2-Diarylaminofluorene derivatives and organic electronic devices containing them

Abstract

Electroluminescent devices and compounds are provided that are suitable for use in electroluminescent devices such as OLEDs, and in particular can be used as hole transport materials and / or hole injection materials and / or matrix materials. The present invention contains the following compound. JPEG2023021983000081.jpg26170 [In the formula, Ar 3 , Ar 4 is the same or different at each occurrence and is selected from substituted or unsubstituted biphenyl and terphenyl.

Description

[Technical Field]

[0001] The present invention relates to novel organic compounds, their use in electroluminescent devices and electroluminescent devices containing at least one of the compounds. The present invention further relates to methods for preparing the compounds and compositions and formulations containing at least one of the compounds.

[0002] The development of functional compounds for electronic devices is currently a subject of intensive research, where the aim is to develop compounds that can achieve improved properties of electroluminescent devices, in particular in one or more relevant respects, such as power efficiency, lifetime or emission color coordinate.

[0003] According to the present invention, the term electroluminescent device is used in particular to mean organic light-emitting transistors (OLETs), organic field-quenched devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

[0004] Of particular interest is the provision of compounds for use in the last-mentioned electronic devices, so-called OLEDs, the general structure and functional principles of which are known to those skilled in the art and are described, inter alia, in US 4,539,507, US 5,151,629, EP 0 676 461 and WO 1998 / 27136.

[0005] Further improvements are still needed in the performance data of OLEDs, especially in the context of widespread commercial use, for example, as display devices or light sources. Of particular importance in this regard are the lifetime, efficiency, and driving voltage of OLEDs, and the color values achieved. In addition, it is desirable for compounds for use as functional materials in electronic devices to have high thermal stability, high glass transition temperatures, and to sublime without decomposition.

[0006] In this regard, there is a need, in particular, for alternative hole transport materials. In prior art hole transport materials, the voltage generally increases with the thickness of the hole transport layer. In fact, a larger layer thickness of the hole transport layer is often desirable, but this often results in a higher driving voltage and worse performance data. In this regard, there is a need for new hole transport materials that have high charge carrier mobility, so that a thicker hole transport layer can be achieved with only a slight increase in driving voltage.

[0007] The prior art describes the use of various fluorenes as charge transport materials in electronic and electroluminescent devices.

[0008] JP3824385 B2 discloses 2- and 7-substituted fluorenes substituted with dibenzofuran or carbazole.

[0009] US2012 / 20012832 discloses fluorenes substituted with fused aromatic groups.

[0010] WO2004 / 020387 discloses fluorenes substituted in the 2-position by amino groups, where the amino groups are themselves disubstituted, in each case by one phenyl group.

[0011] JP05-303221 discloses 2- and 4-substituted fluorenes as photosensitizing compounds. Their use in electroluminescent devices such as OLEDs or OLECs is not described therein.

[0012] Notwithstanding previously known compounds, there continues to be a need for new hole-transporting and hole-injecting materials for use in OLEDs. In particular, there is a need for materials that can achieve the above-mentioned highly desirable improvements in OLED performance data and properties.

[0013] Similarly, there is a need for new matrix materials for use in OLEDs and other electronic devices, particularly matrix materials for phosphorescent emitters and mixed matrix systems that preferably result in good efficiency, long lifetimes, and low driving voltages for the electronic devices.

[0014] The present invention is therefore based on the object of providing electroluminescent devices and compounds which are suitable for use in electroluminescent devices, such as, for example, OLEDs, and which can in particular be used as hole transport materials and / or hole injection materials and / or matrix materials.

[0015] As part of the present invention, it has surprisingly been found that compounds of formula (1) shown below are highly suitable for the above electroluminescent device applications.

[0016] The present invention therefore relates to an electroluminescent device comprising at least one compound of formula (1); [ka]

[0017] The following applies to the symbols and subscripts used: Ar 1 , Ar 2 are identical or different at each occurrence and are aromatic or heteroaromatic ring structures having 10 to 60 aromatic ring atoms, and are joined by one or more groups R 4 where two groups Ar 1 and Ar 2 each contains at least two aromatic or heteroaromatic rings; R 1 are the same or different for each occurrence, H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, NO2, P(=O)(R 5 )2, S(=O)R 5 , S(=O)2R5 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms (the above-mentioned groups each may be joined by one or more groups R 5 and one or more CH groups in the above-mentioned groups may be substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=S, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, P(=O)(R 5 ), -O-, -S-, SO or SO2, where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2; or in each case one or more groups R 5 or in each case one or more groups R 5 wherein in the case of an aromatic or heteroaromatic fused ring, up to 10 ring atoms may be present; and two groups R 1 may form a ring closure with each other, thereby forming a spiro compound, where the aromatic or heteroaromatic ring is bound by two groups R 1 not fused onto the ring formed by R 2 , R 3 and R 4 are the same or different for each occurrence, H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, NO2, P(=O)(R 5 )2, S(=O)R 5 , S(=O)2R 5, a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms (the above-mentioned groups each may be joined by one or more groups R 5 and one or more CH groups in the above-mentioned groups may be substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=S, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, P(=O)(R 5 ), -O-, -S-, SO or SO2, where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2; or in each case one or more groups R 5 an aromatic or heteroaromatic ring structure having 6 to 30 ring atoms, optionally substituted by R 5 are the same or different for each occurrence, H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, NO2, P(=O)(R 6 )2, S(=O)R 6 , S(=O)2R 6 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms (the above-mentioned groups each may be joined by one or more groups R 6 and one or more CH groups in the above-mentioned groups may be substituted by -R 6 C=CR 6 -, -C≡C-, Si(R 6 )2, C=O, C=S, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, P(=O)(R 6), -O-, -S-, SO or SO2, where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2; or in each case one or more groups R 6 an aromatic or heteroaromatic ring structure having 5 to 30 aromatic ring atoms, optionally substituted by one or more groups R 6 an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, optionally substituted by R 6 are identical or different at each occurrence and are H, D, F, an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 C atoms, and further, one or more H atoms may be replaced by D or F; n is 0, 1, 2, 3 or 4; m is 0, 1, 2 or 3; However, the compounds of formula (1) do not contain any further polycyclic or fused groups, except for one fluorene, and except for a possible fused or polycyclic group at the 9-position of the fluorene.

[0018] Here, the numbering on the fluorene is defined as follows: [ka]

[0019] Preferably, the electroluminescent device comprises at least one compound of formula (1) and two groups R 1 are identical.

[0020] It is preferred that the electroluminescent device comprises at least one compound of formula (1), wherein m is 1 or 0, very preferably m is 0.

