Ar 1 -48, Ar 1-50, Ar 1 -74, Ar 1 -78, Ar 1 -140, Ar 1 -141, Ar 1 -144, Ar 1 -149, Ar 1 -193, Ar 1 -195, Ar 1 -257 to Ar 1 -264, Ar 1 -265, Ar 1 -266, Ar 1 -268 and Ar 1 -271 groups.

[0079] Preferably, both Ar 1 groups are selected from the groups of formula (Ar 1 -1) to formula (Ar 1 -10) and formula (Ar 1 -139) to formula (Ar 1 -171) as defined above.

[0080] Among formula (Ar 1 -1) to formula (Ar 1 -10), preferably formula (Ar 1 -1), formula (Ar 1 -2), formula (Ar 1 -3), formula (Ar 1 -6), formula (Ar 1 -7), formula (Ar 1 -8) and formula (Ar 1 -9).

[0081] In an alternative embodiment, it may be preferred that one or both Ar 1 groups, preferably both Ar 1 groups, are selected from the groups Ar 1 -2, Ar 1 -5, Ar 1 -48, Ar 1 -50, Ar 1 -78, Ar 1 -140, Ar 1 -141, Ar 1 -149, Ar 1 -139 to Ar 1 -171, Ar 1 -193, Ar 1 -265, Ar 1-266, Ar 1 -268 and Ar 1 -271, more preferably Ar 1 -2, Ar 1 -139 and Ar 1 -141.

[0082] In a preferred embodiment, Ar 1 groups do not contain a carbazole group as substituent R 4 , R 6 or R 7 .

[0083] It is preferably the case that two Ar 1 groups are connected only via the nitrogen atom bonded to the two Ar 1 groups, rather than via a substituent R 4 , R 6 or R 7 that can form a ring system.

[0084] Ar 2 is the same or different in each case and is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by R 5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted by R 5 groups. Preferably, Ar 2 is the same or different in each case and is selected from aromatic ring systems having 6 to 25 aromatic ring atoms and substituted by R 5 groups and heteroaromatic ring systems having 5 to 25 aromatic ring atoms and substituted by R 5 groups.

[0085] Preferred Ar 2 groups are the same or different in each case and are selected from vicinal divalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene (especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene), benzofluorene, spirobifluorene, indenofluorene, indolocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the divalent groups is substituted by R 5 groups. In addition, preferably, Ar 2 groups are the same or different in each case and are selected from combinations of 2 to 4 groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene (especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene), benzofluorene, spirobifluorene, indenofluorene, indolocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the groups is substituted by R5 Group substitution. More preferably, Ar 2 Groups are the same or different in each case and are selected from vicinal divalent groups, said vicinal divalent groups being derived from benzene, biphenyl, terphenyl, quaterphenyl, fluorene, benzofluorene, spirobifluorene, more preferably derived from biphenyl, terphenyl, fluorene, spirobifluorene, wherein said divalent groups are each substituted by R 5 Groups.

[0086] Ar 2 Are preferably the same or different in each case and are selected from groups of the following formulas:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Wherein the dashed line represents a bond connected to a nitrogen atom or a bond connected to a V group, and wherein the group may be substituted by R 5 Groups, preferably only H at the positions shown as unsubstituted. Among the above groups, preferably Ar 2 -1 to Ar 2 -79 and Ar2 -104 to Ar 2 -220 group, particularly preferably Ar 2 -2 to Ar 2 -47 and Ar 2 -104 to Ar 1 -220 group. Very particularly preferably one or two Ar 2 groups, preferably two Ar 2 groups are each independently selected from Ar 2 -2, Ar 2 -4, Ar 2 -35, Ar 2 -37, Ar 2 -107, Ar 2 -109, Ar 2 -110, Ar 2 -111, Ar 2 -125, Ar 2 -126, Ar 2 -213, Ar 2 -214, Ar 2 -215 and Ar 2 -220 group.

[0103] Preferably, two Ar 2 are each independently selected from the groups of formula (Ar 2 -1) to formula (Ar 2 -7) and formula (Ar 2 -104) to formula (Ar 2 -151) as defined above.

[0104] Among formula (Ar 2 -1) to formula (Ar 2 -7), preferably formula (Ar 2 -1), formula (Ar 2 -2), formula (Ar 2 -3), formula (Ar 2 -4) and formula (Ar 2 -5).

[0105] In an alternative embodiment, it may be preferred that one or two Ar 2 groups, preferably two Ar 2 groups are each independently selected from Ar 2 -2, Ar 2 -4, Ar 2 -35, Ar 2 -37, Ar 2 -107, Ar 2 -109, Ar 2-110, Ar 2 -111, Ar 2 -125, Ar 2 -126, Ar 2 -213, Ar 2 -214, Ar 2 -215 and Ar 2 -220 groups, more preferably selected from Ar 2 -2, Ar 2 -104 and Ar 2 -105.

[0106] In a preferred embodiment, Ar 2 group does not contain a carbazole group as substituent R 5 , R 6 or R 7 .

[0107] In a preferred embodiment, V is selected from a bond, O, Si(R 5 )2 and C(R 5 )2, preferably a bond, Si(R 5 )2 and C(R 5 )2. More preferably, V is a bond. In this case, together with the Ar 2 group and the nitrogen atom, a carbazole-type structure is formed.

[0108] R 1 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R 6 )3, N(R 6 )2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned, and the heteroaromatic ring system mentioned are each substituted by R 6 groups; and one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -. More preferably, R 1 is the same or different in each case and is selected from H, D, F, CN, Si(R 6)3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14, aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by R 6 groups.

[0109] Preferably, in a compound of one of formula (I) and formula (II), each formula has zero, one, two, or three R 1 groups that are not H or D. These groups that are not H or D are preferably selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14, aromatic ring atoms, and a heteroaryl group having 5 to 40, preferably 5 to 25, more preferably 6 to 14, aromatic ring atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by R 6 groups. Preferably, zero or one of the R 1 groups in each formula is not H or D, and more preferably zero of the R 1 groups in each formula is not H or D.

[0110] More preferably, all of the R 1 groups in formula (I) and formula (II) are H or D, and more preferably H.

[0111] In an alternative configuration, it may be preferable that a compound of one of formula (I) and formula (II) has at least one R 1 group selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted by R 6 groups; a compound of one of formula (I) and formula (II) more preferably has at least one R 1 group selected from aryl groups having 6 to 25, preferably 6 to 14, aromatic ring atoms and substituted by R 6 groups.

