Organic electroluminescent devices

Abstract

Electronic device containing at least one compound of formula I: wherein the symbols and indices used have the following meanings: W is the same or different in each occurrence N or CR 1 ; Y is the same or different at each occurrence N or CR 2 ; E is either a covalent single bond or is a bivalent unit selected from the group consisting of N(R) 3 ), C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; X is either equal to or different from a bivalent unit chosen from the group consisting of C(R) at each occurrence. 3 )2, N(R 3 ), Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3consists, with the proviso that if E is a covalent single bond, X is a bivalent unit selected from the group consisting of C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; n, m are independently 0 or 1, with the proviso that the sum of n and m is equal to 1 or 2; Ar is a bivalent or trivalent, mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups. 4a may be substituted; Ar 1 is an electron-deficient, mono- or polycyclic heteroaromatic group with 5 to 10 aromatic ring atoms, coupled with one or more R substituents 4b may be substituted; L is either a covalent single bond or represents a bivalent unit selected from the group consisting of -C(O)-, -Ar 2 C(O)- and -Ar 2 - exists, whereby in the case that the bivalent unit -Ar 2 -C(O)- is the group Ar 2 binds to N and C(O) to the group Ar 1 binds; Ar 2 is a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups 4a or R 4b may be substituted; R 1 , R 2 are the same or different in each occurrence, selected from the group consisting of: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3, CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , C=O, C=S, , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 1 and / or R 2 can be linked to each other via a covalent single bond or a bivalent group Z; R 3 is the same or different in each occurrence selected from the group consisting of the following: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CR 5 =CR 5 Ar 3 , CN, NO2, Si(R 5 )3, B(OR 5 )2, OSO2R 5 , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 3 can be linked to each other via a covalent single bond or a bivalent group Z; R4a , R 4b are selected from the group consisting of the following, and are either the same or different in each occurrence: D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , C=O, C=S, , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 4a or R 4b can be linked to each other via a covalent single bond or a bivalent group Z; Ar 3 is a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups 6 may be substituted; R 5is the same or different at each occurrence H, D, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is further divided by one or more R groups 6 can be substituted; where two or more substituents R are also possible 5 can be linked to each other via a covalent single bond or a bivalent group Z; R Sis the same or different at each occurrence H, D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F; wherein two or more substituents R 6 can be linked to each other via a covalent single bond or a bivalent group Z; Z represents a bivalent group -(CH2) q - dar, where q is 1, 2, 3, 4 or 5, preferred 1, 2, 3 or 4, more preferred 1, 2 or 3, and most preferred 1 or 2.

Description

[0001] The present invention describes indenocarbazole derivatives that can preferably be used as matrix materials for phosphorescent dopants or as electron transport materials, in particular for use in the emission and / or charge transport layer of electroluminescent devices. The invention further relates to polymers containing these compounds as structural units, a method for preparing the compounds according to the invention, and electronic devices containing these compounds.

[0002] Organic semiconductors are being developed for a variety of electronic applications. The construction of organic electroluminescent devices (OLEDs), in which these organic semiconductors are used as functional materials, is described, for example, in US 4539507, US 5151629, EP 0676461, and WO 98 / 27136. However, further improvements are still needed. In particular, there is a need for improvement regarding the lifetime, efficiency, and operating voltage of organic electroluminescent devices. Furthermore, it is necessary that the compounds exhibit high thermal stability and a high glass transition temperature and can be sublimated without decomposition.

[0003] Improvements to the aforementioned properties are still needed, particularly in phosphorescent electroluminescence devices. Specifically, there is a need for improvements in matrix materials for phosphorescent emitters that simultaneously offer good efficiency, long lifetime, and low operating voltage. The properties of the matrix materials are often the limiting factor for the lifetime and efficiency of organic electroluminescence devices.

[0004] According to the current state of the art, carbazole derivatives, e.g., bis(carbazolyl)biphenyl, are frequently used as matrix materials. There is still room for improvement here, particularly with regard to the lifetime and glass transition temperature of the materials.

[0005] Ketones (WO 2004 / 093207, WO 2010 / 006680), phosphine oxides, and sulfones (WO 2005 / 003253) are also used as matrix materials for phosphorescent emitters. Low operating voltages and long lifetimes are achieved, particularly with ketones. However, there is still room for improvement, especially regarding efficiency and compatibility with metal complexes containing ketoketonate ligands, such as acetylacetonate.

[0006] Furthermore, metal complexes, such as BAlq or bis[2-(2-benzothiazole)phenolate]-zinc(II), are used as matrix materials for phosphorescent emitters. There is still room for improvement here, particularly regarding operating voltage and chemical stability. Purely organic compounds are often more stable than these metal complexes. For example, some of these metal complexes are sensitive to hydrolysis, which complicates their handling.

[0007] In particular, there is still a need for improvement in matrix materials for phosphorescent emitters that simultaneously lead to high efficiencies, long lifetimes and low operating voltages, and which are also compatible with phosphorescent emitters that carry ketoketonate ligands.

[0008] Improvements in the properties of electron transport materials are also desirable, as these properties significantly influence the aforementioned properties of the organic electroluminescence device. In particular, there is a need for improvements in electron transport materials that simultaneously offer good efficiency, a long lifetime, and low operating voltage.

[0009] It would be desirable to have electron transport materials available that lead to better electron injection into the emitting layer, since a more electron-rich emission layer results in greater efficiency. Furthermore, improved injection allows for a reduction in the operating voltage. Therefore, further improvements to the electron transport material are necessary. Electroluminescent devices using AlQ3 as an electron conductor have been known for a long time and were described as early as 1993 in US 4,539,507. Since then, AlQ3 has been frequently used as an electron transport material, but it has several disadvantages: It cannot be deposited without leaving residues, as it partially decomposes at the sublimation temperature, which poses a significant problem, especially for production facilities. Consequently, the deposition sources must be cleaned or replaced repeatedly.Furthermore, decomposition products of AlQ3 enter the OLED, contributing to a reduced lifetime and lower quantum and power efficiency. AlQ3 also has low electron mobility, leading to higher voltages and thus lower power efficiency. To avoid short circuits in the display, increasing the layer thickness would be desirable; however, this is not possible with AlQ3 due to its low charge carrier mobility and the resulting voltage increase. The charge carrier mobility of other electron conductors (US 4,539,507) is also too low to allow for thicker layers, and the lifetime of the OLED is even worse than when using AlQ3. The inherent color (yellow in the solid state) of AlQ3 also proves disadvantageous, as it can lead to color shifts, especially in blue OLEDs, due to reabsorption and weak re-emission. In this case, blue OLEDs can only be represented with significant losses in efficiency and / or color accuracy.

[0010] There is therefore still a need for electron transport materials in organic electroluminescence devices that achieve both high efficiency and long lifetimes. It has now been surprisingly found that organic electroluminescence devices containing certain indenofluorene derivatives—listed below—as electron transport materials exhibit significant improvements over the prior art. These materials make it possible to achieve both high efficiency and long lifetimes, which is not possible with prior art materials. Furthermore, it has been found that the operating voltages can also be significantly reduced, resulting in higher power efficiencies.

[0011] Furthermore, it was found that electronic devices containing these indenofluorene derivatives as electron transport materials in combination with an organic alkali metal compound exhibit significant improvements over the prior art. This material combination achieves high efficiency and long lifetimes while simultaneously reducing operating voltages.

[0012] EP 1860097, WO 2006 / 100896, DE 102006025846, WO 2006 / 122630, WO 2008 / 132103, WO 2008 / 006449, WO 2008 / 056746, WO 2008 / 149691, WO 2008 / 146839 and WO 2008 / 006449 disclose indenofluorene derivatives for use in electronic devices. These patents report good lifetimes when used as hole transport materials or as deep blue emitters. However, these compounds sometimes exhibit the problem that, due to their crystallinity, they crystallize at the evaporation source during mass production, thereby clogging the evaporation source. The use of these materials in production is therefore subject to increased technical effort. Further improvements are therefore desirable.

[0013] Consequently, there remains a need for both improved matrix materials for phosphorescent dopants that are suitable for improving the efficiency of organic electroluminescence devices, while simultaneously leading to long lifetimes and being technically easy to process, and for improved electron transport materials.

[0014] The object of the present invention is therefore to provide such compounds.

[0015] It was surprisingly found that electroluminescent devices using indenocarbazole derivatives according to the invention exhibit significant improvements over the prior art, particularly when used as matrix materials for phosphorescent dopants or as electron transport materials. These improvements result in longer lifetimes, lower operating voltages due to changes in the interface morphology, and a reduced dependence of the voltage on the transport layer thickness, possibly due to improved electron mobility.