[0021] It is further preferred that the electroluminescent device comprises at least one compound of formula (1), wherein n is 2, 1 or 0, and very preferably n is 0 or 1.

[0022] The compound of formula (1) is preferably selected from the compounds of formula (2): [ka]

[0023] wherein the symbols are defined as indicated above.

[0024] Most preferably, two groups R 1 are the same as compounds of formula (2).

[0025] In a further preferred embodiment of the present invention, the electroluminescent device comprises at least one compound of formula (3), further preferably a group R 1 are the same as compounds of formula (3). [ka]

[0026] In a highly preferred embodiment of the present invention, R 2 is H, a linear alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms (the above-mentioned groups each contain one or more groups R 5 wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2) or in each case by one or more groups R 5 an aromatic ring structure having 6 to 30 aromatic ring atoms which may be substituted by; R 2 is particularly preferably H or in each case one or more radicals R 5 It is an aromatic ring structure having 6 to 30 aromatic ring atoms which may be substituted by:

[0027] In a very particularly preferred embodiment, the electroluminescent device comprises at least one compound of formula (3), R 2 is H and two R 1are identical or different at each occurrence, preferably identical, and in each case one or more groups R 5 The aromatic or heteroaromatic ring structure has 6 to 30 aromatic ring atoms and may be substituted by:

[0028] R in formulas (1) to (3) 2 are particularly preferably each one or more groups R 5 and n is 0 or 1. Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl or quaterphenyl groups, which may be substituted by: wherein these are more preferably unsubstituted or H.

[0029] In a further very particularly preferred embodiment, the electroluminescent device comprises at least one compound of formula (3), R 2 is in each case one or more groups R 5 an aromatic ring structure having 6 to 30 aromatic ring atoms, which may be substituted by R 1 are identical or different from each other at each occurrence, preferably identical, and are selected from linear alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms (the above-mentioned groups each contain one or more groups R 5 wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2.

[0030] More preferably, the electroluminescent device comprises at least one compound of formula (4): [ka]

[0031] wherein X is the same or different at each occurrence and is N or CR 4 where only three of the groups X per ring may be N. Highly preferably, X in formula (4) is CR 4 where the above definitions apply to the group R 1 , R 2 and R 4 applies to.

[0032] Preferred groups Ar 1 , Ar 2 is selected from groups having formulae (5) to (60) shown in the table below, where the groups may be substituted as previously indicated and may contain one or more R 4 may be replaced by [ka] [ka] [ka] [ka] [ka]

[0033] Preferred electroluminescent devices in the sense of the present invention comprise at least one compound of formula (1) and 1 and Ar 2 contains only aromatic rings and no heteroaromatic rings Ar 1 and Ar 2 are particularly preferably identical or different and each represent one or more groups R 4 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein more preferably, they are unsubstituted.

[0034] In a further highly preferred embodiment of the present invention, in the compound of formula (1) Two groups R 1 are identical and are linear alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms (the above-mentioned groups are each optionally joined by one or more groups R 5wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2) or in each case by one or more groups R 5 or in each case one or more groups R 5 wherein in the case of an aromatic or heteroaromatic fused ring, up to 10 ring atoms may be present; and two groups R 1 may form a closed ring, thereby forming a spiro compound, in which the aromatic or heteroaromatic ring is bound by two groups R 1 not fused onto the ring formed by n is 1 and the group R 2 is at position 7 of fluorene; m is 0; R 2 is an alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a pyridyl, phenyl, biphenyl, terphenyl or quaterphenyl group, each of which is represented by one or more groups R 5 wherein the unsubstituted aromatic or heteroaromatic group is further preferably unsubstituted or H; Ar 1 and Ar 2 are the same or different and each represent one or more groups R 4 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0035] In a further highly preferred embodiment of the present invention, in the compound of formula (1) Two groups R 1 are identical and are a linear alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms (each of which is represented by one or more groups R 5wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2; n is 1 and the group R 2 is at position 7 of fluorene; m is 0; R 2 is H or a pyridyl, phenyl, biphenyl, terphenyl or quaterphenyl group, each of which is represented by one or more groups R 5 wherein unsubstituted aromatic or heteroaromatic groups are further preferred; Ar 1 and Ar 2 are the same or different and each represent one or more groups R 4 Preferably, the aryl group is selected from biphenyl, terphenyl and quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0036] In a further highly preferred embodiment of the present invention, in the compound of formula (1) Two groups R 1 are identical and in each case contain one or more groups R 5 or in each case one or more groups R 5 wherein in the case of an aromatic or heteroaromatic fused ring, up to 10 ring atoms may be present; n is 1 and the group R 2 is at position 7 of fluorene; m is 0; R 2 is an alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a pyridyl, phenyl, biphenyl, terphenyl or quaterphenyl group, each of which is represented by one or more groups R 5 wherein the unsubstituted aromatic or heteroaromatic group is further preferably unsubstituted or H, wherein R 2is preferably H; Ar 1 and Ar 2 are the same or different and each represent one or more groups R 4 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0037] Further preferred in the sense of the present invention, electroluminescent devices comprising at least one compound of formula (1) do not contain further polycyclic or fused groups, apart from one fluorene.

[0038] The compounds according to the invention can be synthesized by processes generally known to those skilled in the art, for example by halogenation, Buchwald coupling and Suzuki coupling.

[0039] The following scheme illustrates a preferred synthetic route for the preparation of compounds (1) of the present invention. For the synthesis of compounds of the present invention, fluorene compound A is prepared by Buchwald coupling with a fluorene of formula Ar 1 -NH-Ar 2 reacts with amine B. [ka]

[0040] Another preferred synthetic route for the preparation of compounds of the present invention is depicted in the following scheme. The carboxylate group in compound C is converted to the corresponding alcohol D by addition of an alkyl- or aryl-metal compound, such as an alkyl- or aryl-lithium compound, or an alkyl- or aryl-Grignard compound. This alcohol can be cyclized under acidic conditions to give compound E. Finally, a compound of formula Ar 1 -NH-Ar 2 Buchwald coupling of to amine B is carried out. [ka]

[0041] The following scheme illustrates a further preferred synthetic route for the preparation of compounds of the present invention. To this end, fluorene A is converted by Suzuki coupling to a compound of formula Ar 3 -B(OH)2 with a boronic acid F. Bromination of the resulting compound can be used to prepare, for example, a compound of formula Ar 1 -NH-Ar 2 Buchwald coupling of to amine B followed by bromination provides the corresponding compounds of the invention. [ka]

[0042] The synthetic routes for the starting compounds A, B and C used in the synthesis of the compounds of the present invention are known to those skilled in the art. In addition, some obvious synthetic processes are described in detail in the Examples.