[0112] In an alternative embodiment, it may be more preferable that a compound of one of formula (I) and formula (II) has at least one R 1 group that is a phenyl group substituted by R 6 groups.

[0113] R 2 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R 6 )3, N(R 6) 2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned, and the heteroaromatic ring system mentioned are each substituted by R 6 groups; and one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -.

[0114] More preferably, R 2 is the same or different in each case and is selected from H, D, F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, more preferably 6 to 14 aromatic ring atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by R 6 groups.

[0115] Preferably, in the compound of one of formula (I) and formula (II), each formula has zero, one, two or three R 2 groups that are not H or D. These groups that are not H or D are preferably selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, more preferably 6 to 14 aromatic atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by R 6 groups. Preferably, zero or one of the R 2 groups in each formula is not H or D, and more preferably zero of the R 2 groups in each formula is not H or D.

[0116] R 3 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R 6)3, N(R 6 )2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned, and the heteroaromatic ring system mentioned are each substituted by R 6 groups; and one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -.

[0117] Preferably, in a compound of one of formula (I) and formula (II), each formula has zero, one, two or three R 3 groups that are not H or D. These groups that are not H or D are preferably selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, more preferably 6 to 14 aromatic atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by R 6 groups. Preferably, zero or one of the R 3 groups in each formula is not H or D, and more preferably zero of the R 3 groups in each formula is not H or D.

[0118] More preferably, all R 3 groups in formula (I) and formula (II) are H or D, and more preferably H.

[0119] In an alternative configuration, it may be preferable that a compound of one of formula (I) and formula (II) has at least one R 3 group selected from an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by R 6 groups; a compound of one of formula (I) and formula (II) more preferably has at least one R 3 group selected from an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms and substituted by R 6 groups.

[0120] In an alternative embodiment, it may be more preferred that a compound of formula (I) or formula (II) has at least one R 3 group being a phenyl group substituted by an R 6 group.

[0121] It may be preferred that all R 1 and R 3 groups in formula (I) and formula (II) are H or D.

[0122] R 4 is preferably the same or different in each case and is selected from H, D, F, CN, Si(R 6 )3, N(R 6 )2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned, and the heteroaromatic ring system mentioned are each substituted by an R 6 group; and one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -.

[0123] Preferably, in a compound of formula (I) or formula (II), zero, one, two, three, or four R 1 groups of each Ar 4 group are not H or D. These groups that are not H or D are preferably selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, more preferably 6 to 14 aromatic atoms, wherein the alkyl group, the aryl group, and the heteroaryl group are each substituted by an R 6 group. It is preferred that zero, one, or two of the R 4 groups in each formula are not H or D, and more preferably zero or one of the R 4 groups in each formula are not H or D.

[0124] R5 Preferably the same or different in each case and selected from H, D, F, CN, Si(R 6 )3, N(R 6 )2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned are each substituted by R 6 groups; and wherein one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 -.

[0125] Preferably, in a compound of one of formula (I) and formula (II), zero, one, two, three or four R 2 groups of each Ar 5 group are not H or D. These groups which are not H or D are preferably selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms and a heteroaryl group having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, more preferably 6 to 14 aromatic atoms, wherein the alkyl group, the aryl group and the heteroaryl group are each substituted by R 6 groups. Preferably zero, one or two of the R 5 groups in each formula are not H or D, more preferably zero or one of the R 5 groups in each formula are not H or D.

[0126] R 6 Preferably the same or different in each case and selected from H, D, F, CN, Si(R 7 )3, N(R 7 )2, a straight-chain 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 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 and alkoxy groups mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned are each substituted by R7 Group substitution; and one or more CH2 groups in the alkyl or alkoxy groups mentioned may be replaced by -C≡C-, -R 7 C=CR 7 -, Si(R 7 )2, C=O, C=NR 7 , -NR 7 -, -O-, -S-, -C(=O)O- or -C(=O)NR 7 -.

[0127] Formula (I) preferably conforms to one of the following formulas:

[0128]

[0129] The groups present are the same as those defined above.

[0130] The preferred embodiments of the above formulas conform to the following formula:

[0131]

[0132]

[0133] The groups present are the same as those defined above. Formula (II) preferably conforms to one of the following formulas:

[0134]

[0135] The groups present are the same as those defined above. The preferred embodiments of the above formulas conform to the following formula:

[0136]

[0137]

[0138] The groups present are the same as those defined above. The preferred compounds according to the present application are as follows:

[0139]

[0140]

[0142]

[0143]

[0144]

[0145]

[0146] The compounds according to the present application can be prepared using the synthetic methods described below.

[0147] According to the method shown in Scheme 1, the Hartwig - Buchwald coupling can start from an indeno[1,2 - b:5,4 - b']difuran derivative, whereby an amino group is introduced into the molecule. The compound according to the present application is thus obtained, where the label k = 0.

[0148] Scheme 1

[0149]

[0150] As shown in Schemes 2 and 3, an alternative is the Suzuki coupling, whereby an aromatic ring system is introduced into the molecule. The compound according to the present application is thus obtained, where the label k>0.

[0151] Scheme 2

[0152]

[0153] Scheme 3

[0154]

[0155] The definitions of the variable groups in the schemes shown above are the same as those defined above, where the other groups are as follows:

[0156] R = H or an organic group

[0157] Q = a reactive group

[0158] Ar = an optionally substituted aromatic or heteroaromatic group, corresponding to Ar defined above L 、Ar 1 、Ar 2 and the V group.

[0159] Accordingly, the present application provides a method for preparing a compound according to the present application, characterized in that an indeno[1,2-b:5,4-b']dibenzofuran derivative a) substituted with a reactive group reacts with a secondary amine in a coupling reaction, or b) reacts with an aromatic or heteroaromatic substance bearing a reactive group in a coupling reaction. In variant b), the reactive group on the indeno[1,2-b:5,4-b']dibenzofuran derivative preferably contains boron, and the reactive group on the aromatic or heteroaromatic system is preferably selected from Cl, Br, and I. Alternatively, the reactive group on the indeno[1,2-b:5,4-b']dibenzofuran derivative is selected from Cl, Br, and I, and the reactive group on the aromatic or heteroaromatic system preferably contains boron. In a first embodiment of variant b), the indeno[1,2-b:5,4-b']dibenzofuran derivative substituted with a reactive group reacts with an aromatic or heteroaromatic system bearing a boron-containing group in a coupling reaction. In a second embodiment of variant b), the indeno[1,2-b:5,4-b']dibenzofuran derivative substituted with a boron-containing group reacts with an aromatic or heteroaromatic system bearing a reactive group in a coupling reaction.

