Materials for organic electroluminescent devices

Abstract

Amine compounds having dibenzofuran, dibenzothiophene, and fluorene groups are provided for use as triplet matrix materials in organic electroluminescent devices. Also provided are methods for preparing the compounds of the invention and electronic devices containing them. Specifically, for example, an amine compound obtained by the reaction of the following formula is shown. JPEG2022184899000091.jpg42170

Description

SUMMARY OF THE INVENTION

[0001] The present invention describes amines having dibenzofuran, dibenzothiophene and fluorene groups for use as triplet matrix materials, in particular in organic electroluminescent devices. The present invention further relates to a method for preparing the compounds of the present invention and to electronic devices comprising these compounds.

[0002] The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US4539507, US5151629, EP0676461 and WO98 / 27136. The luminescent materials used are often organometallic complexes that exhibit phosphorescence. For quantum mechanical reasons, the use of organometallic compounds as phosphorescent emitters allows for up to four times the energy efficiency and power efficiency. In general, improvements are still sought in OLEDs, particularly in OLEDs that exhibit phosphorescence, with regard to, for example, efficiency, operating voltage and lifetime.

[0003] The properties of phosphorescent OLEDs are not determined solely by the triplet emitters used. More specifically, other materials used, such as matrix materials, are also particularly important in this regard. Therefore, improvements in these materials can also lead to a clear improvement in the properties of OLEDs.

[0004] According to the prior art, amines having fluorene and dibenzofuran groups are known from US2014 / 0284578. Compounds having carbazole are also known from EP2421064. US2013 / 0234118 discloses amines having condensed aromatic groups, such as amines having condensed aromatic groups such as pyrene.

[0005] In general, for these materials used as matrix materials, improvements are still sought, particularly with regard to lifetime and oxidation sensitivity, but also with regard to the efficiency and operating voltage of the device.

[0006] In particular, it is an object of the present invention to provide compounds suitable for use in phosphorescent or fluorescent OLEDs as the matrix material. More specifically, it is an object of the present invention to provide a matrix material suitable for red, yellow and green phosphorescent OLEDs and possibly also for blue phosphorescent OLEDs, leading to long life, good efficiency and low operating voltage. In particular, the properties of the matrix material also have a very important influence on the life and efficiency of the organic electroluminescence device.

[0007] Surprisingly, it has been found that electroluminescent devices containing the compound of formula (1) below have improvements over the prior art, especially when used as a matrix material for phosphorescent dopants.

[0008] Therefore, the present invention provides the following formula (1):

[0009]

Chemical formula

[0010] [where the symbols used are as follows: X is O or S; Y is O, S or CR2; Ar is, in each case, the same or different and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R radicals, where Ar contains only aryl or heteroaryl groups having a maximum of 15 aromatic ring atoms and does not contain a carbazolyl group as a heteroaryl group and does not contain a 9,9'-spirobifluorene group; R is, in each case, the same or different and is H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1)2. B(Ar 1 )2. A linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 4 radicals, and one or more non-adjacent CH2 groups may be replaced by R 4 C=CR 4 , C=O, C=S, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4 , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, in each case optionally substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, optionally substituted by one or more R 1 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, optionally substituted by one or more R 4 radicals; simultaneously, two R substituents bonded to the same carbon atom or adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic ring system which may be substituted by one or more R 4 radicals; R 1 is in each case the same or different and is H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1) 2. A linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 4 radicals, and one or more non-adjacent CH2 groups may be replaced by R 4 C=CR 4 , C=O, C=S, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4 , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, and may be substituted by one or more R 4 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and may be substituted by one or more R 4 radicals, selected from the group consisting of; simultaneously, two R 1 substituents or two R 1 and R 3 substituents bonded to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 4 radicals; R 2 is in each case the same or different, H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1) 2. A straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 4 radicals, and one or more non-adjacent CH2 groups may be replaced by R 4 C=CR 4 , C=O, C=S, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4 , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, in each case optionally substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, optionally substituted by one or more R 4 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, optionally substituted by one or more R 4 radicals, selected from the group consisting of; simultaneously, two R 2 substituents attached to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system optionally substituted by one or more R 4 radicals; R 3 is in each case the same or different and is H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1) 2. A linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 4 radicals, and one or more non-adjacent CH2 groups may be R 4 C=CR 4 , C=O, C=S, C=NR 4 , P(=O)(R 4 ), SO, SO2, NR 4 , O, S or CONR 4 replaced, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and may be substituted by one or more R 4 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and may be substituted by one or more R 4 radicals, selected from the group consisting of; simultaneously, two R 3 and R 1 substituents bonded to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 4 radicals; Ar 1 is in each case the same or different, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and may be substituted by one or more non-aromatic R 4 radicals; simultaneously, two Ar 1 radicals bonded to the same phosphorus atom or boron atom are a single bond or N(R 4 ), C(R 4)2. They may be crosslinked to each other by a crosslink selected from O and S, R 4 in each case, is the same or different and is H, D, F, Cl, Br, I, CN, NO2, N(R 5 )2, C(=O)R 5 , a linear alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R 5 radicals, and one or more non-adjacent CH2 groups may be R 5 C=CR 5 , C=O, C=S, C=NR 5 , P(=O)(R 5 ), SO, SO2, NR 5 , O, S or CONR 5 and may be replaced by, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2), having 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R 5 radicals, an aromatic or heteroaromatic ring system, having 5 to 40 aromatic ring atoms, and may be substituted by one or more R 5 radicals, an aryloxy or heteroaryloxy group, or having 5 to 40 aromatic ring atoms, and may be substituted by one or more R 5 radicals, and is selected from the group consisting of aralkyl or heteroaralkyl groups; simultaneously, two R 4 substituents bonded to the same carbon atom or adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 5 radicals; R 5In each case, they are the same or different and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms (in this ring system, one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, or CN, and this ring system may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms); simultaneously, two or more adjacent Rs 5 The substituents can together form a monocyclic or polycyclic aliphatic ring system; Here, by way of example, a nitrogen atom is bonded to the corresponding carbon atom instead of R 1 or R 3 and in the case of R 3 Y is not CR2] to provide a compound.