[0016] The invention provides a compound of the following formula I: where the symbols and indices used have the following meanings: W is the same or different in each occurrence N or CR 1 ; Y is the same or different at each occurrence N or CR 2 ; E is either a covalent single bond or is a bivalent unit selected from the group consisting of N(R) 3 ), C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; X is either equal to or different from a bivalent unit chosen from the group consisting of C(R) at each occurrence. 3 )2, N(R 3 ), Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3 consists, with the proviso that if E is a covalent single bond, X is a bivalent unit selected from the group consisting of C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; n, m are independently 0 or 1, with the proviso that the sum of n and m is equal to 1 or 2; Ar is a bivalent or trivalent, mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups. 4a may be substituted; Ar 1 is a mono- or polycyclic heteroaromatic group with 5 to 40 aromatic ring atoms, coupled with one or more R groups 4b may be substituted; L is either a covalent single bond or represents a bivalent unit selected from the group consisting of -C(O)-, -Ar 2 -C(O)- and -Ar 2 - exists, whereby in the case that the bivalent unit -Ar 2 -C(O)- is the group Ar 2 binds to N and C(O) to the group Ar 1 binds; Ar 2is a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups 4a or R 4b may be substituted; R 1 , R 2 are the same or different in each occurrence, selected from the group consisting of: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , C=O, C=S, P(=O)(R 5 ), SO, SO2, NR 5, O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 1 and / or R 2 can be linked to each other via a covalent single bond or a bivalent group Z; R 3 is the same or different in each occurrence selected from the group consisting of the following: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CR5 =CR 5 Ar 3 , CN, NO2, Si(R 5 )3, B(OR 5 )2, OSO2R 5 , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C≡C , Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 3 can be linked to each other via a covalent single bond or a bivalent group Z; R 4a , R 4b are selected from the group consisting of the following, and are either the same or different in each occurrence: D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms, each with one or more R groups 5can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C≡C , C=O, C=S, , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 4a or R 4b can be linked to each other via a covalent single bond or a bivalent group Z; Ar 3is a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups 6 may be substituted; R 5 is the same or different at each occurrence H, D, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is further divided by one or more R groups 6 can be substituted; where two or more substituents R are also possible 5 can be linked to each other via a covalent single bond or a bivalent group Z; R 6is the same or different at each occurrence H, D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F; wherein two or more substituents R 6 can be linked to each other via a covalent single bond or a bivalent group Z; Z represents a bivalent group -(CH2) q - dar, where q is 1, 2, 3, 4 or 5, preferred 1, 2, 3 or 4, more preferred 1, 2 or 3, and most preferred 1 or 2.

[0017] In a preferred embodiment of the invention, a maximum of two symbols Y and W simultaneously represent N, more preferably a maximum of one symbol Y and W.

[0018] A bivalent or trivalent mono- or polycyclic aromatic or heteroaromatic unit, such as for Ar or Ar 2The unit is defined as containing preferably 5 to 40, more preferably 5 to 20, most preferably 5 to 10 aromatic ring atoms. If the unit is an aromatic unit, it preferably contains 6 to 40, more preferably 6 to 20, most preferably 6 to 10 carbon atoms as ring atoms. If the unit is a heteroaromatic unit, it contains 5 to 40, more preferably 5 to 20, most preferably 5 to 10 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic unit is understood to be either a simple aromatic cycle, i.e., benzene, or a simple heteroaromatic cycle, for example, pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, for example, naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, benzothiophene, benzofuran and indole, etc.

[0019] Examples of the aromatic or heteroaromatic unit according to the invention are accordingly: benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, benzanthracene, perylene, naphthacene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole. Phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine,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, 1,2,3-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.,

[0020] The aforementioned compounds exist as bivalent or trivalent units in such a way that two or three hydrogen substituents are missing and these compounds are bonded at these positions - as indicated in formula I.

[0021] In the present invention, a mono- or polycyclic aromatic or heteroaromatic group is understood to be a monovalent residue that is otherwise defined in the same way as the mono- or polycyclic aromatic or heteroaromatic unit. The examples mentioned above are also illustrative here.

[0022] Within the scope of the present invention, a straight-chain, branched, or cyclic alkyl group is understood to be an alkyl, alkenyl, or alkynyl group with preferably 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, or 3 to 40 carbon atoms, more preferably 3 to 20 carbon atoms. Cyclic alkyl groups can be mono-, bi-, or polycyclic alkyl groups. Individual -CH or -CH2 groups can be replaced by N, NH, O, or S. Preferred are the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 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, pentinyl, hexynyl, heptynyl or octynyl understood. Under a C1 to C 40-Alkoxy group is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.

[0023] An alkoxy group or thioalkyl group is an alkyl group as defined above, which is bonded via an O or S atom.

[0024] The alkyl groups, alkoxy groups or thioalkyl groups can also be modified by one or more R groups as defined above. 5 be substituted.

[0025] For the purposes of this invention, a mono- or polycyclic aromatic ring system is preferably understood to be an aromatic ring system with 6 to 40 carbon atoms, preferably 6 to 30, and particularly preferably 6 to 12 carbon atoms. An aromatic ring system within the meaning of the present invention is understood to be a system that does not necessarily contain only aromatic groups, but also includes several aromatic groups separated by a short non-aromatic unit (< 10% of the non-hydrogen atoms, preferably < 5% of the non-hydrogen atoms), such as sp 3These aromatic ring systems can be interrupted by a hybridized C, O, N, etc., or a CO group. They can be monocyclic or polycyclic, meaning they can have one ring (e.g., phenyl) or two or more rings, which can also be fused (e.g., naphthyl) or covalently linked (e.g., biphenyl), or a combination of fused and linked rings. However, fused rings are particularly preferred.

[0026] Preferred aromatic ring systems include, for example, benzene, biphenyl, terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, benzanthracene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, spirobifluorene, and indene.

[0027] For the purposes of this invention, a mono- or polycyclic heteroaromatic ring system is preferably understood to be a heteroaromatic ring system with 5 to 40 ring atoms, more preferably 5 to 30, and more preferably 5 to 14 ring atoms. The heteroaromatic ring system contains at least one heteroatom selected from N, O, and S (the remaining atoms being carbon). Furthermore, a heteroaromatic ring system is understood to be a system that does not necessarily contain only aromatic or heteroaromatic groups, but in which several aromatic or heteroaromatic groups are also separated by a short non-aromatic unit (< 10% of the non-H atoms, preferably < 5% of the non-H atoms), such as sp 3-hybridized C, O, N, etc., or a CO group. These heteroaromatic ring systems can be monocyclic or polycyclic, i.e., they can have one ring (e.g., pyridyl) or two or more rings, which may also be fused or covalently linked, or a combination of fused and linked rings. Condensed rings are particularly preferred.

[0028] Bevorzugte heteroaromatische Ringsysteme sind z. B. 5-gliedrige Ringe wie Pyrrol, Pyrazol, Imidazol, 1,2,3-Triazol, 1,2,4-Triazol, Tetrazol, Furan, Thiophen, Selenophen, Oxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 6-gliedrige Ringe wie Pyridin, Pyridazin, Pyrimidin, Pyrazin, 1,3,5-Triazin, 1,2,4-Triazin, 1,2,3-Triazin, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, oder kondensierte Gruppen wie Indol, Isoindol, Indolizin, Indazol, Benzimidazol, Benzotriazol, Purin, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, Benzothiazol, Benzofuran, Isobenzofuran, Dibenzofuran, Chinolin, Isochinolin, Pteridin, Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Benzoisochinolin, Acridin, Phenothiazin, Phenoxazin, Benzopyridazin,Benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno-[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups. Imidazole, benzimidazole, and pyridine are particularly preferred.

[0029] Form two substituents, e.g., two R 1 or R 1 and R 2 If the two elements form a bivalent mono- or polycyclic aromatic or heteroaromatic ring system, the aforementioned short non-aromatic unit can also bind directly to Y or W. In this case, the short non-aromatic unit is particularly preferably a CO group.

[0030] An aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms is defined as a group that, via an oxygen atom, carries a mono- or polycyclic aromatic or heteroaromatic group with 5 to 40 ring atoms, as defined above. The aryloxy or heteroaryloxy group may also bear one or more substituents, as defined above.

[0031] In one embodiment of the present invention, Y is preferably equal to or different from CR. 1 .

[0032] It is also an embodiment of the present invention that W is preferably equal to or different from CR 2 is.

[0033] In a further embodiment of the present invention, E is preferably either a covalent single bond or a bivalent unit selected from N(R 3 ), C(R 3 )2, O and S. E is even more strongly preferred as a covalent single bond.

[0034] In a further embodiment of the present invention, X is preferably, at each occurrence, the same or different as a bivalent unit selected from the group consisting of C(R). 3 )2, S and O. X is particularly preferred as C(R 3 )2.

[0035] In a further embodiment, Ar is preferably a bivalent or trivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms, coupled with one or more R groups. 4a Ar can be substituted. In particular, Ar is preferably equal to phenylene or naphthylene, phenylene is most preferred.

[0036] In a further embodiment of the present invention, Ar 1 preferably a mono- or polycyclic heteroaromatic group with 5 to 10 aromatic ring atoms, coupled with one or more R groups 4b It may be substituted. Ar is particularly preferred.1 an electron-deficient heteroaromatic group containing one or more R substituents 4b can be substituted. Even more preferred are heteroaromatic groups with 6 aromatic ring atoms, at least one of which is a nitrogen atom, or heteroaromatic groups with 5 aromatic ring atoms, at least 2 of which are heteroatoms, preferably at least one of which is a nitrogen atom bonded to R 4b These groups can be substituted, and further aryl or heteroaryl groups may be fused to each of these groups. Preferred examples of electron-deficient heteroaromatic groups are: pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5-triazine, quinoline, isoquinoline, quinoxaline, pyrazole, imidazole, benzimidazole, thiazole, benzothiazole, oxazole, or benzooxazole, each with R 4b They can be substituted. Ar is the most preferred option. 1 one with R 4b substituted or unsubstituted 1,3,5-triazine.