[0160] For a particular reaction, the reactive groups are known to the person skilled in the art. One of the said reactive groups is preferably selected from Cl, Br, and I, more preferably from Br and I. a) The coupling reaction in the following reaction is preferably a Hartwig-Buchwald coupling reaction. b) The following coupling reaction is preferably a Suzuki coupling reaction. In the Suzuki coupling reaction, it is preferred to select one reactive group as described above, and the other reactive group is preferably a group containing a boron atom, preferably a boric acid or borate group.

[0161] The indeno[1,2-b:5,4-b']dibenzofuran derivative substituted with a reactive group is preferably prepared by reacting a dibenzofuran derivative substituted with two reactive groups with a carbonyl compound in an organometallic addition reaction.

[0162] Compounds having a group containing a boron atom (preferably a boric acid or borate group) can preferably be obtained by reacting with an organometallic compound (preferably an organolithium compound). Unsubstituted indeno[1,2-b:5,4-b']dibenzofuran derivatives can also be used here. In addition, by reacting with an organometallic compound (preferably an organolithium compound), unsubstituted indeno[1,2-b:5,4-b']dibenzofuran derivatives can also be used to obtain indeno[1,2-b:5,4-b']dibenzofuran derivatives having a reactive group selected from Cl, Br, and I, more preferably from Br and I.

[0163] The process procedures and synthesis stages detailed above are particularly disclosed in the documents WO 2015 / 090504 and WO 2015 / 022051 A1. These publications are hereby expressly incorporated herein by reference.

[0164] The compounds of the present invention described above, in particular those substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or borate esters, can be used as monomers for the production of the corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boric acid, borate esters, amines, alkenyl or alkynyl groups having a terminal C-C double bond or C-C triple bond, ethylene oxide, oxetane, groups participating in cycloaddition (e.g., 1,3-dipolar cycloaddition), such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0165] Accordingly, the present invention also provides an oligomer, polymer or dendrimer, said oligomer, polymer or dendrimer containing one or more compounds of formula (I) or formula (II), wherein one or more of the bonds connecting to the polymer, oligomer or dendrimer may be located at any desired position substituted by R 1 、R 2 、R 3 、R 4 or R 5 in formula (I) or formula (II). Depending on the connection of the compounds of formula (I) or formula (II), the compounds are part of the side chain or the main chain of the oligomer or polymer. In the context of the present invention, an oligomer should be understood to mean a compound formed from at least three monomer units. In the context of the present invention, a polymer should be understood to mean a compound formed from at least ten monomer units. The polymers, oligomers or dendrimers of the present invention can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers of the present invention can be linear, branched or dendritic. In a structure with linear connection, the units of formula (I) or formula (II) can be directly connected to each other, or they can be connected to each other through a divalent group, such as through a substituted or unsubstituted alkylene group, through a heteroatom or through a divalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units of formula (I) or formula (II) can be connected through a trivalent or higher-valent group, such as through a trivalent or higher-valent aromatic or heteroaromatic group, to produce a branched or dendritic oligomer or polymer.

[0166] For the repeating units of formula (I) or formula (II) in oligomers, dendrimers and polymers, the preferred options described above for the compounds of formula (I) or formula (II) also apply.

[0167] To prepare the oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorene, spirobifluorene, phenylene, carbazole, thiophene, dihydrophenanthrene, cis- and trans-indeno[1,2-b]fluorene, ketone, phenanthrene or two or more of these units. The polymers, oligomers and dendrimers usually also contain other units, such as luminescent (fluorescent or phosphorescent) units, such as vinyltriarylamine or phosphorescent metal complexes, and / or charge transport units, especially those based on triarylamine.

[0168] The polymers, oligomers and dendrimers of the present invention have advantageous properties, especially high lifetime, high efficiency and good color coordinates.

[0169] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomer types, wherein at least one monomer results in repeating units of formula (I) or formula (II) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that produce C-C and C-N couplings are as follows:

[0170] (A) Suzuki polymerization;

[0171] (B) Yamamoto polymerization;

[0172] (C) Stille polymerization; and

[0173] (D) Hartwig-Buchwald polymerization.

[0174] How to carry out the polymerization by these methods and then how to separate and purify the polymer from the reaction medium are known to those skilled in the art and are described in detail in the literature.

[0175] To process the compounds of the present invention from the liquid phase, for example, by spin coating or by printing methods, formulations of the compounds of the present invention are required. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, decalin, veratrole, THF, methyl-THF, THP, chlorobenzene, di Alkane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenyl ethyl 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.

[0176] Therefore, the present invention also provides a formulation, especially a solution, dispersion or emulsion, which contains at least one compound of formula (I) or formula (II) or at least one polymer, oligomer or dendrimer containing at least one unit of formula (I) or formula (II), and at least one solvent, preferably an organic solvent. The manner of preparing such a solution is known to those skilled in the art.

[0177] The compounds of formula (I) or formula (II) are suitable for use in electronic devices, especially in organic light-emitting diodes (OLEDs). Depending on the substitution, the compounds of formula (I) or formula (II) can be used in different functions and layers. Preferably, they are used as hole-transporting materials in the hole-transporting layer and / or as matrix materials in the light-emitting layer, more preferably in combination with phosphorescent emitters.

[0178] Therefore, the present invention also provides the use of the compounds of formula (I) or formula (II) in electronic devices. The electronic device is preferably selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic light-emitting transistors (OLET), organic solar cells (OSC), organic photodetectors, organic photoreceptors, organic field quenching devices (OFQD), organic light-emitting electrochemical cells (OLEC), organic laser diodes (O-lasers), more preferably organic light-emitting diodes (OLEDs).

[0179] The present invention also provides an electronic device containing at least one compound of formula (I) or formula (II). The electronic device is preferably selected from the above devices.

[0180] Particularly preferred is an organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, characterized in that there is at least one organic layer in the device containing at least one compound of formula (I) or formula (II). Preferred is an organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, characterized in that at least one organic layer selected from the hole-transporting layer and the light-emitting layer in the device contains at least one compound of formula (I) or formula (II).