[0043] Here, the coupling reaction is preferably Buchwald coupling.

[0044] The compounds described above, in particular those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, can be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers, where oligomerization or polymerization preferably occurs via the halogen or boronic acid functional group.

[0045] Preferred compounds for use in the electroluminescent device of the present invention are illustrated by the examples in the following table. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0046] The present invention also relates to a compound of the general formula (167): [ka]

[0047] In equation (167), the following applies to the symbols used: Ar 3 , Ar 4 are identical or different at each occurrence and are aromatic or heteroaromatic ring structures having 10 to 60 ring atoms, and are each independently selected from one or more groups R 5 where two groups Ar 3and Ar 4 each contains at least two aromatic or heteroaromatic rings, preferably aromatic rings; R 7 are identical or different at each occurrence and are a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, an alkenyl or alkynyl group having 2 to 20 C atoms (the above-mentioned groups may each be joined by one or more groups R 5 wherein one or more H atoms in the above-mentioned groups may be replaced by D, CN or NO2; or in each case by one or more groups R 5 (R 5 is defined as indicated above. An aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more groups R 5 wherein in the case of an aromatic or heteroaromatic fused ring, up to 10 ring atoms may be present in the fused ring structure; 7 may also form closed rings with each other, thereby forming spiro compounds, in which the aromatic or heteroaromatic ring is bound by two groups R 7 is not fused onto a ring formed by 7 If is a linear or branched alkyl, then R 8 in each case one or more groups R 5 (R 5 is an aromatic or heteroaromatic ring structure having 6 to 30 ring atoms, optionally substituted by (as defined above); R 8 is H, D, in each case one or more groups R 5 (R 5 is defined as above. An aromatic or heteroaromatic ring structure having 6 to 30 ring atoms, optionally substituted by R 8 If is H, then R 7 in each case one or more groups R 5 (R5 is defined as above. is an aromatic or heteroaromatic ring structure having 6 to 30 aromatic ring atoms, optionally substituted by; a is 1, 2, 3 or 4, preferably 1 or 2, very preferably 1; with the proviso that the compound of formula (167) contains, apart from one fluorene group, and apart from a possible fused or polycyclic group at the 9-position of the fluorene, no further polycyclic or fused groups; and, with the proviso that the compound does not contain a halogen.

[0048] Preferably, the compound of formula (167) contains no further polycyclic or fused groups, except for one fluorene group.

[0049] a=1 and R 8 is at the 7-position of the fluorene, ie, the compound of formula (168).

[0050] In particular, preferred compounds of formula (167) and (168) are those in which the following applies to the symbols used: [ka]

[0051] Ar 3 , Ar 4 are identical or different in each occurrence and each contain one or more groups R 5 wherein the aryl, ... R 7 are identical or different at each occurrence and in each case represent one or more groups R 5 (R 5 is defined as indicated above. An aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more groups R 5wherein in the case of an aromatic or heteroaromatic fused ring, up to 10 ring atoms may be present in the fused ring structure; with the proviso that the compound of formula (168) contains, apart from one fluorene group, and apart from a possible fused or polycyclic group at the 9-position of the fluorene, no further polycyclic or fused groups; and, with the proviso that the compound does not contain a halogen.

[0052] Further preferred compounds of formula (167) are compounds of general formula (169): [ka]

[0053] where X is the same or different for each occurrence and is N or CR 5 and R 5 , Ar 3 and Ar 4 is as shown above. Preferred X in formula (169) is CR 5 It is preferable that:

[0054] Ar in formula (169) 1 and Ar 3 are identical or different in each occurrence and each contain one or more groups R 5 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein these are preferably unsubstituted.

[0055] Most preferred is the compound of formula (170): [ka]

[0056] Ar in formula (170) 1 and Ar 3 are preferably identical or different at each occurrence and each contain one or more groups R 5Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0057] In a further preferred embodiment of the present invention, the compound is selected from the general formula (171): [ka]

[0058] The above definitions apply to the symbols used.

[0059] Ar in formula (171) 1 and Ar 3 are preferably identical or different at each occurrence and each contain one or more groups R 5 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0060] A more preferred compound of formula (5) is a compound of formula (172): [ka]

[0061] where the following applies to the symbols used: X may be identical or different for each occurrence and may be N or CR 5 and preferably CR 5 and R 5 is defined as shown above, R 7 is a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms (the above-mentioned groups each contain one or more groups R 5 wherein one or more H atoms in the above-mentioned groups may be replaced by D, CN or NO2. 7may also form closed rings with each other, thereby forming spiro compounds, in which the aromatic or heteroaromatic ring is bound by two groups R 7 It does not condense onto the ring formed by

[0062] Ar in formula (172) 1 and Ar 3 are preferably identical or different at each occurrence and each contain one or more groups R 5 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0063] In a further preferred embodiment of the present invention, the compound is selected from compounds of general formula (173): [ka]

[0064] where the following applies to the symbols used: R 7 represents a linear alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms (the above-mentioned groups each contain one or more groups R 5 wherein one or more H atoms in the above-mentioned groups may be replaced by D, CN or NO2. 7 may also form closed rings with each other, thereby forming spiro compounds, in which the aromatic or heteroaromatic ring is bound by two groups R 7 It does not condense onto the ring formed by

[0065] Ar in formula (173) 1 and Ar 3 are preferably identical or different at each occurrence and each contain one or more groups R 5 Preferably, the aryl group is selected from biphenyl, terphenyl or quaterphenyl groups, which may be substituted by, wherein it is more preferred that they are unsubstituted.

[0066] Very particularly preferred are the compounds of the following formulae (174) to (236), which are illustrated by way of example: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0067] The compounds of the present invention can be used in compositions with other organic functional materials used in electronic devices. Many possible organic functional materials are known to those skilled in the art. Therefore, the present invention also relates to compositions comprising one or more compounds of formula (167) and at least one additional organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials, and hole blocking materials.

[0068] Processing of the compounds of the present invention from a liquid phase, for example by spin coating or by a printing process, requires a formulation of the compounds of the present invention. These formulations can be, for example, solutions, dispersions, or miniemulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, or a mixture of these solvents.

[0069] The present invention therefore also relates to a formulation, in particular a solution, dispersion or miniemulsion, comprising at least one compound of formula (167) or at least one polymer, oligomer or dendrimer comprising units of formula (167) and at least one solvent, preferably an organic solvent. Methods by which solutions of this type can be prepared are known to those skilled in the art and are described, for example, in applications WO 2002 / 072714, WO 2003 / 019694 and the documents cited therein.

[0070] The compounds of the present invention are suitable for use in electroluminescent devices, in particular organic electroluminescent devices (such as OLEDs or OLECs). Depending on the substitution, the compounds are used in various functions and layers.