[0037] In a further embodiment of the present invention, L is preferably a covalent single bond or a bivalent unit -Ar 2 - is preferred. 2 This is a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms, coupled with one or more R groups. 4a or R 4b It can be substituted. Particularly favored examples of this are phenylene and naphthylene, with phenylene being even more favored.

[0038] In another embodiment, R 1 and R 2 each independently selected preferably from the group consisting of H, D, N(Ar 3 )2, C(=O)Ar 3, a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms and a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is separated by one or more R groups 6 It can be substituted, exists. R is particularly preferred. 2 equal to H and one of the two R 1 is H and the other is selected from H, N(Ar 3 )2, C(=O)Ar 3 and a mono- or polycyclic aromatic ring system with 5 to 20 aromatic ring atoms, each separated by one or more R groups 6 can be substituted. Alternatively, two Rs can also be used. 1 or R 1 and R 2together they form a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms. Preferred examples are the following: where the bivalent systems are linked across the dashed lines.

[0039] In a further embodiment of the present invention, R 3 Preferably selected from the group consisting of H, D, a straight-chain alkyl group with 1 to 10 carbon atoms, a branched or cyclic alkyl group with 3 to 10 carbon atoms, and a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 10 aromatic ring atoms. Methyl, phenyl, diphenylamino-p-phenyl, and 3-(N-phenyl)carbazolyl are preferred. Alternatively, two R groups can also be selected. 3together they form a bivalent mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms. A preferred example of this is: where the dashed lines represent the connections to X.

[0040] In a further embodiment of the present invention, R 4a preferably the same or different for each occurrence selected from the group consisting of the following: N(Ar 3 )2, C(=O)Ar 3 , a straight-chain alkyl group with 1 to 6 carbon atoms, or a branched or cyclic alkyl group with 3 to 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by fluorine, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms. Particularly preferred examples are phenyl, diphenylamine, and C(=O)-Ph.

[0041] In a further embodiment of the present invention, R4b Preferably selected, either identically or differently at each occurrence, from the group consisting of: CN, F, a straight-chain alkyl group with 1 to 6 carbon atoms, a branched or cyclic alkyl group with 3 to 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms. Particularly preferred examples are phenyl, naphthyl, and carbazolyl.

[0042] In a further embodiment of the present invention, Ar 3 preferably a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms.

[0043] In a further embodiment of the present invention, the sum of the indices n + m = 1.

[0044] It is an integral part of the present invention that the aforementioned embodiments, or preferred areas or definitions of the present invention, can be combined with one another as desired.

[0045] Therefore, the following applies preferably to the symbols and indices: Y is the same or different in each occurrence CR 1 ; W is the same or different in each occurrence CR 2 ; E is either a covalent single bond or a bivalent unit selected from N(R) 3 ), C(R 3 )2, O and S, in particular a covalent single bond; X is either equal to or different from a bivalent unit chosen from the group consisting of C(R) at each occurrence. 3 )2, S and O consists, in particular C(R 3 )2; Ar is a bivalent or trivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms coupled with one or more R groups. 4a may be substituted, especially phenylene or naphthylene, phenylene being the preferred substitute; Ar 1 is a mono- or polycyclic heteroaromatic group with 5 to 10 aromatic ring atoms, coupled with one or more R groups 4b may be substituted, preferably an electron-deficient heteroaromatic group, which may be joined with one or more R groups 4b may be substituted, in particular pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5-triazine, quinoline, isoquinoline, quinoxaline, pyrazole, imidazole, benzimidazole, thiazole, benzothiazole, oxazole or benzooxazole, each with R 4b They can be substituted, preferably one with R 4b substituted or unsubstituted 1,3,5-triazine; L is a covalent single bond or a bivalent unit -Ar 2 -; Ar 2 is a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms, coupled with one or more R groups 4a or R 4b may be substituted, especially phenylene and naphthylene; R 1 , R 2 are each independently selected from the group consisting of H, D, N(Ar 3 )2, C(=O)Ar 3 , a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms and a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is separated by one or more R groups 6 can be substituted, exists; R 3is selected from the group consisting of H, D, a straight-chain alkyl group with 1 to 10 C atoms, a branched or cyclic alkyl group with 3 to 10 C atoms, and a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 10 aromatic ring atoms; R 4a is the same or different for each occurrence selected from the group consisting of: N(Ar 3 )2, C(=O)Ar 3 , a straight-chain alkyl group with 1 to 6 C atoms or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein one or more H atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms; R 4bis selected from the group consisting of the following, whether the same or different at each occurrence: CN, F, a straight-chain alkyl group with 1 to 6 C atoms, a branched or cyclic alkyl group with 3 to 6 C atoms, where one or more H atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms; Ar 3 is a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms;

[0046] For the sum of the indices n + m, the following holds true: n + m = 1.

[0047] It is further preferred that the compounds of general formulas I satisfy the following structural formulas: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (75) (76) (77) (78) (79) (80) (81) (82) (83) (84) (85) (86) (87) (88) (89) (90) (91) (92) (93) (94) (95) (96) (97) (98) (99) (100) (101) (102) (103) (104) (105) (106) (107) (108) (109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121) (122) (123) (124) (125) (126) (127) (128) (129) (130) (131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) (146) (147) (148) (149) (150) (151) (152) (153) (154)

[0048] The compounds according to the invention can be prepared by synthesis steps known to those skilled in the art, such as bromination, Suzuki coupling, Hartwig-Buchwald coupling, etc. The synthesis of compounds according to the invention is generally illustrated in the following Schemes 1 to 3.

[0049] The synthesis starts, for example, from 9,9-dimethylfluorenyl-2-boronic acid (Synlett, 2006, 5, 737-740), which is coupled to 1-bromo-2-nitrobenzene in a Suzuki coupling. The nitro group is closed to form a ring under the action of a phosphite, for example, triethyl phosphite, yielding the corresponding indenocarbazole derivative. The nitrogen can then be alkylated by alkylating agents or arylated in a Hartwig-Buchwald reaction. Thus, the Ar group can be removed. 1 can be introduced. The structures can, of course, also be substituted by further substituents.

[0050] An alternative manufacturing method is shown in Scheme 2.

[0051] The synthesis starts with a 2-bromocarbazole derivative. This is reacted with a 1-boronic acid-2-methylcarbonyl derivative of benzene in a Suzuki coupling. Subsequently, the nitrogen is protected with a thionyl group. The carbonyl group is reduced to a hydroxyl group with methyllithium. The subsequent ring closure can be achieved under the influence of polyphosphoric acid. After elimination of the thionyl protecting group, the nitrogen can then be alkylated by alkylating agents or arylated in a Hartwig-Buchwald reaction. Thus, the Ar group can be removed. 1 be introduced.

[0052] Another alternative manufacturing method is shown in Scheme 3.

[0053] The synthesis starts with a 2-bromofluorene derivative. This is reacted with a 1-boron-2-methylcarbonyl derivative of benzene in a Suzuki coupling. Subsequently, the methylcarbonyl group is reduced to a 1-hydroxyisopropyl group with methyllithium. The subsequent ring closure can be carried out under the influence of polyphosphoric acid. The nitrogen is then either alkylated by alkylating agents or arylated in a Hartwig-Buchwald reaction. Thus, the Ar group can be 1 be introduced.

[0054] Another object of the invention is a method for producing a compound of general formula I, comprising the steps: a) Coupling of a carbazole derivative or fluorene derivative with a benzene derivative, and b) Arylation of carbazole nitrogen to introduce Ar 1 .

[0055] The compounds described above can also be used to produce polymers, oligomers, or dendrimers. This is usually achieved via polymerizable functional groups. Compounds substituted with reactive leaving groups such as bromine, iodine, boronic acid, boronic esters, tosylate, or triflate are particularly preferred. These can be used as comonomers to generate corresponding conjugated, partially conjugated, or non-conjugated polymers, oligomers, or as the core of dendrimers. Polymerization preferably proceeds via the halogen or boronic acid functionality. The polymers can also possess or be crosslinkable groups. Crosslinkable groups are particularly suitable, as they can then be crosslinked within the layer of the electronic device.

[0056] A further object of the invention is thus polymers, oligomers, or dendrimers containing one or more compounds according to formula I, wherein one or more residues or hydrogen atoms of the compounds defined above form a bond to the polymer, oligomer, or dendrimer. The polymers, oligomers, or dendrimers can be conjugated, partially conjugated, or non-conjugated. Also included are mixtures (blends) of the polymers, oligomers, or dendrimers according to the invention with further polymers, oligomers, or dendrimers.

[0057] For the purposes of this invention, an oligomer is defined as a compound having approximately three to nine repeating units. A polymer, for the purposes of this invention, is defined as a compound having ten or more repeating units.