[0181] The hole-transporting layer should be understood herein to mean all the layers provided between the anode and the light-emitting layer, preferably the hole injection layer, the hole transport layer and the electron blocking layer. The hole injection layer should be understood herein to mean the layer directly adjacent to the anode. The hole transport layer should be understood herein to mean the layer located 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 either. The electron blocking layer should be understood herein to mean the layer located 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 and thus prevents electrons from escaping from the light-emitting layer.

[0182] In addition to the cathode, anode and light-emitting layer, the electronic device may further comprise other layers. For example, these are in each case selected from one or more of the hole injection layer, the hole transport layer, the hole blocking layer, the electron transport layer, the electron injection layer, the electron blocking layer, the exciton blocking layer, the intermediate layer, the charge generation layer and / or the organic or inorganic p / n junction. However, it should be noted that not all of these layers are necessarily present, and the selection of layers always depends on the compounds used, in particular also on whether the device is a fluorescent electroluminescent device or a phosphorescent electroluminescent device.

[0183] The order of the layers in the electronic device is preferably as follows:

[0184] - Anode -

[0185] - Hole injection layer -

[0186] - Hole transport layer -

[0187] - Optionally other hole transport layers -

[0188] - Light-emitting layer -

[0189] - Optionally hole blocking layer -

[0190] - Electron transport layer -

[0191] - Electron injection layer -

[0192] - Cathode -.

[0193] At the same time, it should be noted again that not all of the mentioned layers need to be present and / or other layers may additionally be present.

[0194] The organic electroluminescent device of the present invention may contain two or more light-emitting layers. More preferably, these light-emitting layers altogether have a plurality of emission peaks between 380 nm and 750 nm, such that the overall result is white light emission; in other words, a variety of light-emitting compounds that can emit fluorescence or phosphorescence and emit blue, green, yellow, orange or red light are used in the light-emitting layer. A three-layer system, i.e., a system having three light-emitting layers, is particularly preferred, wherein one of the three layers exhibits blue light emission in each case, one of the three layers exhibits green light emission in each case, and one of the three layers exhibits orange or red light emission in each case. The compounds of the present invention are preferably present in the hole-transporting layer or the light-emitting layer herein. It should be noted that in order to generate white light, it may also be suitable to use a luminescent compound that emits light in a wide wavelength range alone instead of a luminescent compound that emits light of multiple colors.

[0195] Preferably, a compound of formula (I) or formula (II) is used as the hole-transporting material. The light-emitting layer herein may be a fluorescent light-emitting layer, or it may be a phosphorescent light-emitting layer. The light-emitting layer is preferably a blue fluorescent layer or a green phosphorescent layer.

[0196] When the device containing a compound of formula (I) or formula (II) contains a phosphorescent light-emitting layer, preferably this layer contains two or more, preferably exactly two different host materials (mixed host system). The preferred embodiments of the mixed host system are described in more detail below.

[0197] If the compound of formula (I) or formula (II) is used as the hole-transporting material in the hole-transporting layer, the hole-injecting layer or the electron-blocking layer, the compound may be used as a pure material, i.e., used in a proportion of 100% in the hole-transporting layer, or it may be used in combination with one or more other compounds.

[0198] In a preferred embodiment, the hole-transporting layer containing a compound of formula (I) or formula (II) further contains one or more other hole-transporting compounds. These other hole-transporting compounds are preferably selected from triarylamine compounds, more preferably selected from mono-triarylamine compounds. They are most preferably selected from the preferred embodiments of the hole-transporting materials described further below. In the described preferred embodiments, the compound of formula (I) or formula (II) and one or more other hole-transporting compounds are preferably each present in a proportion of at least 10%, more preferably each present in a proportion of at least 20%.

[0199] In a preferred embodiment, the hole-transporting layer containing a compound of formula (I) or formula (II) further contains one or more p-type dopants. The p-type dopants used according to the present invention are preferably organic electron acceptor compounds that can oxidize one or more other compounds in the mixture.

[0200] Particularly preferred as p-type dopants are quinodimethane compounds, azaindene diones, aza-phenalenes, aza-triphenylenes, I2, metal halides (preferably transition metal halides), metal oxides (preferably metal oxides containing at least one transition metal or group 3 main group metal), and transition metal complexes (preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a binding site). Also preferred as dopants are transition metal oxides, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. Additionally more preferred are complexes of bismuth in the (III) oxidation state, more particularly bismuth(III) complexes with electron-deficient ligands, more particularly carboxylate ligands.

[0201] The p-type dopant is preferably distributed substantially uniformly 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%.

[0202] Preferred p-type dopants are in particular the following compounds:

[0203]

[0204]

[0205] In a preferred embodiment, a hole injection layer conforming to one of the following embodiments is present in the device: a) it contains a triarylamine and a p-type dopant; or b) it contains a single electron-deficient material (electron acceptor). In a preferred embodiment of embodiment a), the triarylamine is a mono-triarylamine, in particular one of the preferred triarylamine derivatives mentioned further below. In a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755.

[0206] The compound of formula (I) or formula (II) can be present in the hole injection layer, hole transport layer, and / or electron blocking layer of the device. When the compound is present in the hole injection layer or hole transport layer, it is preferably p-type doped, which means it is present in the layer in a form mixed with the p-type dopant as described above.

[0207] The compound of formula (I) or formula (II) is preferably present in the electron blocking layer. In this case, it is preferably not p-type doped. More preferably, in this case, it is preferably present in the layer in the form of a single compound without the addition of other compounds.

[0208] In an alternative preferred embodiment, a compound of formula (I) or (II) is used as a matrix material in combination with one or more luminescent compounds, preferably phosphorescent compounds, in a light-emitting layer. The phosphorescent compounds are preferably selected herein from red phosphorescent compounds and green phosphorescent compounds.

[0209] In this case, the proportion of the matrix material in the light-emitting layer is between 50.0% by volume and 99.9% by volume, preferably between 80.0% by volume and 99.5% by volume, more preferably between 85.0% by volume and 97.0% by volume.

[0210] 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, more preferably between 3.0% by volume and 15.0% by volume.

[0211] The light-emitting layer of the organic electroluminescent device may also contain a system comprising a plurality of matrix materials (mixed matrix system) and / or a plurality of luminescent compounds. Also in this case, the luminescent compounds are generally those compounds with a smaller proportion in the system, while 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 luminescent compound.