[0071] The present invention therefore further relates to the use of compounds of formula (167) in electronic devices and to electronic devices themselves comprising one or more compounds of formula (1), preferably selected from organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quenched devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and particularly preferably organic electroluminescent devices (OLEDs or OLECs).

[0072] As mentioned above, the present invention relates to an electronic device comprising at least one compound of formula (167), wherein the electronic device is preferably selected from the above-mentioned devices, particularly preferably an organic electroluminescent device (OLED) comprising an anode, a cathode and at least one light-emitting layer, wherein at least one organic layer, which may be a light-emitting layer, a hole-transporting layer or other layer, comprises at least one compound of formula (167).

[0073] An aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms; a heteroaryl group in the sense of the present invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and S. This is the basic definition. If other preferences are indicated in the description of the present invention, for example with regard to the number of aromatic ring atoms or heteroatoms present, these also apply.

[0074] Here, aryl or heteroaryl is used to mean either a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused aromatic or heteroaromatic polycyclic group, such as naphthalene, phenanthrene, quinoline or carbazole. A fused aromatic or heteroaromatic polycyclic group in the sense of the present invention consists of two or more simple aromatic or heteroaromatic rings fused together.

[0075] The aryl or heteroaryl radicals may in each case be substituted by the above-mentioned groups and may be linked to the aromatic or heteroaromatic system via any desired position, but in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6, 7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthroimidazole, pyridine imidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2, It is used to mean groups derived from 3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0076] According to the definition of the present invention, an aryloxy group is used to mean an aryl group, as defined above, which is bonded via an oxygen atom. The same definition applies to heteroaryloxy groups.

[0077] An aromatic ring structure in the sense of the present invention comprises 6 to 60 C atoms in the ring structure. A heteroaromatic ring structure in the sense of the present invention comprises 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring structure in the sense of the present invention is not necessarily a structure containing only aryl or heteroaryl groups; in addition, multiple aryl or heteroaryl groups may be present, for example, in a ring structure such as sp 3 Hybridized C, Si, N or O atoms, sp 2 It is understood to mean a structure which may be linked by non-aromatic units (preferably less than 10% of atoms other than H) such as hybridized C or N atoms or sp hybridized C atoms. Thus, structures such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also used in the sense of aromatic ring structure in the sense of the present invention, since they are structures in which two or more aryl groups are linked, for example, by linear or cyclic alkyl, alkenyl or alkynyl groups, or by silyl groups. Furthermore, structures in which two or more aryl or heteroaryl groups are linked to each other via a single bond, such as, for example, biphenyl, terphenyl or diphenyltriazine, are also used in the sense of aromatic or heteroaromatic ring structure in the sense of the present invention.

[0078] The aromatic or heteroaromatic ring structures having 5 to 60 aromatic ring atoms may in each case be substituted by the groups mentioned above and may be linked to the aromatic or heteroaromatic system at any desired position, but are in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzphenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo 7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridine imidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diaza Anthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,It is used to mean a group derived from 3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or a combination of these groups.

[0079] For the purposes of the present invention, linear alkyl groups having 1 to 40 C atoms or branched or cyclic alkyl groups having 3 to 40 C atoms or alkenyl or alkynyl groups having 2 to 40 C atoms, in which in addition individual H atoms or CH groups may be substituted by the groups mentioned above under the definition of the groups, preferably by the groups methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl , neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl.Alkoxy or thioalkyl groups having 1 to 40 carbon atoms are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n -pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptithiol, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0080] The compounds of formula (1) described above may be substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic acid esters. These can be used as monomers for the preparation of corresponding oligomers, dendrimers, or polymers. Suitable reactive leaving groups include, for example, bromine, iodine, chlorine, boronic acid, boronic acid esters, amines, alkenyl or alkynyl groups containing terminal C—C double or C—C triple bonds, respectively, oxiranes, oxetanes, groups that undergo cyclization, for example, 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0081] Thus, the present invention further relates to oligomers, polymers, or dendrimers comprising one or more compounds of formula (1), wherein the bond to the polymer, oligomer, or dendrimer can be located at any desired position in formula (1). Depending on the bond of the compound of formula (1), the compound is a component of the side chain or main chain of the oligomer or polymer. An oligomer in the sense of the present invention is used to mean a compound constructed from at least three monomer units. A polymer in the sense of the present invention is used to mean a compound constructed from at least 10 monomer units. The polymers, oligomers, or dendrimers of the present invention may be conjugated, partially conjugated, or non-conjugated. The oligomers or polymers of the present invention may be linear, branched, or dendritic. In linearly bonded structures, the units of formula (1) may be directly bonded to each other or may be bonded to each other by divalent groups, such as substituted or unsubstituted alkylene groups, heteroatoms, or divalent aromatic or heteroaromatic groups. In branched and dendritic structures, three or more units of formula (1) may be linked by trivalent or polyvalent groups, such as trivalent or polyvalent aromatic or heteroaromatic groups, resulting in branched or dendritic oligomers or polymers.

[0082] The same preferences as described above for compounds of formula (1) apply to repeat units of formula (1) in oligomers, dendrimers and polymers.

[0083] To prepare oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are fluorene (for example according to EP 842208 or WO 2002 / 22026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), para-phenylene (for example according to WO 1992 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2005 / 014689 or WO 2007 / 006383), cis- and trans-indenofluorenes (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketones (for example according to WO 2005 / 040302), phenanthrenes (for example according to WO 2005 / 104264 or WO 2007 / 017066) or a plurality of these units. The polymers, oligomers and dendrimers also usually contain further units, such as luminescent (fluorescent or phosphorescent) and / or charge transport units, in particular those based on triarylamines, such as vinyltriarylamines (for example according to WO 2007 / 068325) or phosphorescent metal complexes (for example according to WO 2006 / 03000).

[0084] The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long lifetime, high efficiency and good color coordinates.

[0085] The polymers and oligomers according to the invention are generally prepared by the polymerization of one or more types of monomers, at least one of which will give rise to repeat units of formula (1) 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 which give rise to CC or CN bonds are the following: (A) Suzuki polymerization; (B) Yamamoto polymerization; (C) Stille polymerization and (D) Hartwig-Buchwald polymerization The manner in which polymerization can be carried out by these methods and the manner in which the polymer can then be separated from the reaction medium and purified is known to those skilled in the art and is described in detail in the literature, for example in WO 2003 / 048225, WO 2004 / 037887 and WO 2004 / 037887.