[0058] These oligomers or polymers may contain further repeating units. These further repeating units are preferably selected from the group consisting of fluorenes (e.g., according to EP 842208 or WO 2000 / 22026), spirobifluorenes (e.g., according to EP 707020, EP 894107 or EP 04028865.6), triarylamines, para-phenylenes (e.g., according to WO 92 / 18552), carbazoles (e.g., according to WO 2004 / 070772 and WO 2004 / 113468), thiophenes (e.g., according to EP 1028136), dihydrophenanthrenes (e.g., according to WO 2005 / 014689), indenofluorenes (e.g., according to WO 2004 / 041901 and WO 2004 / 113412), aromatic ketones (e.g., according to WO 2005 / 040302), phenanthrenes (e.g., according to WO 2005 / 104264) and / or metal complexes, in particular ortho-metallated iridium complexes. It should be expressly noted that the polymers may also have several different repeating units, which are selected from one or more of the groups mentioned above.

[0059] The compounds of formula I can be used in electronic devices, particularly in organic electroluminescent devices. The specific application of these compounds depends on the substituents.

[0060] Another object of the invention is therefore the use of the compounds according to formula I or the polymers, oligomers or dendrimers defined above in electronic devices.

[0061] A further object of the invention is an electronic device comprising at least one compound as defined above, or a polymer, oligomer, or dendrimer as defined above. Also included in the invention are mixtures (blends) of the oligomers, polymers, or dendrimers according to the invention, optionally with further oligomers, polymers, or dendrimers different from them, or further low-molecular-weight compounds.

[0062] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic integrated circuits (O-ICs), organic solar cells (O-SCs), organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic photoreceptors or organic laser diodes (O-lasers).

[0063] The present invention also relates to organic electroluminescence devices characterized in that several emitting compounds are used in the same layer or in different layers. The compound of formula I according to the invention can be used either as a matrix material in an emitting layer, as an electron transport material in an electron transport layer, or as a hole transport material in a hole transport layer. However, compounds according to the invention can also be used in several of the aforementioned layers. Particularly preferably, these emission layers have several emission maxima between 380 nm and 750 nm, resulting in overall white emission; that is, different emitting compounds are used in the emitting layers that can fluoresce or phosphoresce and emit blue, yellow, orange, or red light.Particularly preferred are three-layer systems, i.e., systems with three emitting layers, wherein at least one of these layers contains at least one compound according to formula I and at least one phosphorescent emitter, and wherein the three layers exhibit blue, green, and orange or red emission (for the basic structure, see, e.g., WO 2005 / 011013). The use of more than three emitting layers may also be preferred. Similarly, emitters exhibiting broadband emission bands and thus displaying white emission are suitable for white emission.

[0064] In addition to the cathode, anode, and at least one of the layers already mentioned, the organic electroluminescent device can contain further layers. These can include, for example, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, and / or a charge-generation layer. It should be noted, however, that not every one of these layers is necessarily required. In particular, when using compounds according to formula I with electron-conducting host materials, very good results are still obtained if the organic electroluminescent device does not contain a separate electron transport layer and the emitting layer is directly adjacent to the electron injection layer or the cathode. Alternatively, the host material can also simultaneously serve as the electron transport material within an electron transport layer.It may also be preferred if the organic electroluminescence device does not contain a separate hole transport layer and the emitting layer is directly adjacent to the hole injection layer or to the anode.

[0065] Within the scope of the invention, it is preferred that the compounds according to formula I or the polymers, oligomers or dendrimers according to the invention are used as matrix material for phosphorescent dopants in the electronic device.

[0066] Within the scope of the invention, it is further preferred that the compounds according to formula I or the polymers, oligomers or dendrimers according to the invention are used in the electronic device as electron transport material in an electron transport layer and / or as hole transport material in the hole transport layer and / or as hole blocking material in a hole blocking layer.

[0067] An organic electroluminescent device is a device comprising an anode, a cathode, and at least one emitting layer arranged between the anode and the cathode. Additionally, it may contain one or more electron transport layers and / or hole transport layers. An organic electroluminescent device according to the invention comprises at least one layer between the anode and the cathode containing a compound of formula I.

[0068] In a further embodiment of the present invention, the compounds of formula I are used as a matrix material for emitting materials, preferably phosphorescent dopants. It is particularly preferred that the compounds of formula I are used as a matrix material for emitting materials in an organic electroluminescence device.

[0069] In a further preferred embodiment of the invention, the organic electroluminescent device can also contain several emitting layers, wherein at least one emitting layer contains at least one compound according to formula I and at least one preferably phosphorescent emitter.

[0070] A further subject of the invention is therefore also mixtures of one or more compounds according to formula I with one or more emitting compounds, in particular phosphorescent compounds.

[0071] The mixture of the compound according to Formula I and the phosphorescent emitter used in the emitting layer preferably contains between 99 and 50 vol%, more preferably between 98 and 50 vol%, more preferably between 97 and 60 vol%, and more preferably between 95 and 85 vol% of the compound according to Formula I, based on the total mixture of emitter and matrix material. Similarly, the mixture contains between 1 and 50 vol%, more preferably between 2 and 50 vol%, and more preferably between 3 and 40 vol%, and more preferably between 5 and 15 vol% of the phosphorescent emitter, based on the total mixture of emitter and matrix material.

[0072] Another preferred embodiment of the present invention is the use of the compound according to the invention as a matrix material for a phosphorescent emitter in combination with another matrix material. Particularly suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, etc. B. CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boron esters, e.g.according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilol or tetraazasilol derivatives, e.g. according to the unpublished application DE 102008056688.8, diazaphosphole derivatives, e.g. according to the unpublished application DE 102009022858.6, or indenocarbazole derivatives, e.g. according to the unpublished application DE 102009023155.2.

[0073] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds that emit light, preferably in the visible range, upon suitable excitation and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and especially 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 preferred as phosphor emitters, especially compounds containing iridium or platinum.

[0074] Examples of the emitters described above can be found in applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 019373 and US 2005 / 0258742. In general, all phosphorescent complexes used in phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescence are suitable, and those skilled in the art can use other phosphorescent complexes without inventive effort.

[0075] It may also be advantageous to use two or more different phosphorescent emitters in an emitting layer, particularly emitters with different emission maxima. For example, by using a green and a red phosphorescent emitter, it is possible to achieve red luminescence with improved efficiency.

[0076] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer; i.e., the emitting layer is directly adjacent to the hole injection layer or the anode, and / or the emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, it is possible to use a metal complex that is identical or similar to the metal complex in the emitting layer directly adjacent to the emitting layer as a hole transport or hole injection material, as described, for example, in WO 2009 / 030981.

[0077] In a further embodiment of the present invention, the compounds according to formula I are used as electron transport material, preferably in an electron transport layer. Particularly preferred compounds in this case are compounds of formula I that are used as Ar 1 exhibit an electron-deficient heteroaromatic group, as detailed above.

[0078] If the compounds of formula I are used as electron transport material in an organic electroluminescence device, they can also be used in combination with an organic or inorganic alkali metal compound according to the invention. "In combination with an organic alkali metal compound" means that the compounds of formula I and the alkali metal compound are present either as a mixture in one layer or separately in two successive layers. In a preferred embodiment of the invention, the compounds of formula I and the organic alkali metal compound are present as a mixture in one layer.

[0079] For the purposes of this invention, an organic alkali metal compound is understood to be a compound containing at least one alkali metal, i.e., lithium, sodium, potassium, rubidium, or cesium, and further containing at least one organic ligand. Suitable organic alkali metal compounds are, for example, those disclosed in WO 2007 / 050301, WO 2007 / 050334, and EP 1144543. These are incorporated into the present application by reference.

[0080] Preferred organic alkali metal compounds are the compounds of the following formula A, where R 1 The curved line has the same meaning as described above, representing two or three atoms and bonds required to complete a 5- or 6-membered ring with M, where these atoms are also connected by one or more R groups. 1may be substituted, and M is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium or cesium.

[0081] It is possible that the complex according to formula A exists in monomeric form, as shown above, or that it exists in the form of aggregates, for example consisting of two alkali metal ions and two ligands, four alkali metal ions and four ligands, six alkali metal ions and six ligands, or other aggregates.

[0082] Preferred compounds of formula A are the compounds of the following formulas B and C, where k is equal to 0, 1, 2 or 3 and o is equal to 0, 1, 2, 3 or 4 and the other symbols used have the meanings mentioned above.

[0083] Other preferred organic alkali metal compounds are the compounds according to the following formula D, the symbols used have the same meaning as described above.

[0084] Preferably the alkali metal is selected from lithium, sodium and potassium, especially preferably lithium and sodium, most preferably lithium.

[0085] A compound of formula B is particularly preferred, especially with M = lithium. The index k = 0 is also highly preferred. Therefore, the compound is most preferably unsubstituted lithium quinolinate.

[0086] The organic electroluminescent device most preferably contains a mixture of a compound of formula I with Ar 1 equivalent to an electron-deficient heteroaromatic group and an organic alkali metal compound of formula B, preferably with M = lithium, in particular unsubstituted lithium quinolinate.

[0087] Examples of suitable organic alkali metal compounds are the structures (1) to (45) listed in the following table. (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45)

[0088] When the compound of formula I and the organic or inorganic alkali metal compound are present in a mixture, the ratio of the compound of formula I to the organic alkali metal compound is preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30, most preferably 30:70 to 50:50, and in particular 30:70 to 45:55, in each case based on volume. Thus, it is particularly preferred that the organic alkali metal compound is present in a higher proportion than the compound of formula I.

[0089] When the compound of formula I and the organic or inorganic alkali metal compound are present in a mixture, the thickness of this electron transport layer is preferably between 3 and 150 nm, particularly preferably between 5 and 100 nm, most preferably between 10 and 60 nm, and especially between 15 and 40 nm.