[0212] Preferably, a compound of formula (I) or (II) is used as a component of a mixed matrix system of preferably phosphorescent emitters. 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-transporting properties and the other material is a material with electron-transporting properties. Additionally preferably, one of the materials is selected from compounds having a large energy difference between the HOMO and the LUMO (wide-bandgap materials). The compound of formula (I) or (II) in the mixed matrix system is preferably a matrix material with hole-transporting properties. Accordingly, when a compound of formula (I) or (II) is used as a matrix material for a phosphorescent emitter in the light-emitting layer of an OLED, a second matrix compound with electron-transporting properties is present in the light-emitting layer. The two different matrix materials may be present 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.

[0213] However, the required electron-transporting and hole-transporting properties of the mixed matrix components may also be mainly or completely combined in a single mixed matrix component, in which case the other mixed matrix components fulfill other functions.

[0214] The following material classes are preferably used in the above-mentioned layers of the device:

[0215] Phosphorescent emitters:

[0216] The term "phosphorescent emitter" generally encompasses compounds that emit light through spin-forbidden transitions, such as transitions from an excited triplet state or a state with a higher spin quantum number (e.g., a quintet state).

[0217] Suitable phosphorescent emitters are, in particular, compounds that emit light upon appropriate excitation, preferably emit light in the visible region, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferably used, especially compounds containing iridium, platinum, or copper, as phosphorescent emitters.

[0218] In the context of the present invention, all luminescent iridium, platinum, or copper complexes are regarded as phosphorescent compounds.

[0219] Generally, all phosphorescent complexes that are used in phosphorescent OLEDs according to the prior art and are known to those skilled in the art of organic electroluminescent devices are suitable for the devices of the present invention. The following table shows other examples of suitable phosphorescent emitters:

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226] Fluorescent emitters:

[0227] Preferred fluorescent luminescent compounds are selected from arylamines. In the context of the present invention, arylamine or aromatic amine should be understood to mean a compound 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 a fused ring system having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthrylamines, aromatic anthryldiamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. Aromatic anthrylamines refer to compounds in which the diarylamino group is directly bonded to the anthracene group preferably at the 9-position. Aromatic anthryldiamines refer to compounds in which two diarylamino groups are directly bonded to the anthracene group preferably at the 9,10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are similarly defined, where the diarylamino group is preferably bonded to pyrene at the 1-position or 1,6-positions. Other preferred luminescent compounds are indeno[1,2-b]fluoreneamines or indeno[1,2-b]fluorenediamines, benzo[def]indeno[1,2-b]fluoreneamines or benzo[def]indeno[1,2-b]fluorenediamines and dibenzo[def]indeno[1,2-b]fluoreneamines or dibenzo[def]indeno[1,2-b]fluorenediamines and indeno[1,2-b]fluorene derivatives having fused aryl groups. Also preferred are pyrenearylamines. Also preferred are benzo[def]indeno[1,2-b]fluoreneamines, benzo[def]fluoreneamines, extended benzo[def]indeno[1,2-b]fluorenes, phen azines and fluorene derivatives linked to a furan unit or to a thiophene unit.

[0228] Matrix materials for fluorescent phosphors:

[0229] Preferred matrix materials for fluorescent phosphors are selected from the following classes: oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene), especially oligoarylenes containing fused aromatic groups, oligoarylene vinylene subunits, polypod metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides and sulfoxides; atropisomers, boric acid derivatives or benzanthracenes. Particularly preferred matrix materials are selected from the following classes: oligoarylenes, including naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylene vinylene subunits, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the following classes: oligoarylenes, including anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. In the context of the present invention, oligoarylene should be understood to mean a compound in which at least three aryl or arylene groups are bonded to each other.

[0230] Matrix materials for phosphorescent phosphors:

[0231] Preferred host materials for the phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones, triarylamines, carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl), indolocarbazole derivatives, indacarbazole derivatives, azacarbazole derivatives, bipolar host materials, silanes, borazines or borates, triazine derivatives, zinc complexes, silyldiazoles or silyltetrazoles derivatives, phosphadiazoles derivatives, bridged carbazole derivatives, terphenylidene derivatives or lactams, and compounds of formula (I) or formula (II).

[0232] Electron transporting materials:

[0233] Suitable electron transporting materials are, for example, the compounds disclosed by Y. Shirota et al., Chem. Rev. 2007, 107(4), 953 - 1010, or other materials used in these layers according to the prior art.

[0234] The materials for the electron transport layer can be any materials used as electron transport materials 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, diazole derivatives, aromatic ketones, lactams, boranes, phosphadiazoles derivatives and phosphine oxide derivatives.

[0235] Preferred electron transport materials and electron injection materials are shown on pages 73 to 75 of WO2020 / 109434A1.

[0236] Hole transporting materials:

[0237] Other compounds preferably used in the hole transport layer of the OLEDs of the present invention, in addition to the compounds of formula (I) and formula (II), are indeno[1,2-b]fluoreneamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with a fused aromatic system, monobenzylindeno[1,2-b]fluoreneamine, dibenzylindeno[1,2-b]fluoreneamine, spirobifluoreneamine, fluoreneamine, spirodibenzopyranamine, dihydroacridine derivatives, spirodibenzofuran and spirodibenzothiophene, phenanthryldiarylamine, spirotribenzotropone, spirobifluorene with a m-phenylenediamine group, spirodiacridine, xanthenyldiarylamine and 9,10-dihydroanthracene spiro compounds with a diarylamino group.

[0238] Preferred hole transporting compounds are shown in the table on pages 76 to 80 of WO2020 / 109434A1.

[0239] The following compounds HT-1 to HT-35 are particularly suitable for use in layers with hole-transporting functions in OLEDs. This applies not only to OLEDs according to the definitions and claims of the present application, but also to OLEDs in general:

[0240]

[0241]

[0242]

[0243]

[0244]

[0245] Compounds HT-1 to HT-35 can generally be used in any hole-transporting layer of an OLED. The term "hole-transporting layer" herein refers to any layer in an OLED between the anode and the light-emitting layer. The term "OLED" is not particularly limited and applies to all OLEDs, especially the OLED structures customary at the filing date of the present application.

[0246] Compounds HT-1 to HT-35 can be prepared by the methods disclosed in the application texts listed in the table above under the respective compounds HT-1 to HT-35. The teachings in the above application texts related to the use of the compounds and the methods for preparing the compounds are hereby expressly incorporated by reference into this disclosure.