[0086] The present invention therefore also relates to a process for the preparation of the polymers, oligomers and dendrimers according to the invention, characterized in that they are prepared by Suzuki polymerisation, Yamamoto polymerisation, Stille polymerisation or Hartwig-Buchwald polymerisation. The dendrimers according to the invention can be prepared by or analogously to methods known to those skilled in the art. Suitable methods are described in the literature, for example, in Fréchet, Jean MJ; Hawker, Craig J., "Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers", Reactive & Functional Polymers (1995), 26(1-3), 127-36; Janssen, HM; Meijer, EW, "The synthesis and characterization of dendritic molecules", Materials Science and Technology (1999), 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A., "Dendrimer molecules", Scientific American (1995), 272(5), 62-6, WO 2002 / 067343 A1 and WO 2005 / 026144 A1.

[0087] In addition to the cathode, anode, and light-emitting layer, organic electroluminescent devices may contain further layers. These may include, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer), and / or organic or inorganic p / n junctions. However, it should be noted that each of these layers does not necessarily have to be present, and the choice of layer always depends on the compound used and, in particular, whether the electroluminescent device is fluorescent or phosphorescent.

[0088] The organic electroluminescent device of the present invention may include multiple light-emitting layers. In this case, these light-emitting layers preferably have multiple maximum emission wavelengths between 380 nm and 750 nm, resulting in white light as a whole. In other words, various light-emitting compounds that emit fluorescence or phosphorescence and can emit blue, yellow, orange, or red light can be used in the light-emitting layers. A three-layer structure, i.e., a structure having three light-emitting layers, which emit blue, green, and orange or red light (see, for example, WO 2005 / 011013 for a basic structure), is particularly preferred. In such a device, the compound of the present invention may be present in a hole-transporting layer, a light-emitting layer, and / or another layer. It should be noted that for generating white light, an individually used emitter compound emitting in a broad wavelength range may be suitable instead of multiple emitter compounds emitting in a certain color.

[0089] According to the present invention, the compound of formula (1) is preferably used in an electroluminescent device containing one or more phosphorescent dopants. Here, the compound can be used in various layers, preferably in the hole transport layer, the hole injection layer or the light-emitting layer. However, according to the present invention, the compound of formula (1) can also be used in an electronic device containing one or more fluorescent dopants.

[0090] The term phosphorescent dopant typically encompasses compounds in which emission occurs via a spin-forbidden transition, such as a transition from an excited triplet state or a state with a relatively high spin quantum number, such as a quintet state.

[0091] Suitable phosphorescent dopants (=triplet emitters) are in particular compounds which, upon suitable excitation, preferably emit light in the visible range and additionally contain at least one atom with an atomic number greater than 20, preferably an atomic number between 38 and 84, particularly preferably an atomic number between 56 and 80. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper.

[0092] For purposes of this invention, all luminescent iridium, platinum or copper complexes are considered phosphorescent compounds.

[0093] Examples of the emitter described above are disclosed in applications WO 00 / 70655, WO 01 / 41512, WO 02 / 02714, WO 02 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373 and US2005 / 0258742.Generally, all phosphorescent complexes that are used according to the prior art for phosphorescent OLEDs and known to those skilled in the art in the field of organic electroluminescent devices are suitable.Those skilled in the art can also use other phosphorescent complexes in combination with the compound of formula (1) in organic electroluminescent devices without requiring inventive step.

[0094] Specific examples of suitable phosphorescent emitter compounds are further illustrated by the following table. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0095] In a preferred embodiment of the present invention, the compounds of formulas (1) to (167) are used as hole transport materials. The compounds are then preferably used in a hole transport layer and / or a hole injection layer. A hole injection layer in the sense of the present invention is a layer directly adjacent to the anode. A hole transport layer in the sense of the present invention is a layer located between the hole injection layer and the light-emitting layer. The hole transport layer may be directly adjacent to the light-emitting layer. If compounds of formula (1) are used as hole transport or hole injection materials, they may preferably be doped with an electron acceptor compound, for example, F4-TCNQ or a compound as described in EP 1 476 881 or EP 1 596 445. In a further preferred embodiment of the present invention, compounds of formula (1) are used as hole transport materials in combination with a hexaazatriphenylene derivative as described in US 2007 / 0092755. Here, the hexaazatriphenylene derivative is particularly preferably used in a separate layer.

[0096] If the compounds of formulas (1) to (167) are used as hole transport materials in a hole transport layer, the compounds can be used as pure materials in the hole transport layer, i.e., in a proportion of 100%, or can be used in combination with one or more further compounds in the hole transport layer.

[0097] In a further embodiment of the present invention, the compounds of formulae (1) to (167) are used as light-emitting materials. For this purpose, the compounds are preferably used in an emitting layer. In addition to at least one compound of formulae (1) to (167), the emitting layer further comprises at least one host material. A person skilled in the art can easily select from known host materials without any difficulty and without requiring an inventive step.

[0098] In a further embodiment of the present invention, the compounds of formulae (1) to (167) are used as matrix materials in combination with one or more dopants, preferably phosphorescent dopants.

[0099] In a system comprising a matrix material and a dopant, the dopant is used to mean the component that is the minor component of the mixture. Correspondingly, in a system comprising a matrix material and a dopant, the matrix material is used to mean the component that is the major component of the mixture.

[0100] In this case, the ratio of the matrix material in the light-emitting layer is 50.0 to 99.9% by volume, preferably 80.0 to 99.5% by volume, and particularly preferably 92.0 to 99.5% by volume for the fluorescent-emitting layer, and 85.0 to 97.0% by volume for the phosphorescent-emitting layer.

[0101] Correspondingly, the proportion of the dopant is 0.1 to 50.0% by volume, preferably 0.5 to 20.0% by volume, and particularly preferably 0.5 to 8.0% by volume for the fluorescent-emitting layer, and 3.0 to 15.0% by volume for the phosphorescent-emitting layer.

[0102] The light-emitting layer of an organic electroluminescent device may also contain multiple matrix materials (mixed matrix system) and / or multiple dopants. In this case, the dopants generally have a smaller proportion in the system, and the matrix materials have a larger proportion in the system. However, in individual cases, the proportion of each matrix material in the system may be smaller than the proportion of each dopant.

[0103] In a further preferred embodiment of the present invention, the compounds of formulas (1) to (167) are used as components of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, particularly preferably two different matrix materials. Here, one of the two materials preferably has hole-transporting properties, and the other has electron-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed matrix components may be primarily or completely combined in a single mixed matrix component, with an additional mixed matrix component performing the other function. Here, the two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, and very particularly preferably 1:4 to 1:1. The mixed matrix system is preferably used in a phosphorescent organic electroluminescent device. More precise information on mixed matrix systems can be found, inter alia, in application WO 2010 / 108579.