[0090] If the compound of formula I and the organic or inorganic alkali metal compound are present in two successive layers, the thickness of the layer containing the compound of formula I is preferably between 3 and 150 nm, particularly preferably between 5 and 100 nm, most preferably between 10 and 60 nm, and especially between 15 and 40 nm. The thickness of the layer containing the organic or inorganic alkali metal compound, which is arranged between the layer with the compound of formula I and the cathode, is preferably between 0.5 and 20 nm, particularly preferably between 1 and 10 nm, most preferably between 1 and 5 nm, and especially between 1.5 and 3 nm.

[0091] It is further an object of the present invention that the compounds according to Formula I are used as hole-blocking material. The compounds are then preferably used in a hole-blocking layer, particularly in a phosphorescent OLED. A hole-blocking layer within the meaning of this invention is a layer arranged between an emitting layer and an electron transport layer.

[0092] It is further an object of the present invention that the compounds according to Formula I are used as hole transport material and / or as hole injection material. The compounds are then preferably used in a hole transport layer and / or in a hole injection layer. A hole injection layer within the meaning of this invention is a layer that is directly adjacent to the anode. A hole transport layer within the meaning of this invention is a layer that lies between the hole injection layer and the emission layer.

[0093] Metals with low work function, metal alloys, or multilayer structures of different metals are preferred as cathodes, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In multilayer structures, additional metals with relatively high work functions, such as Ag, can also be used, typically in combinations of these metals, such as Mg / Ag, Ca / Ag, or Ba / Ag. Metal alloys are also preferred, particularly alloys of an alkali metal or alkaline earth metal and silver, and especially an alloy of Mg and Ag. It may also be preferred to insert a thin interlayer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li₂O, CsF, Cs₂CO₃, BaF₂, MgO, NaF, etc.). The thickness of this layer is preferably between 0.5 and 5 nm.

[0094] Materials with a high work function are preferred as anodes. Preferably, the anode has a work function greater than 4.5 eV against a vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Alternatively, metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , Al / PtO x, WoO3). For some applications, at least one of the electrodes must be transparent or semi-transparent to allow either the irradiation of the organic material (O-SC) or the extraction of light (OLED / PLED, O-Laser). Preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred.

[0095] The device is structured accordingly (depending on the application), contacted, and finally hermetically sealed, as the lifespan of such devices is drastically reduced in the presence of water and / or air.

[0096] Compounds according to formula I can also be used in polymers, oligomers or dendrimers either as a hole-transporting unit and / or as an electron-transporting unit and / or as a matrix for phosphorescent units.

[0097] A further preferred organic electroluminescence device is characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 The initial pressure is vapor-deposited at mbar. However, it should be noted that the initial pressure can also be lower, for example less than 10 mbar. -7 mbar.

[0098] A preferred option is an organic electroluminescence device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation. The materials are coated at a pressure between 10 -5 mbar and 1 bar are applied. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0099] A further preferred organic electroluminescent device is characterized in that one or more layers are produced from solution, e.g., by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds according to Formula I are required for this purpose. High solubility can be achieved by suitable substitution of the compounds. These layer production methods are particularly suitable for polymers, oligomers, or dendrimers.

[0100] The organic electroluminescent device can also be fabricated as a hybrid system by depositing one or more solution layers and then evaporating one or more other layers. For example, it is possible to deposit an emitting layer containing a compound of formula I and a phosphorescent dopant from solution and then evaporate a hole-blocking layer and / or an electron transport layer onto it under vacuum. Similarly, the emitting layer containing a compound of formula I and a phosphorescent dopant can be evaporated under vacuum, and one or more other layers can be deposited from solution. Alternatively or additionally, it is also possible, for example, to deposit an emitting layer from solution and then evaporate an electron transport layer containing a compound of formula I, possibly in combination with an organic alkali metal compound, onto it under vacuum.

[0101] These methods are generally known to those skilled in the art and can be applied by them without difficulty to organic electroluminescent devices containing compounds according to formula I or the preferred embodiments listed above.

[0102] For application from solution, solutions or formulations of the compound according to the invention are required. A further object of the present invention is therefore a formulation containing at least one compound of formula I and at least one organic solvent. Any organic solvent commonly used for the manufacture of organic electroluminescent devices can be used.

[0103] Another object of the present invention is mixtures containing at least one phosphorescent emitter and at least one compound according to formula I.

[0104] The compounds according to the invention offer the following surprising advantages over the prior art when used in organic electroluminescence devices: 1. The compounds according to the invention are very well suited for use as matrix material for phosphorescent emitters and lead to good efficiencies, long lifetimes and low operating voltages in this use. 2. The power efficiency of such devices is higher compared to prior art systems, particularly when using thick layers. This applies especially when the compound according to the invention is used in an electron transport layer. 3. The stability of such devices is higher compared to systems according to the state of the art, which is reflected above all in a significantly longer service life, especially when using thick layers. 4. The organic electroluminescence devices according to the invention simultaneously have a reduced operating voltage. 5. The organic electroluminescence devices according to the invention exhibit very high efficiency. The improved efficiency is possibly due to improved electron injection from the electron transport layer into the emitting layer.

[0105] Finally, it should be noted that all preferred and all features not explicitly mentioned as preferred of the above-mentioned compounds according to the invention, their use in electronic devices, and the electronic devices themselves can be combined with one another as desired. All resulting combinations are also part of this invention.

[0106] The invention will now be explained in more detail by the following examples, without thereby limiting its scope. A person skilled in the art can synthesize further compounds according to the invention and use them in electronic devices without having to perform any inventive work. Examples

[0107] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. Example 1: 2-(2-Nitrophenyl)-9,9-dimethyl-9H-fluorene

[0108] A well-stirred suspension of 23.8 g (100 mmol) of 9,9-dimethylfluorenyl-2-boronic acid, 20.6 g (102 mmol) of 1-bromo-2-nitrobenzene, and 51 g (221 mmol) of tripotassium phosphate in a mixture of 380 mL toluene, 190 mL dioxane, and 480 mL water is treated with 913 mg (3 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate and subsequently heated under reflux for 16 h. After cooling, the precipitated solid is filtered off, washed three times with 50 mL toluene, three times with 50 mL ethanol:water (1:1, v:v), and three times with 100 mL ethanol, and recrystallized three times from DMF (approx. 10 mL / g). Yield: 25.3 g (80 mmol), 81%. Example 2: 12,12-Dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene

[0109] A mixture of 75 g (238 mmol) of 2-(2-nitrophenyl)-9,9-dimethyl-9H-fluorene and 290.3 mL (1669 mmol) of triethyl phosphite is heated under reflux for 12 h. The remaining triethyl phosphite is then distilled off (72–76 °C / 9 mm Hg). The residue is treated with water / MeOH (1:1), the solid is filtered off, and recrystallized. Yield: 61.3 g (216 mmol), 92%. Example 3a: 6-(4,6-Diphenyl-[1,3,5]triazin-2-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene

[0110] 1.5 g (37.5 mmol) of NaH (60% in oil) is placed in 150 ml of dichloromethane. A solution of 8 g (28 mmol) of 12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene in dichloromethane is added dropwise at room temperature. After 1 hour, 8.5 g (31 mmol) of 2-chloro-4,6-diphenyl-(1,3,5)-triazine is added dropwise, and the mixture is stirred at room temperature for 8 hours. The precipitated solid is recrystallized from toluene. The precipitated crystals are collected by filtration, washed with a small amount of MeOH, and dried under vacuum; yield: 11.6 g; 80% of theory; purity: 99.9% by HPLC.

[0111] The following connections are obtained analogously: Example . Reagent 1 product yield 3b 83 % 3c 78 % 3d 86 % 3e 77 % 3f 72 % 3g 76 % 3h 81 % 3j 85 % 3i 76% Example 4a: 12,13-Bis-(4,6-diphenyl-[1,3,5]triazin-2-yl)-12,13-dihydroindolo[3,2-c]acridin-7-one

[0112] 3 g (75 mmol) of NaH (60% in oil) are placed in 150 ml of dichloromethane. A solution of 8.4 g (28 mmol) of 3-((Z)-propenyl)-2-vinyl-1H,11H-1,11-diaza-cyclopenta[a]anthracen-6-one in dichloromethane is added dropwise at room temperature. After 1 h, 17 g (62 mmol) of 2-chloro-4,6-diphenyl-(1,3,5)-triazine is added dropwise, and the mixture is stirred at room temperature for 8 h. The precipitated solid is recrystallized from toluene. The precipitated crystals are collected by filtration, washed with a small amount of MeOH, and dried under vacuum; yield: 14.6 g; 70% of theory; purity: 99.9% by HPLC.

[0113] The following connections are obtained analogously: Example . Reagent 1 product yield 4b 69% 4c 66% Example 5a: 6-(2,6-Diphenyl-pyridin-4-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorena) 2,6-dibromo-4-nitropyridine

[0114] A solution of 50 g (211 mmol) of 2,6-dibromopyridine in 250 ml of trifluoroacetic acid is heated to 90 °C. To this, 53 ml (515 mmol) of a 33% hydrogen peroxide solution is added dropwise. After 3 h, the reaction mixture is cooled and poured onto 200 ml of ice water. The filtrate is extracted three times with dichloromethane, and the combined organic phases are washed four times with a 0.5 M K₂CO₃ solution, dried over Na₂SO₄, and concentrated. The residue of 2,6-dibromopyridine-1-oxide (41.2 g) is used further.