[0247] Compounds HT-1 to HT-35 have excellent properties when used in OLEDs, especially excellent lifetime and efficiency. This is especially the case when they are used in the hole-transporting layer of an OLED.

[0248] A preferred cathode of the electronic device is a metal, metal alloy or multi-layer structure having a low work function. The metal alloy or multi-layer structure is composed of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanide elements (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as an alloy composed of magnesium and silver. In the case of a multi-layer structure, in addition to the metals mentioned, other metals having a relatively high work function, such as Ag or Al, can also be used. In this case, combinations of metals, such as Ca / Ag, Mg / Ag or Ba / Ag, are usually used. It is also preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. For this purpose, examples of materials that can be used are alkali metal or alkaline earth metal fluorides, and can also be the corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinolate (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0249] The preferred anode is a material having a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. First, metals having a high redox potential are suitable for this purpose, such as Ag, Pt or Au. Second, metal / metal oxide electrodes (such as Al / Ni / NiOx, Al / PtOx) can also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to irradiate the organic material (organic solar cell) or couple out light (OLED, O-laser). Here, the preferred anode material is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. In addition, conductive doped organic materials, especially conductive doped polymers, are preferred. In addition, the anode can also be composed of two or more layers, such as an inner layer of ITO and an outer layer of metal oxide. The metal oxide is preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0250] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by sublimation. In this case, the material is applied by vapor deposition at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar in a vacuum sublimation system. However, in this case, the initial pressure can even be lower, such as below 10 -7 mbar.

[0251] Also preferred is an electronic device characterized in that one or more layers are coated by the OVPD (organic vapor deposition) method or by carrier gas sublimation. In this case, at 10 -5The material is applied under a pressure between millibar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and thereby structured (e.g., M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0252] Also preferably, an electronic device is characterized in that one or more layers are produced from a solution, for example by spin coating or by any printing method, such as screen printing, flexographic printing, nozzle printing or lithographic printing, but more preferably LITI (light-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, compounds of formula (I) or formula (II) that are soluble are required. High solubility can be achieved by suitable substitution of the compounds.

[0253] It is also preferred to produce the electronic device of the present invention by applying one or more layers from a solution and by applying one or more layers by a sublimation method.

[0254] After applying the layers, depending on the use, the device is structured, contact connections are provided and finally sealed to eliminate the damaging effects of water and air.

[0255] According to the present invention, an electronic device containing one or more compounds of formula (I) or formula (II) can be used in a display, as a light source in lighting applications, and as a light source in medical and / or cosmetic applications. Examples

[0256] A) Synthetic examples

[0257] 1) Synthesis of compound 1a

[0258]

[0259] 33.4 g (63 mmol) of CAS 1799406-63-5, 32.4 (63 mmol), 21.1 g (94 mmol) of potassium phosphate monohydrate and 1.6 g (1.9 mmol) of XPhos Palladacycle Gen.3 were dissolved in 60 ml of THF / water (4:1) and stirred at 60 °C for 16 hours. Then the reaction mixture was concentrated on a rotary evaporator, and the residue was dissolved in dichloromethane. The organic phase was washed twice with water, and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were filtered, dried over sodium sulfate, and concentrated to dryness on a rotary evaporator. The residue was repeatedly subjected to hot extraction (toluene / heptane 1:1) on alumina and crystallized until the HPLC purity > 99.9%. Finally, the product was obtained in solid form after sublimation (10 -6 bar, 325 °C).

[0260] Yield: 25.9 g (30.7 mmol; 49%)

[0261] The following compounds were prepared in a similar manner:

[0262]

[0263]

[0264]

[0265] 2) Synthesis of Int-2

[0266]

[0267] The synthesis of Int-1 was similar to the synthesis of CAS 2459761-30-7 described in WO 2020 / 159333 A1.

[0268] 3) Synthesis of Int-3a

[0269]

[0270] The synthesis of Int-3a was similar to the two-step synthesis of Int-7 described in WO 2015 / 022051 A1 (see page 85 and following).

[0271] The following compounds were prepared in a similar manner:

[0272]

[0273]

[0274] * This reaction formed a mixture of isomers, which could be separated by chromatography.

[0275] 4) Synthesis of Int-4a

[0276]

[0277] The preparation of boric acid was similar to the synthesis of the compound CAS 1799406-63-5 described in WO 2015 / 090504, starting from Int-3c.

[0278] The following compounds were synthesized in a similar manner:

[0279]

[0280] 5) Synthesis of reference compound 2a

[0281]

[0282] 15.4 g (35 mmol) of Int-4, 8.3 g (35 mmol) of CAS 952431-30-0, and 10.6 g (70 mmol) of cesium fluoride were suspended in 400 ml of dichloromethane. To this suspension was added 1.02 g (1.40 mmol) of bis(tricyclohexylphosphine)palladium(II) dichloride, and the reaction mixture was refluxed for 18 h. The reaction mixture was then cooled to room temperature, and the organic phase was washed three times with 100 ml of water and concentrated to dryness on a rotary evaporator. The residue was dissolved in toluene and filtered through silica gel. The residue was purified by recrystallization from toluene / heptane to an HPLC purity > 99.9% and finally sublimed under high vacuum. Yield: 10.4 g (13 mmol; 37% of theory).

[0283] The following compounds were prepared similarly:

[0284]

[0285] 6) Synthesis of Compound 3a

[0286]

[0287] 13.4 g (26 mmol) of Int-1a, 8.83 g (26 mmol) of CAS 1879963-55-9, 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 h. After completion of the conversion, 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 toluene / heptane 1:1 and filtered through silica gel. Further purification was achieved by repeated crystallization from heptane / toluene until the HPLC purity > 99.9%. Finally, the product was obtained in solid form after two sublimations under high vacuum.

[0288] Yield: 6.7 g (9 mmol; 35%)

[0289] The following compounds were prepared in a similar manner:

[0290]

[0291]

[0292] B) Device Examples

[0293] 1) General manufacturing method of OLED and characterization of OLED

[0294] A glass plate coated with 50 nm thick structured ITO (indium tin oxide) formed the substrate for applying the OLED.