[0104] The mixed matrix system may contain one or more dopants, preferably one or more phosphorescent dopants. Generally, the mixed matrix system is preferably used in a phosphorescent organic electroluminescent device. Matrix materials that are particularly suitable as matrix components of mixed matrix systems in combination with the compounds of the present invention are selected from the preferred matrix materials for phosphorescent dopants or the preferred matrix materials for fluorescent dopants shown below, depending on which type of dopant is used in the mixed matrix system.

[0105] Preferred phosphorescent dopants for use in mixed matrix systems are those shown in the table above.

[0106] Materials preferably used in the relevant functions in the device of the present invention are listed below.

[0107] Preferred fluorescent dopants are selected from the arylamine class. An arylamine or aromatic amine in the sense of the present invention comprises three substituted or unsubstituted aromatic or heteroaromatic ring structures directly bonded to the nitrogen atom. At least one of these aromatic or heteroaromatic ring structures is preferably a fused ring structure, particularly preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines, and aromatic chrysenediamines. Aromatic anthracenamines are used to refer to compounds in which one diarylamino group is directly bonded to the anthracene group, preferably at the 9-position. Aromatic anthracenediamines are used to refer to compounds in which two diarylamino groups are directly bonded to the anthracene group, preferably at the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are similarly defined, where the diarylamino group is preferably bonded to the pyrene group at the 1- or 1,6-position.

[0108] Preferably, suitable matrix materials for fluorescent dopants are materials from various classes in addition to the compounds of the present invention. Preferred matrix materials are oligoarylenes (for example 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (for example DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (for example according to WO 2004 / 081017), hole-conducting compounds (for example according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (for example according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (for example according to WO 2006 / 048268), boronic acid derivatives (for example according to WO 2006 / 177052) or benzanthracenes (for example WO 2008 / 145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. Oligoarylene in the sense of the present invention is used to mean a compound in which at least three aryl or arylene groups are bonded to one another.

[0109] Preferred matrix materials for phosphorescent dopants, in addition to the compounds of the invention, are aromatic amines, in particular triarylamines, for example carbazole derivatives (e.g. CBP (NN-biscarbazolylbiphenyl)) according to US 2005 / 0069729 or compounds according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, for example bridged carbazole derivatives according to applications WO 2011 / 088877 and WO 2011 / 128017, for example indenocarbazole derivatives according to WO 2010 / 0136109 and WO 2011 / 000455, for example EP 1617710, EP 1617711, EP 1731584, JP azacarbazole derivatives according to, for example, WO 2005 / 347160, indolocarbazole derivatives according to, for example, WO 2007 / 063754 or WO 2008 / 056746, ketones according to, for example, WO 2004 / 093207 or 2010 / 006680, phosphine oxides, sulfoxides and sulfones according to, for example, WO 2005 / 003253, oligophenylenes, bipolar matrix materials according to, for example, WO 2007 / 137725, silanes according to, for example, WO azaboroles or boronic esters according to, for example, WO 2006 / 117052, triazine derivatives according to, for example, WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes according to, for example, EP 652273 and WO 2009 / 062578, aluminum complexes such as BAlq, diazasirol and tetraazasirol derivatives according to, for example, WO 2010 / 054729, diazaphosphole derivatives and aluminum complexes according to, for example, WO 2010 / 054730, for example BAlq Suitable charge transport materials that can be used in the hole injection or hole transport layer or in the electron transport layer of the organic electroluminescent device of the present invention are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art.

[0110] The cathode of an organic electroluminescent device preferably comprises a metal with a low work function, a metal alloy containing various metals, or a multilayer structure, such as alkaline earth metals, alkali metals, main group metals, or lanthanide metals (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys containing alkali metals or alkaline earth metals and silver, such as alloys containing magnesium and silver. In the case of multilayer structures, additional metals with relatively high work functions, such as Ag or Al, can be used in addition to the metals mentioned above. In such cases, metal combinations such as Ca / Ag, Mg / Ag, or Ag / Ag are commonly used. It may also be preferable to insert a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Furthermore, lithium quinolinate (LiQ) can be used for this purpose. The layer thickness of this layer is preferably 0.5 to 5 nm.

[0111] The anode preferably comprises a material with a high work function. The anode preferably has a work function higher than 4.5 eV vs. vacuum. Suitable for this purpose are, on the one hand, metals with a high reduction potential, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (e.g., Al / Ni / NiO x , Al / PtO x) may also be preferred. For some applications, at least one electrode must be transparent or partially transparent to allow either illumination of the organic material (organic solar cells) or light outcoupling (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Further preferred are conductive doped organic materials, in particular conductive doped polymers.

[0112] The element is appropriately structured (depending on the application), provided with contacts and finally sealed, since the lifetime of the element according to the invention is shortened in the presence of water and / or air.

[0113] In a preferred embodiment, the organic electroluminescent device of the present invention is one or more layers applied by a sublimation process, and the materials are -5 less than 10 mbar, preferably less than 10 -6 characterized by vacuum vapor deposition in a vacuum sublimation unit at an initial pressure of less than 10 mbar. However, the initial pressure may be even lower, for example, 10 -7 Even below mbar is possible.

[0114] Similarly preferred organic electroluminescent devices are those in which one or more layers are applied by OVPD (organic vapor phase deposition) process or carrier gas sublimation, and the materials are -5 It is applied at pressures between mbar and 1 bar. A special case of this process is the OVJP (organic vapor jet printing) process, in which the material is applied directly by a nozzle and thereby structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0115] Furthermore, preferred organic electroluminescent devices are characterized in that one or more layers are produced from solution, for example by spin coating, or by any desired printing process, such as screen printing, flexographic printing, nozzle printing or offset printing, particularly preferably LITI (light-induced thermal imaging, thermal transfer printing), or inkjet printing. For this purpose, soluble compounds of formula (1) are required. High solubility can be achieved by appropriate substitution of the compound.

[0116] For the production of the organic electroluminescent device of the present invention it is further preferred to apply one or more layers from solution and one or more layers by a sublimation process.

[0117] According to the present invention, electronic devices comprising one or more compounds of formulae (1) to (167) can be used as light sources for lighting applications, as light sources for medical and / or cosmetic applications (e.g., phototherapy), and in display devices.

[0118] Devices containing compounds of formulas (1) to (167) can be used in a very versatile manner. Thus, for example, electroluminescent devices comprising one or more compounds of formulas (1) to (167) can be used in screens for televisions, mobile phones, computers, and cameras. However, the devices can also be used for lighting applications. Furthermore, electroluminescent devices comprising at least one compound of formulas (1) to (167), such as OLEDs or OLECs, can be used in medical or cosmetic phototherapy. Thus, numerous diseases (psoriasis, atopic dermatitis, inflammation, acne, skin cancer, etc.) can be treated, or skin wrinkles, redness, and aging can be prevented or reduced. Furthermore, light-emitting devices can be used to keep drinks, food, or food fresh, or to sterilize devices (e.g., medical devices).