[0115] A solution of 20 g (78 mmol) of 2,6-dibromopyridine-1-oxide is heated to 40 °C in 70 mL of H₂SO₄. At this temperature, the solution is treated with nitrating acid (70 mL of H₂SO₄ and 34 mL of fuming HNO₃). The reaction mixture is heated to 90 °C for 3 h. After cooling, the reaction mixture is poured onto 800 mL of ice water. The precipitated solid is filtered and washed with water. After drying, 17.9 g of 2,6-dibromo-4-nitropyridine-1-oxide is suspended in 200 mL of chloroform and, at room temperature, treated with 6 mL of phosphorus tribromide (64 mmol). The mixture is stirred for 1 h and then heated under reflux for 2 days. After cooling, the solution is poured onto 500 mL of ice water and neutralized with solid NaHCO₃. The aqueous phase is separated and extracted several times with CHCl3. The combined organic phases are washed with a sodium thiosulfate solution and then with water, dried, and concentrated. The residue is recrystallized from EtOH.Yield: 41.7 g (148 mmol), 70% of theory. b) 6-(2,6-Diphenyl-pyridin-4-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene

[0116] 20 g (70.7 mmol) of 12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene are dissolved in 50 mL of dimethylformamide under a protective atmosphere and mixed with 3.1 g of 60% NaH in mineral oil (78 mmol). After 1 h at room temperature, a solution of 2,6-dibromo-4-nitropyridine (20 g, 70.7 mmol) in 20 mL of DMF is added dropwise. The reaction mixture is stirred for 12 h at room temperature. Then the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na₂SO₄ and concentrated. The residue is recrystallized from toluene. Yield: 29.6 g (80 mmol), 95% of theory.

[0117] 25 g (48 mmol) of 6-(2,6-dibromopyridin-4-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene and 12.9 g of phenylboronic acid (106 mmol) are suspended in 300 ml of ethylene glycol dimethyl ether. The reaction mixture is treated with 75 ml of a 2 M Na₂CO₃ solution. To this suspension, 2.8 g (2.4 mmol) of Pd(PPh₃)₄ are added. The reaction mixture is heated under reflux for 12 h. After cooling, the precipitated solid is filtered off, washed with water and ethanol, and dried. The residue is extracted hot with toluene, recrystallized from toluene, and finally sublimed under high vacuum; the purity is 99.9%. Yield: 18 g, 72% of theory.

[0118] The following connections are obtained analogously: Example . Reagent 1 product yield 5b 81 % 5c 75% Example 6a: 6-(3,5-Di-pyrimidin-2-yl-phenyl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorena) 5-iodo-1,3-(2'-pyrimidyl)benzene

[0119] 40 g (127 mmol) of tribromobenzene are dissolved in 800 ml of ethanol and cooled to -78 °C. 88 ml (140 mmol) of n-BuLi (1.6 M solution in hexane) are added dropwise to this solution. After stirring for 3 h at this temperature, 19.4 ml of chlorotrimethylsilane are added dropwise, and the reaction mixture is stirred for another 1 h at room temperature. The mixture is then separated between heptane and water, the aqueous phase is extracted three times with heptane, dried over sodium sulfate, and rotary precipitate is applied. The remaining residue, 31.4 g (80% yield), is distilled and reacted further.

[0120] 25 g (79.4 mmol) of 5-trimethylsilyl-1,3-bromobenzene, 37.7 g (159 mmol) of bis(pinacolato)diborane, and 4 g (350 mmol) of potassium acetate are suspended in 700 mL of DMSO. To this suspension, 11.9 g (16 mmol) of a 1,1-bis(diphenylphosphino)ferrocene-dichloropalladium(II) complex with dichloromethane are added. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 200 mL of water, and then concentrated to dryness. The residue is recrystallized from toluene. Yield: 24 g, 75% of theory.

[0121] 20 g (49.7 mmol) of 5-trimethylsilylbenzene-1,3-bis(pinachol boronate) and 15.8 g (99.5 mmol) of 2-bromopyrimidine are suspended in 600 ml of ethylene glycol dimethyl ether. The reaction mixture is treated with 100 ml of a 2 M Na₂CO₃ solution. To this suspension, 1.5 g (4.9 mmol) of Pd(PPh₃)₄ are added. The reaction mixture is heated under reflux for 12 h. After cooling, the precipitated solid is filtered off, washed with water and ethanol, and dried. The residue is recrystallized from toluene. Yield: 9.5 g, 60% of theory.

[0122] 15 g (49 mmol) of 5-trimethylsilyl-1,3-(2'-pyrimidyl)benzene are dissolved in 200 mL of dichloromethane under a protective atmosphere and treated with 8.1 g (50 mol) of illuminin (I-Cl) at 0 °C. The reaction mixture is stirred at this temperature for 12 h. After this time, the reaction mixture is poured onto water and extracted three times with dichloromethane. The combined organic phases are washed with a sodium dithionite solution, dried over Na₂SO₄, and concentrated. The residue is recrystallized from heptane / ethyl acetate. Yield: 12.6 g (80 mmol), 60% of theory. b) 6-(3,5-Di-pyrimidin-2-yl-phenyl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene

[0123] 10.9 g (38.32 mmol) of 12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene, 12 g (38.32 mmol) of 5-iodo-1,3-(2'-pyrimidyl)benzene, and 16 g of K₂CO₃ are suspended in 300 mL of p-xylene. To this suspension, 0.86 g (3.84 mmol) of Pd(OAc)₂ and 7.6 mL of a 1 M tri-tert-butylphosphine solution are added. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 200 mL of water, and then concentrated to dryness. The residue is extracted hot with toluene, recrystallized from toluene, and finally sublimed under high vacuum; the purity is 99.9%. Yield: 16.4 g (26.6 mmol), 96% of theory.

[0124] The following connections are obtained analogously: Example . Reagent 1 product yield 6b 86 % 6c 76% Example 7a: 6-(4,6-Diphenyl-pyrimidin-2-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorena) 2-chloro-4,6-diphenyl-pyrimidine

[0125] 75 g (0.41 mmol) of 1,3,5-trichloropyrimidine, 100 g (0.82 mol) of phenylboronic acid, and 625 mL of 4 M NaHCO3 solution are suspended in 2.5 L of ethylene glycol dimethyl ether. To this suspension, 2.3 g (10.23 mmol) of Pd(OAc)2 and 10.35 g (34 mmol) of (o-Tol)3P are added, and the reaction mixture is heated under reflux for 16 h. The mixture is then dispersed between ethyl acetate and water, the organic phase is washed three times with water, and dried and rotated over Na2SO4. The remaining residue is recrystallized from heptane / toluene. The yield is 43 g (0.15 mol, 38%). b) 6-(4,6-Diphenyl-pyrimidin-2-yl)-12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene

[0126] 4.2 g of 60% NaH in mineral oil (0.106 mol) are dissolved in 300 mL of dimethylformamide under a protective atmosphere. 30 g of 12,12-dimethyl-6,12-dihydro-6-aza-indeno[1,2-b]fluorene (0.106 mol) are dissolved in 250 mL of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3]pyrimidine (34.5 g, 0.122 mol) in 200 mL of THF is added dropwise. The reaction mixture is then stirred for 12 h at room temperature. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na₂SO₄ and concentrated. The residue is hot-extracted with toluene, recrystallized from toluene / n-heptane, and finally sublimed under high vacuum; purity is 99.9%. The yield is 27 g (51%).

[0127] The following connections are obtained analogously: Example . Reagent 1 product yield 7b 55 % 7c 59% Device examples: Manufacturing of OLEDs (Examples 1 to 31 and comparison examples 1 to 7)

[0128] The production of OLEDs according to the invention as well as OLEDs according to the prior art is carried out according to a general method according to WO 2004 / 058911, which is adapted to the conditions described here (layer thickness variation, materials used).

[0129] In the following comparative examples 1 to 7 and examples 1 to 31 (see Tables 1 and 2), the data for various OLEDs are presented. Glass platelets coated with 150 nm thick structured ITO (indium tin oxide) are coated with 20 nm PEDOT (spinner-coated from water; sourced from HC Starck, Goslar, Germany; poly(3,4-ethylenedioxy-2,5-thiophene)) for improved processing. These coated glass platelets are the substrates onto which the OLEDs are deposited. The OLEDs have the following layer structure: substrate / optional hole injection layer (HIL1) 5 nm / hole transport layer (HTM1) / electron blocking layer (EBL) 20 nm / emission layer (EML) / optional hole blocking layer (HBL) 10 nm / electron transport layer (ETM) and finally a cathode.The cathode is formed by a 100 nm thick aluminum layer, with a 1 nm thick LiF electron injection layer between the cathode and the electron transport layer, depending on the electron transport material used. The exact structure of the OLEDs is explained in connection with the examples listed below. The materials used to fabricate the OLEDs are shown in Table 3.