[0295] An OLED basically has the following layer structure: a substrate / a hole injection layer (HIL) / a hole transport layer (HTL1) / an optional second hole transport layer (HTL2) / an electron blocking layer (EBL) / a light emitting layer (EML) / an optional hole blocking layer (HBL) / an electron transport layer (ETL1) / an optional second electron transport layer (ETL2) / an electron injection layer (EIL), and finally a cathode. The cathode is formed of an aluminum layer 100 nm thick. The exact structure of the OLED can be seen in the following table. The materials required for manufacturing the OLED are shown in the following table.

[0296] All materials are applied by hot vapor deposition in a vacuum chamber. In this case, the light emitting layer consists of at least one matrix material (host material) and a light emitting dopant (lumophore) added to one or more of the said matrix materials by co-evaporation in a specific volume ratio. Details given in the form of H:SEB (95%:5%) herein refer to the material H being present in the layer in a volume ratio of 95% and SEB being 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 the OLED are shown in Table 7. The compound HTM-B used is 2-aminofluorene with a substituent on one of the aromatic six-membered rings of fluorene. The compound EBM-B used contains an amino group and a 1-spirobifluorenyl group.

[0297] The OLED is characterized in a standard manner. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in %) as a function of the luminous density calculated from the current-voltage-luminous density characteristics showing Lambertian emission characteristics, and the lifetime are measured. The parameter EQE@10 mA / cm 2 refers to the external quantum efficiency achieved at 10 mA / cm 2 The lifetime LT is defined as the time after which the luminous density drops from the initial luminous density to a certain proportion during operation at a constant current density. The number LT90 herein refers to the reported lifetime corresponding to the time after the luminous density has dropped to 90% of its initial value. The number @60 mA / cm 2 herein refers to the lifetime in question being measured at 60 mA / cm 2 under the condition.

[0298] 2) Use as an electron blocking material in a blue fluorescent OLED

[0299] Manufacture an OLED having the following structure:

[0300]

[0301] OLEDs 1 to 4 indicate that the compounds of the present invention are very suitable as materials in OLEDs. The OLEDs show very good properties as hole transport materials, especially in the EBL layer, where they particularly lead to very high external quantum efficiency, low operating voltage, and very good lifetime.

[0302] The OLEDs have good results in terms of lifetime, efficiency, and operating voltage, as shown in the following table:

[0303]

[0304] 3) Examples in the electron blocking layer for green phosphorescent OLEDs

[0305] Fabricate OLEDs with the following structure:

[0306]

[0307]

[0308] OLEDs 5 and 6 indicate that the compounds of the present invention are very suitable as electron blocking materials for green fluorescent OLEDs. The OLEDs show very good properties as hole transport materials or electron blocking materials, where they particularly lead to low operating voltage, good external quantum efficiency, and excellent lifetime.

[0309] The OLEDs have good results in terms of lifetime, efficiency, and operating voltage, as shown in the following table:

[0310]

[0311] 4) Examples of using as the hole transport layer in blue fluorescent OLEDs

[0312] Fabricate OLEDs with the following structure:

[0313]

[0314] This example (OLED 7) indicates that the compound HTM-1 of the present invention is very suitable as a hole transport material for blue fluorescent OLEDs. The OLED shows very good properties as a hole transport material, as well as low operating voltage, good external quantum efficiency, and excellent lifetime.

[0315] The OLEDs have good results in terms of lifetime, efficiency, and operating voltage, as shown in the following table:

[0316]

[0317] HTM-2 can also be used in the stack as shown in Table 5, with good OLED performance.

[0318] 5) In addition, the following blue fluorescent OLEDs containing the compound of the present invention in the EBL were fabricated:

[0319]

[0320] OLEDs 8 and 9 show that the compound of the present invention is very suitable as an electron blocking material for blue fluorescent OLEDs. The OLEDs achieve a low operating voltage, good external quantum efficiency, and good lifetime:

[0321]

[0322] 6) In addition, the following green phosphorescent OLEDs containing the compounds HTM-1, HTM-2, or HTM-3 of the present invention in the EBL were fabricated:

[0323]

[0324]

[0325] OLEDs 10 to 12 show that the compounds of the present invention are very suitable as materials in the electron blocking layer of green phosphorescent OLEDs. The OLEDs achieve a low operating voltage, good external quantum efficiency, and excellent lifetime:

[0326]

[0327] 7) In addition, the following blue fluorescent OLEDs containing the compound HTM-3 of the present invention in the HTL were fabricated:

[0328]

[0329] This OLED (Example 13) shows that the compound HTM-3 of the present invention is suitable as a hole transport material for blue fluorescent OLEDs. The OLED has very good efficiency, as well as good voltage and lifetime:

[0330]

[0331]

[0332] 8) In addition, the compounds HTM-1 and HTM-2 were used as hole transport materials for blue fluorescent OLEDs, and compared with each of the compounds CE-1 and CE-2 in a stack structure that was the same in other aspects:

[0333]

[0334] Examples 14 and 15 demonstrate that the compounds of the present invention are highly suitable as hole transport materials for blue fluorescent OLEDs. The OLEDs achieve low operating voltages, good external quantum efficiencies, and excellent lifetimes (see below). The comparison between Example 14 and Experimental Comparative Example 1 shows that, compared with the comparative compound CE-1, the compound HTM-1 of the present invention results in lower operating voltages, higher efficiencies, and longer lifetimes of the OLEDs. The comparison between Example 15 and Experimental Comparative Example 2 shows that, compared with the comparative compound CE-2, the compound HTM-2 of the present invention also results in lower operating voltages, higher efficiencies, and longer lifetimes of the OLEDs.

[0335]

[0336]

[0337]

[0338]