[0119] The compounds according to the present invention and the organic electroluminescent devices according to the present invention differ from the prior art by the following surprising advantages over the prior art:

[0120] 1. The compounds according to the invention are highly suitable for use in hole transport layers or hole injection layers in electronic devices, such as organic electroluminescent devices, due to their high hole mobility.

[0121] 2. The compounds according to the invention have a relatively low sublimation temperature, high temperature stability, high oxidative stability and high glass transition temperature, which is advantageous both for processability, e.g. from solution or from the gas phase, and for use in electronic devices.

[0122] 3. The use of the compounds according to the present invention in electronic devices, as materials for hole transport layers or hole injection layers, and also as light emitting materials, results in high efficiency, low driving voltage and long life.

[0123] It should be pointed out that variations of the described embodiments of the present invention fall within the scope of the present invention. Each feature disclosed in the present invention may, unless expressly excluded, be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless otherwise specified, each feature disclosed in the present invention should be considered as an example of a generic series or as an equivalent or similar feature.

[0124] All features of the present invention may be combined with one another in any way, provided that certain features and / or steps are not mutually exclusive. This applies particularly to preferred features of the present invention. Similarly, features of non-essential combinations may be used separately (and not in combination).

[0125] Many features, particularly those of preferred embodiments of the present invention, are inventive in their own right and must be considered as not merely part of an embodiment of the present invention. Independent protection may be afforded for these features in addition to or as an alternative to the presently claimed invention.

[0126] The teachings regarding the technical features disclosed in the present invention can be extracted and combined with other examples.

[0127] The present invention will be explained in more detail by the following use examples, but the present invention is not limited to the scope of the examples.

[0128] example material [ka] [ka] [ka]

[0129] The materials HIL1, HIL2 (EP 0676461), H1 (WO 2008 / 145239), ETM1 (WO 2005 / 053055), SEB1 (WO 2008 / 006449), LIQ, and NPB are well known to those skilled in the art. Their properties and synthesis are known from the prior art. Compounds (3-3), (3-1), (2-1), (2-2), and (2-7) are in accordance with the present invention.

[0130] Example 1 Synthesis of compound biphenyl-2-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (1-1) and compounds (1-2) to (1-5) [ka]

[0131] 23.5 g of biphenyl-2-ylbiphenyl-4-ylamine (73 mmol) and 20.0 g of 2-bromofluorene (73 mmol) are dissolved in 500 ml of toluene, and the solution is degassed and saturated with N2. 2.52 g (2.93 mmol) of tri-tert-butylphosphine and 0.33 g (1.46 mmol) of palladium(II) acetate are then added. 10.8 g of sodium tert-butoxide (110 mmol) are then added. The reaction mixture is heated to boiling under a protective atmosphere for 6 hours. The mixture is then partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na2SO4, and evaporated in a rotary evaporator. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from heptane / toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 32.0 g (85% of theory).

[0132] The following compounds (1-2) to (1-5) are prepared in the same manner. [ka]

[0133] Example 2 Synthesis of compound biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1) and compounds (2-2) to (2-10) [ka]

[0134] 2-Bromo-9,9-diphenyl-9H-fluorene (2-1) 30 g (103 mmol) of methyl 4'-bromobiphenyl-2-carboxylate is dissolved in 500 ml of anhydrous THF in a heat-dried flask. The clear solution is cooled to -10 °C, and 102 ml (307 mmol) of a freshly prepared 3 M solution of 2-phenylmagnesium bromide is then added. The reaction mixture is slowly warmed to room temperature and then cooled using NH4Cl (500 ml). The mixture is then partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na2SO4, and evaporated in a rotary evaporator. 400 ml of acetic acid is carefully added to the residue. 80 ml of fuming HCl is then added. The batch is heated to 75 °C and maintained at this temperature for 5 hours. A white solid precipitates during this period. The batch is then cooled to room temperature, and the precipitated solid is filtered off with suction and rinsed with methanol. The residue is dried in vacuo at 40° C. The yield is 29.4 g (74 mmol) (72% of theory).

[0135] The following brominated compounds are prepared similarly: [ka]

[0136] Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1) 17 g of biphenyl-2-ylbiphenyl-4-ylamine (53 mmol) and 21 g of 2-bromo-9,9-diphenyl-9H-fluorene (53 mmol) were dissolved in 350 ml of toluene, and the solution was degassed and saturated with N2. 2.1 ml (2.1 mmol) of a 1 M solution of tri-tert-butylphosphine and 0.24 g (1.06 mmol) of palladium(II) acetate were then added, followed by 12.7 g of sodium tert-butoxide (132 mmol). The reaction mixture was heated to boiling under a protective atmosphere for 5 hours. The mixture was then partitioned between toluene and water, and the organic phase was washed three times with water, dried over Na2SO4, and evaporated in a rotary evaporator. The crude product was filtered through silica gel with toluene, and the remaining residue was recrystallized from heptane / toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 25 g (74% of theory).

[0137] The following compounds (2-2) to (2-10) can be prepared in a similar manner. [ka] [ka] [ka]

[0138] Example 3 Synthesis of compound biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine (3-1) and compounds (3-2) to (3-8) [ka]

[0139] 9,9-dimethyl-7-phenyl-9H-fluorene 8.9 g (73 mmol) of benzeneboronic acid and 20 g (73 mmol) of 2-bromo-9,9'-dimethyl-9H-fluorene were dissolved in 330 ml of dimethoxyethane and 110 ml of 2M The mixture is suspended in a Na2SO4 solution. 2.54 g (2.0 mmol) of tetrakis(triphenylphosphine)palladium are added to the suspension. The reaction mixture is heated under reflux for 16 hours. After cooling, the reaction mixture is diluted with ethyl acetate, the organic phase is separated, washed three times with 100 ml of water, and then evaporated to dryness. The crude product is filtered through silica gel with heptane / ethyl acetate (20:1) to give 18.8 g (95%) of 9,9-dimethyl-7-phenyl-9H-fluorene.

[0140] The following fluorenes are prepared similarly: [ka]

[0141] 2-Bromo-9,9-dimethyl-7-phenyl-9H-fluorene 29.0 g (107 mmol) of 9,9-dimethyl-2-phenyl-9H-fluorene was dissolved in 250 ml of CHCl3, and 17.2 g (107 mmol) of bromine dissolved in 50 ml of CHCl3 was slowly added at -10 °C. When the reaction was complete, water was added, and the organic phase was separated, dried, and evaporated. The crude product was then washed multiple times by stirring with hot MeOH / heptane (1:1). The yield of the product as a white solid was 33.3 g (89% of theoretical).