[0130] All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host) and one dopant, which is added to the host material(s) by cover vapor deposition. A specification such as H2:TER1 (85%:15%) means that material H2 is present in the layer at a volume fraction of 85% and TER1 at a volume fraction of 15%. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0131] The OLEDs are characterized according to standard procedures. This involves determining the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in imp / W), and external quantum efficiency (EQE, measured in percent) as a function of brightness, calculated from current-voltage-luminosity curves (IUL curves), as well as the lifetime. Lifetime is defined as the time it takes for the brightness to decrease from a specific initial brightness to half its initial value. This value can be converted to values ​​for other initial brightness levels using conversion formulas known to those skilled in the art. Here, the lifetime for an initial brightness of 1000 cd / m² is given. 2 a common statement.

[0132] The following section explains some of the examples in more detail to illustrate the advantages of the compounds according to the invention. It should be noted, however, that this represents only a selection of the data shown. As can be seen from the tables, significant improvements compared to the prior art are also achieved when using the compounds according to the invention, which are not described in detail below. In some cases, improvements are observed in all parameters, while in others, only improvements in efficiency, voltage, or lifetime are seen. However, even an improvement in just one of these parameters represents significant progress, because different applications require optimization with respect to different parameters. Use of compounds according to the invention as electron transport materials

[0133] Table 1 shows data for several OLEDs, demonstrating the advantages of using compounds according to the invention in the electron transport layer. The OLEDs consist of the following layer sequence: substrate / hole injection layer (HIL1) 5 nm / hole transport layer (HTM1) 140 nm / NPB 20 nm / emission layer 30 nm / electron transport layer (ETM) 20 nm / optional 1 nm LiF / aluminum 100 nm. The emission layer consists of the host material H1, which is doped with the blue-emitting dopant D1 to a volume fraction of 5%. In comparative example 2 and examples 2 and 4, a mixed layer of an electron transport material and LiQ, produced by cover evaporation, is used as the electron transport layer. The volume fraction of LiQ is 60% in this case.

[0134] The OLEDs corresponding to comparison examples 1 and 2 and examples 1 to 4 show comparable CIE color coordinates and a comparable lifespan of approximately 150 h at a starting brightness of 6000 cd / m². 2 This corresponds to approximately 5500 hours at a starting brightness of 1000 cd / m². 2 , if one uses extrapolation formulas known to experts.

[0135] The use of the materials ETM2 and ETM3 according to the invention leads to a significant improvement in both the external quantum efficiency (EQE), the current efficiency (in cd / A), and, above all, the operating voltage and thus the power efficiency (in Im / W). The increase in power efficiency is particularly important with regard to mobile applications. Here, an increase of 10% is already considered a significant improvement.

[0136] The highest improvement in power efficiency is achieved with LiF as the electron injection layer. Here, the use of the compounds ETM2 and ETM3 according to the invention increases the power efficiency by approximately 40% compared to the use of Alq3 (comparison of Comparative Example 1 with Examples 1 and 3). Even when using a mixed electron transport layer, which already achieves good power efficiency with the electron transport material ETM1 according to the prior art (Comparative Example 2), a significant improvement of approximately 15% can be achieved by using ETM2 or ETM3 (comparison of Comparative Example 2 with Examples 2 and 4).

[0137] Furthermore, the compound ETM3 according to the invention exhibits significantly improved processability compared to the prior art compound ETM1. Under the same evaporation conditions (evaporation rate of 0.1 nm / s), approximately 1 µm thick layers are deposited from the materials. The material ETM3 according to the invention does not exhibit clogging of the evaporation source. In contrast, when using ETM1, a ring-shaped layer of the material grows inwards at the upper edge of the evaporation source. As a result, controlled layer deposition is no longer possible after approximately 1.5 hours of evaporation time. The compounds according to the invention are therefore significantly better suited for use in mass production than the prior art compound ETM1. Table 1: Use of compounds according to the invention as electron transport materials ETM EIM Voltage for 1000 cd / m² 2 Efficiency at 1000 cd / m² 2 Efficiency at 1000 cd / m² 2 EQE bei1000 cd / m 2 CIE x / y bei1000 cd / m 2 Comparative example 1 Alq3 LiF 1 nm 6.4 V 5.1 cd / A 2.5 lm / W 4.2% 0.142 / 0.151 Comparative example 2 ETM1:LiQ --- 4.7 V 8.1 cd / A 5.4 Im / W 6.3% 0.142 / 0.155 Example 1 ETM2 LiF 1 nm 5.8 V 6.2 cd / A 3.4 lm / W 4.9% 0.141 / 0.154 Example 2 ETM2:LiQ --- 4.5 V 8.8 cd / A 6.1 Im / W 6.9% 0.142 / 0.156 Example 3 ETM3 LiF 1nm 5.6 V 6.4 cd / A 3.6 lm / W 5.0% 0.141 / 0.152 Example 4 ETM3:LiQ --- 4.5 V 9 cd / A 6.3 lm / W 7.1% 0.143 / 0.157 Use of compounds according to the invention as host materials for phosphorescent dopants

[0138] The compounds according to the invention can also be used as host materials for phosphorescent dopants. In addition to compound H5, the materials ETM2 and ETM3 described in the previous section are used, which for clarity will be referred to below as H3 and H4. Compound H2 is used for comparison with the prior art. OLEDs with the green-emitting dopant TEG1 and the red-emitting dopants TER1 and TER2 are compared.

[0139] The OLEDs have the following structure: substrate / hole transport layer (HTM1) / electron blocking layer (EBL) 20 nm / emission layer (EML) / optional hole blocking layer (HBL) 10 nm / electron transport layer (ETM) / optional LiF 1 nm / aluminum 100 nm. In the OLEDs of comparison examples 3-5 and examples 5-7, as well as 13, 14, and 25, the hole transport layer is 20 nm thick, the electron blocking layer is formed by NPB, and the electron transport layer is a 20 nm thick Alq3 layer with a 1 nm thick LiF electron injection layer. The OLEDs of comparison example 5 and example 7 additionally contain a 10 nm thick hole blocking layer of material H2 between the emission layer and the electron transport layer.

[0140] The OLEDs in comparison examples 6 and 7 and examples 8-12, 15-24, and 26-31 contain a 160 nm thick hole transport layer and an electron blocking layer formed by the material EBM1. The electron transport layer in these OLEDs is a 50%:50 volume mixture of ETM1 and LiQ; an electron injection layer is not present. The OLEDs in comparison examples 6, 11, 13, 24, and 32 contain a 10 nm thick hole blocking layer made of material H2; the thickness of the electron transport layer is 30 nm. The hole blocking layer is not present in the OLEDs of comparison example 7 and examples 9, 11, 12, 15-20, 22-24, 26-28, 30, and 31; the thickness of the electron transport layer in these examples is 40 nm.

[0141] The use of the compounds H3, H4 and H5 according to the invention results in significant improvements in terms of efficiency, operating voltage and service life compared to the use of H2 according to the prior art (see Table 2).

[0142] In red-emitting OLEDs, the use of host material H5 results in a 25-50% increase in power efficiency, depending on whether the dopant TER1 or TER2 is used and whether another host material is present (comparison of examples 3 to 5 with examples 5 to 7). Furthermore, the lifetime increases by 20-35% when using H5 compared to components using material H2 according to the prior art. The compounds according to the invention thus result in significant improvements in all relevant parameters when used as host material in red-emitting phosphorescent OLEDs.