Claims

1. A compound of one of the following formulas, wherein: W is the same or different in each case and is selected from O and S; Z is the same or different in each case and is selected from CR 1 and N; i is 0 or 1, where when i = 0, the Y group is absent; When i = 0, Z 1 identical or different in each case and selected from CR 1 and N; When i = 1, Z 1 is C; Y is the same or different in each case and is selected from a bond, C(R 1 )2, O, and S; Ar L identical or different in each case and selected from aromatic ring systems having from 6 to 40 aromatic ring atoms and substituted with R 2 groups and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms and substituted with R 2 groups; k is 0, 1, 2 or 3, where when k = 0, the Ar L group does not exist, and the two groups bonded to Ar L in formula (I) and formula (II) are directly bonded to each other, where when k = 2, the two Ar L groups are successively chain-bonded, and where when k = 3, the three Ar L groups are successively chain-bonded; Ar 1 which are the same or different in each case and are selected from aromatic ring systems having 6 to 40 aromatic ring atoms and substituted with R 4 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and substituted with R 4 groups; Ar 2 identical or different in each case and selected from an aromatic ring system having 6 to 40 aromatic ring atoms and substituted by R 5 groups and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted by R 5 groups, wherein the aromatic or heteroaromatic ring system is attached ortho to the V group and the nitrogen atom; V is the same or different in each case and is selected from a bond, O, S, Si(R 5 )2 and C(R 5 )2; R 1 identical or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 1 groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 (-), NR 6 , P(=O)(R 6 )-, -O-, -S-, SO or SO2; R 2 identical or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 2 groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 (-), NR 6 , P(=O)(R 6 )-, -O-, -S-, SO or SO2; R 3 the same or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 3 groups may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 (-), NR 6 , P(=O)(R 6 )-, -O-, -S-, SO or SO2; R 4 identical or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 4 groups may be linked to each other and may form a ring; wherein said alkyl, alkoxy, alkenyl, and alkynyl groups, and said aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl, and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 ]-, NR 6 , P(=O)(R 6 ) , -O-, -S-, SO or SO2; R 5 identical or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , a straight-chain 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 R 5 groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring system and heteroaromatic ring system are each substituted by an R 6 group; and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 (-), NR 6 , P(=O)(R 6 )-, -O-, -S-, SO or SO2; R 6 identical or different in each case and selected from H, D, F, Cl, Br, I, C(=O)R 7 , CN, Si(R 7 )3, N(R 7 )2, P(=O)(R 7 )2, OR 7 , S(=O)R 7 , S(=O)2R 7 , a straight-chain 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; where two or more R 6 groups may be linked to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring system and heteroaromatic ring system mentioned are each substituted by an R 7 group; and where one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R 7 C=CR 7 -, -C≡C-, Si(R 7 )2, C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 (-), NR 7 , P(=O)(R 7 )-, -O-, -S-, SO or SO2; R 7 identical or different in each case and 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; where two or more R 7 groups may be linked to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more groups selected from F and CN.

2. The compound according to claim 1, wherein Z is CR 1 。 3. The compound according to claim 1 or 2, characterized in that Ar L identical or different in each case and selected from phenyl, biphenyl, naphthyl and fluorenyl each substituted by an R 2 group.

4. A compound according to one or more of claims 1 to 3, characterized in that i is 1 and Y is a bond.

5. A compound according to one or more of claims 1 to 4, characterized in that Ar 1 identical or different in each case and selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indolocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where the monovalent groups are each substituted by R 4 groups.

6. The compound according to one or more of claims 1 to 5, characterized in that Ar 2 identical or different in each case and selected from vicinal divalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indolocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine and pyridazine, wherein the monovalent groups are each substituted by R 5 groups.

7. The compound according to one or more of claims 1 to 6, characterized in that In a compound of one of formula (I) and formula (II), zero, one, two or three R in each formula 1 groups are not H or D, and characterized in that these groups which are not H or D are the same or different in each case and are selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, wherein the alkyl group mentioned, the aryl group mentioned and the heteroaryl group mentioned are each substituted by R 6 groups.

8. A compound according to one or more of claims 1 to 7, characterized in that In a compound of one of formula (I) and formula (II), zero, one, two or three R 3 groups in each formula are not H or D, and characterized in that these groups which are not H or D are the same or different in each case and are selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, wherein the alkyl group mentioned, the aryl group mentioned and the heteroaryl group mentioned are each substituted by R 6 groups.

9. A compound according to one or more of claims 1 to 8, characterized in that All Rs in formula (I) and formula (II) 1 and R 3 groups are H or D.

10. A compound according to one or more of claims 1 to 9, characterized in that Each Ar 1 group contains zero, one, two, three or four R 4 groups which are not H or D, and is characterized in that these groups which are not H or D are the same or different in each case and are selected from F, CN, Si(R 6 )3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 25, preferably 6 to 14 aromatic ring atoms, and heteroaryl groups having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned, the aryl groups mentioned and the heteroaryl groups mentioned are each substituted by R 6 groups.

11. The compound according to one or more of claims 1 to 10, characterized in that Each Ar 2 group has zero, one, two, three or four R 5 groups which are not H or D, and is characterized in that these groups which are not H or D are the same or different in each case and are selected from F, CN, Si(R 6 )3, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 25, preferably 6 to 14 aromatic ring atoms, and a heteroaryl group having 5 to 40 aromatic ring atoms, wherein the alkyl group mentioned, the aryl group mentioned and the heteroaryl group mentioned are each substituted by an R 6 group.

12. A compound according to one or more of claims 1 to 11, characterized in that The compound conforms to one of the following formulas: where the groups present are the same as those defined in one or more of the preceding claims; or characterized in that the compound conforms to one of the following formulas: where the groups present are the same as those defined in one or more of the preceding claims.

13. The compound according to any one of claims 1 to 12, characterized in that The compound conforms to one of the following formulas: where the groups present are the same as those defined in one or more of the preceding claims; or characterized in that the compound conforms to one of the following formulas: where the groups present are the same as those defined in one or more of the preceding claims.

14. A method for preparing a compound according to one or more of claims 1 to 13, characterized in that The indeno[1,2-b:5,4-b']dibenzofuran derivative substituted with a reactive group a) reacts with a secondary amine in a coupling reaction, or b) reacts with an aromatic or heteroaromatic substance bearing a reactive group in a coupling reaction.

15. An oligomer, polymer or dendrimer, said oligomer, polymer or dendrimer containing one or more compounds according to one or more of claims 1 to 13, wherein one or more of the bonds linking to said polymer, oligomer or dendrimer may be at any desired position substituted by R 1 、R 2 、R 3 、R 4 or R 5 at any desired position.

16. A formulation comprising at least one compound according to one or more of claims 1 to 13 or at least one polymer, oligomer or dendrimer according to claim 15 and at least one solvent.

17. An electronic device comprising at least one compound according to one or more of claims 1 to 13 or at least one polymer, oligomer or dendrimer according to claim 15.

18. The electronic device according to claim 17, wherein The electronic device is an organic electroluminescent device and comprises an anode, a cathode and at least one light-emitting layer, and is characterized in that the compound is present in the hole-transporting layer or the light-emitting layer of the device.

19. Use of a compound according to one or more of claims 1 to 13 in an electronic device.

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