[0142] The following brominated compounds are prepared similarly: [ka]

[0143] Biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine (3-1) 19.9 g of biphenyl-2-ylbiphenyl-4-ylamine (62 mmol) and 21.6 g of 2-bromo-9,9-dimethyl-7-phenyl-9H-fluorene (62 mmol) are dissolved in 400 ml of toluene. The solution is degassed and saturated with N2. 3 ml (3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.57 g (2 mmol) of palladium(II) acetate are then added. 14.9 g of sodium tert-butoxide (155 mmol) are then added. The reaction mixture is heated to boiling under a protective atmosphere for 5 hours. The mixture is then partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na2SO4, and evaporated in a rotary evaporator. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from heptane / toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 29.7 g (82% of theory).

[0144] Compounds (3-2) to (3-8) are prepared in the same manner. [ka] [ka]

[0145] Example 4 Synthesis of comparative compounds HTMV1 to HTMV6 The following comparative compounds (HTMV1) to (HTMV6) are also prepared in the same manner as in the synthesis of compound (3-1) described in Example 3. [ka] [ka]

[0146] Example 5 Compound characterization The OLEDs according to the invention and according to the prior art are manufactured by the general process according to WO 04 / 058911, but adapted to the conditions described therein (layer thickness variations, materials).

[0147] Data for various OLEDs are given in the examples below (see Tables 1, 3 and 2, 4). The substrate used is a glass plate coated with a 50 nm thick structured ITO (indium tin oxide). The OLED basically has the following layer structure: substrate / optionally hole injection layer (HIL1) / hole transport layer (HTL) / hole injection layer (HIL2) / electron blocking layer (EBL) / emissive layer (EML) / electron transport layer (ETL) / optionally electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLED is shown in Tables 1 and 3. The materials required for the production of the OLED have been described above.

[0148] All materials are applied by thermal vapor deposition in a vacuum chamber. Here, the light-emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter) premixed with one or more matrix materials in a certain volumetric proportion by coevaporation. Here, an expression such as H1:SEB1 (95%:5%) means that the material H1 is present in the layer in a proportion of 95% by volume and the material SEB1 is present in the layer in a proportion of 5% by volume. Similarly, the electron-transporting layer may also consist of a mixture of two materials.

[0149] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A) as a function of luminance, calculated from the current / voltage / luminance characteristic line (IUL characteristic line) assuming Lambertian emission characteristics, the power efficiency (measured in Im / W), the external quantum efficiency (EQE, measured in percent), and the lifetime are measured. The electroluminescence spectrum is measured at a luminance of 1000 cd / m 2 The CIE 1931 x and y color coordinates are calculated from this. 2 EQE at driving brightness of 1000cd / m2 The external quantum efficiency at 6000 cd / m 2 The LT80 has an OLED display with a brightness of 6000 cd / m 2 From this, 80% of the initial luminance, i.e., 4800 cd / m 2 The data for various OLEDs are summarized in Tables 2 and 4.

[0150] Use of compounds according to the invention as hole transport materials in fluorescent and phosphorescent OLEDs The compounds according to the present invention are particularly suitable as HILs, HTLs, or EBLs in OLEDs. They are suitable not only as single layers, but also as mixed components as HILs, HTLs, EBLs, or in EMLs. Compared with NPB reference components (V1, V8), samples containing the compounds according to the present invention show significantly improved lifetimes as well as higher efficiencies in both singlet blue and triplet green.

[0151] Compared to the reference materials HTMV1-HTMV6 (V2-V10), the compounds according to the invention have the same or better efficiency and improved lifetime. [Table 1] [Table 2] [Table 3] [Table 4]

Claims

1. Compounds of general formula (167); 【Chemical 1】 The following applies to the symbols used in equation (167): Ar ３ , Ar ４ are terphenyl, each of which contains one or more groups R ５ may be substituted by; R ５ are the same or different for each occurrence, H, D, C(=O)R ６ , CN, Si(R ６ ) ３ , NO ２ , P(=O)(R ６ ) ２ , S(=O)R ６ , S(=O) ２ R ６ , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms (the above-mentioned groups are each optionally joined by one or more groups R ６ and one or more of the CH ２ The group is -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=S, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, P(=O)(R ６ ), -O-, -S-, SO or SO ２ wherein one or more H atoms in the above mentioned groups may be replaced by D, CN or NO ２ or in each case one or more groups R ６ a heteroaromatic ring structure having 5 to 30 aromatic ring atoms, which may be substituted by one or more groups R ６ an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms optionally substituted by R ６ is identical or different at each occurrence and is H, D, an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 C atoms, in which one or more H atoms may be replaced by D; R ７ are identical on each occurrence and denote a linear alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms (the above-mentioned groups are in each case bound to one or more groups R ５ wherein two groups R ７ may also form closed rings with each other, thus forming spiro compounds, in which the aromatic or heteroaromatic ring is joined by two groups R ７ is not fused onto the ring formed by R ８ is H or D; a is 1, 2, 3, or 4; with the proviso that the compound of formula (167) contains, apart from one fluorene group, and apart from a possible fused or polycyclic group at the 9-position of the fluorene, no further polycyclic or fused groups; and, with the proviso that the compound does not contain a halogen.

2. 2. The compound according to claim 1, wherein a is 1 or 2.

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

4. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 3, wherein the bond to the polymer, oligomer or dendrimer may be located at any desired position.

5. A composition comprising one or more compounds according to any one of claims 1 to 3 and at least one further organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

6. A formulation comprising at least one compound according to any one of claims 1 to 3, or at least one polymer, oligomer or dendrimer according to claim 4, or at least one composition according to claim 5, and at least one solvent.

7. An electronic device comprising at least one compound according to any one of claims 1 to 3, or at least one polymer, oligomer or dendrimer according to claim 4, or at least one composition according to claim 5.

8. 8. The electronic device according to claim 7, characterized in that it is selected from organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenched devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

9. 9. An electronic device according to claim 7 or 8, selected from the group of organic electroluminescent devices, characterized in that a compound according to any one of claims 1 to 3, or a polymer, oligomer or dendrimer according to claim 4, or a composition according to claim 5 is used in one or more of the following functions: as a hole transport material in a hole transport layer or hole injection layer, as a matrix material in a light-emitting layer, as an electron blocking material or as an exciton blocking material.

10. 10. The electronic device of claim 9, which is an organic light emitting diode (OLED).

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