[0143] By using the materials H3 and H4 according to the invention in green phosphorescent OLEDs, efficiency, operating voltage, and lifetime can be improved even more significantly than in the red-emitting OLEDs described above. The use of H4 as the host material results in an improvement of 35-40% in power efficiency and an increase of approximately 30-40% in lifetime compared to the use of H2 (comparison of Example 6 with Example 10, and Example 7 with Example 11). The very high increase in power efficiency results primarily from the significant reduction in operating voltage of approximately 1 V. Compared to the prior art H2, the use of the compound H3 according to the invention also results in a significant improvement in power efficiency of approximately 20%, and the lifetime increases by 20-30% (comparison of Example 6 with Example 8, and Example 7 with Example 9). Table 2: Use of compounds according to the invention as host materials in phosphorescent OLEDs EML HBL Voltage for 1000 cd / m 2 Efficiency at 1000 cd / m² 2 Efficiency at 1000 cd / m² 2 CIE x / y bei 1000cd / m 2 Lifespan from 1000 cd / m² 2 Comparative example 3 H2:TER1(85%:15%) --- 5.0 V 7.2 cd / A 4.5 lm / W 0.69 / 0.31 14000 Comparative example 4 H2:TER2 (85%:15%) --- 6.5 V 9.0 cd / A 4.3 lm / W 0.66 / 0.33 18000 Comparative example 5 H2:CBP:TER1(45%:45%:10%) H2 5.2 V 8.1 cd / A 4.9 lm / W 0.68 / 0.32 15000 Comparative example 6 H2:TEG1 (90%:10%) H2 4.7 V 55 cd / A 37 lm / W 0.36 / 0.61 27000 Comparative example 7 H2:TEG1 (90%:10%) --- 4.6 V 54 cd / A 37 lm / W 0.37 / 0.60 24000 Example 5 H5:TER1(85%:15%) --- 4.4 V 8.1 cd / A 5.8 lm / W 0.69 / 0.31 17000 Example 6 .H5:TER2(85%:15%) --- 4.7 V 9.9 cd / A 6.6 lm / W 0.65 / 0.32 23000 Example 7 H5:CBP:TER1(45%:45%:10%) H2 4.6 V 8.9 cd / A 6.1 lm / W 0.69 / 0.31 20000 Example 8 H3:TEG1 (90%:10%) H2 3.9 V 54 cd / A 44 lm / W 0.37 / 0.60 35000 Example 9 H3:TEG1 (90%:10%) --- 3.8 V 53 cd / A 44 lm / W 0.37 / 0.60 29000 Example 10 H4:TEG1 (90%:10%) H2 3.8 V 60 cd / A 50 lm / W 0.37 / 0.61 37000 Example 11 H4:TEG1 (90%:10%) --- 3.6 V 58 cd / A 51 lm / W 0.38 / 0.60 32000 Example 12 H6:TEG1 (90%:10%) --- 3.7 V 51 cd / A 43 lm / W 0.38 / 0.60 26000 Example 13 H7:TER1(85%:15%) --- 3.9 V 7.1 cd / A 5.7 lm / W 0.69 / 0.31 21000 Example 14 H8:TER1(85%:15%) --- 4.3 V 7.7 cd / A 5.6 ImlW 0.69 / 0.31 19000 Example 15 H9:TEG190%: 10%) --- 3.6 V 56 cd / A 49 lm / W 0.38 / 0.60 39000 Example 16 H10:TEG1(90%:10%) --- 3.4 V 53 cd / A 49 lm / W 0.37 / 0.59 25000 Example 17 H11:TEG1(90%:10%) --- 4.0 V 53 cd / A 41 lm / W 0.38 / 0.60 27000 Example 18 H12:TEG1(90%:10%) --- 3.9 V 49 cd / A 40 lm / W 0.37 / 0.60 28000 Example 19 H13:TEG1(90%:10%) --- 3.9 V 54 cd / A 43 lm / W 0.36 / 0.60 35000 Example 20 H14:TEG1(90%:10%) --- 4.1 V 61 cd / A 47 lm / W 0.36 / 0.61 39000 Example 21 H14:TEG1(90%:10%) H2 4.1 V 63 cd / A 48 lm / W 0.36 / 0.61 42000 Example 22 H15:TEG1(90%:10%) --- 4.2 V 51 cd / A 39 lm / W 0.36 / 0.60 31000 Example 23 H16:TEG1(90%:10%) --- 4.0 V 50 cd / A 39 lm / W 0.36 / 0.60 30000 Example 24 H17:TEG1(90%:10%) --- 3.5 V 58 cd / A 52 lm / W 0.36 / 0.60 38000 Example 25 H17:TER1(85%:15%) --- 4.1 V 7.8 cd / A 6.1 Im / W 0.69 / 0.31 25000 Example 26 H18:TEG1(90%:10%) --- 3.7 V 53 cd / A 45 lm / W 0.36 / 0.60 32000 Example 27 H19:TEG1(90%:10%) --- 3.6 V 48 cd / A 42 lm / W 0.36 / 0.60 28000 Example 28 H2O:TEG1 (90%:10%) --- 3.7 V 52 cd / A 44 lm / W 0.37 / 0.60 30000 Example 29 H2O:TEG1 (90%:10%) H2 3.8 V 52 cd / A 44 ImlW 0.37 / 0.60 35000 Example 30 H21:TEG1(90%:10%) --- 3.8 V 48 cd / A 40 lm / W 0.36 / 0.60 27000 Example 31 H22:TEG1(90%:10%) --- 3.7 V 49 cd / A 42 lm / W 0.36 / 0.60 28000 Table 3: Structures of the materials used HIL1 HTM1 NPB EBM1 Alq3 H1 D1 ETM1 ETM2 = H3 ETM3 = H4 LiQ H2 H5 TEG1 TER1 TER2 CBP H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 H17 H18 H19 H20 H21 H22

Claims

[1] Electronic device comprising at least one compound of formula I:where the symbols and indices used have the following meanings: W is the same or different in each occurrence N or CR 1 ; Y is the same or different at each occurrence N or CR 2 ; E is either a covalent single bond or is a bivalent unit selected from the group consisting of N(R) 3 ), C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; X is either equal to or different from a bivalent unit chosen from the group consisting of C(R) at each occurrence. 3 )2, N(R 3 ), Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3consists, with the proviso that if E is a covalent single bond, X is a bivalent unit selected from the group consisting of C(R 3 )2, Si(R 3 )2, C=O, C=NR 3 , C=C(R 3 )2, S, O, S=O, SO2, P(R 3 ) and P(=O)R 3 consists; n, m are independently 0 or 1, with the proviso that the sum of n and m is equal to 1 or 2; Ar is a bivalent or trivalent, mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups. 4a may be substituted; Ar 1 is an electron-deficient, mono- or polycyclic heteroaromatic group with 5 to 10 aromatic ring atoms, coupled with one or more R substituents 4b may be substituted; L is either a covalent single bond or represents a bivalent unit selected from the group consisting of -C(O)-, -Ar 2 C(O)- and -Ar 2 - exists, whereby in the case that the bivalent unit -Ar 2 -C(O)- is the group Ar 2 binds to N and C(O) to the group Ar 1 binds; Ar 2 is a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 40 aromatic ring atoms, coupled with one or more R groups 4a or R 4b may be substituted; R 1 , R 2 are the same or different in each occurrence, selected from the group consisting of: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3, CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , C=O, C=S, , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 1 and / or R 2 can be linked to each other via a covalent single bond or a bivalent group Z; R 3 is the same or different in each occurrence selected from the group consisting of the following: H, D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CR 5 =CR 5 Ar 3 , CN, NO2, Si(R 5 )3, B(OR 5 )2, OSO2R 5 , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each with one or more R groups 5can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , Si(R 5 )2, Ge(R 5 )2, Sn(R 5 )2, C=O, C=S, C=Se, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 3 can be linked to each other via a covalent single bond or a bivalent group Z; R4a , R 4b are selected from the group consisting of the following, and are either the same or different in each occurrence: D, F, Cl, Br, I, N(Ar) 3 )2, C(=O)Ar 3 , P(=O)(Ar 3 )2, S(=O)Ar 3 , S(=O)2Ar 3 , CN, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms, each with one or more R groups 5 can be substituted and in each case one or more non-adjacent CH2 groups are replaced by R 5 C=CR 5 , C=C , C=O, C=S, , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5can be replaced and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is replaced by one or more R groups 6 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, separated by one or more R groups 5 may be substituted, or a combination of these systems; where two or more adjacent substituents R may also be present. 4a or R 4b can be linked to each other via a covalent single bond or a bivalent group Z; Ar 3 is a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups 6 may be substituted; R 5is the same or different at each occurrence H, D, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F, or a mono- or polycyclic aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is further divided by one or more R groups 6 can be substituted; where two or more substituents R are also possible 5 can be linked to each other via a covalent single bond or a bivalent group Z; R Sis the same or different at each occurrence H, D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by NH, O or S and wherein one or more H atoms may be replaced by F; wherein two or more substituents R 6 can be linked to each other via a covalent single bond or a bivalent group Z; Z represents a bivalent group -(CH2) q - dar, where q is 1, 2, 3, 4 or 5, preferred 1, 2, 3 or 4, more preferred 1, 2 or 3, and most preferred 1 or 2. [2] Electronic device according to claim 1, characterized by that Y is the same or different at each occurrence CR 1 is and that W is the same or different at each occurrence CR 2 is. [3] Electronic device according to claim 1 or 2, characterized by, that E is either a covalent single bond or a bivalent unit selected from N(R 3 ), C(R 3 )2, O and S is. [4] Electronic device according to one or more of claims 1 to 3, characterized by , that X, whether equal or different at each occurrence, is a bivalent unit selected from the group consisting of C(R 3 )2, S and O consists. [5] Electronic device according to one or more of claims 1 to 4, characterized by , that Ar is a bivalent or trivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms coupled with one or more R groups 4a may be substituted, preferably with phenylene or naphthylene, each with one or more R groups 4a may be substituted. [6] Electronic device according to one or more of claims 1 to 5, characterized by , that Ar 1selected is from the group consisting of pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5-triazine, quinoline, isoquinoline, quinoxaline, pyrazole, imidazole, benzimidazole, thiazole, benzothiazole, oxazole or benzooxazole, each with R 4b may be substituted. [7] Electronic device according to one or more of claims 1 to 6, characterized by that L is a covalent single bond or a bivalent unit -Ar 2 - is, whereby Ar 2 preferably represents a bivalent mono- or polycyclic aromatic or heteroaromatic unit with 5 to 10 aromatic ring atoms, which is coupled with one or more R groups 4a or R 4b may be substituted. [8] Electronic device according to one or more of claims 1 to 7, characterized by , that the sum of the indices n + m = 1. [9] Electronic device according to one or more of claims 1 to 8, wherein the electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic integrated circuits (O-ICs), organic solar cells (O-SCs), organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic photoreceptors or organic laser diodes (O-lasers). [10] Electronic device according to one or more of claims 1 to 9, wherein it is an organic electroluminescent device, characterized by, that the compound of formula I is used as a matrix material for phosphorescent dopants in an emitting layer and / or as an electron transport material in an electron transport layer and / or as a hole transport material in the hole transport layer and / or as a hole blocking material in a hole blocking layer. [11] Use of a compound according to formula I, as defined in one or more of claims 1 to 8, in an electronic device.