[0011] Adjacent carbon atoms in the context of the present invention are carbon atoms directly bonded to each other.

[0012] The expression that two or more radicals can together form a ring is, in the context of this description, of course understood to mean, inter alia, that two radicals are connected to each other by a chemical bond by the formal exclusion of two hydrogen atoms. This is illustrated by the following scheme.

[0013]

Chemical formula

[0014] However, furthermore, the above expression is also of course understood to mean that when one of the two radicals is hydrogen, the second radical bonds to the position where the hydrogen atom was bonded to form a ring. This is illustrated by the following scheme.

[0015]

Chemical formula

[0016] A condensed aryl group in the context of the present invention is a group in which two or more aromatic groups are condensed, i.e., they are fused to each other along a common edge, such as in naphthalene. In contrast, for example, fluorene is not a condensed aryl group in the context of the present invention because the two aromatic groups in fluorene do not have a common edge.

[0017] An aryl group in the context of the present invention contains 6 to 40 carbon atoms; a heteroaryl group in the context of the present invention contains 2 to 40 carbon atoms and at least 1 heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. An aryl group or a heteroaryl group is herein understood to mean either a single aromatic ring, i.e., benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a condensed aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0018] In the context of the present invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system. A heteroaromatic ring system in the context of the present invention contains 1 to 40 carbon atoms and at least 1 heteroatom in the ring system, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of the present invention does not necessarily consist only of aryl or heteroaryl groups, and it is of course understood to mean a system in which two or more aryl or heteroaryl groups are intervened by non-aromatic units (preferably less than 10% of atoms other than H), for example, carbon, nitrogen or oxygen atoms or carbonyl groups. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., and further systems in which two or more aryl groups are intervened by, for example, linear or cyclic alkyl or silyl groups are also naturally regarded as aromatic ring systems in the context of the present invention. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, for example, biphenyl, terphenyl, quarterphenyl or bipyridine, are likewise naturally regarded as aromatic or heteroaromatic ring systems.

[0019] In the context of the present invention, cyclic alkyl, alkoxy or thioalkoxy groups are understood to mean monocyclic, bicyclic or polycyclic groups.

[0020] In the context of the present invention, C1 - C 20-An alkyl group (in this group, individual hydrogen atoms or CH2 groups may also be substituted by the above groups) means, for example, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl, and 1-(n-decyl)cyclohex-1-yl radicals.The alkynyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. The alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. C1 - C. 40 - The alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n - propoxy, i - propoxy, n - butoxy, i - butoxy, s - butoxy, t - butoxy, or 2 - methylbutoxy.

[0021] An aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and, in each case, optionally substituted by the above radicals and optionally connected at any desired position to an aromatic or heteroaromatic system is, for example, benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, torquene, isotorquene, spirotorquene, spiroisotorquene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, 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, fluorubine, naphthyridine, azacarbazole, benzocarbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,It is understood to mean a group derived from 3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.,

[0022] Preferably, in formula (1), when Y is CR2, the nitrogen atom is bonded to the corresponding carbon atom instead of R 1 ; when Y is O or S, the nitrogen atom is bonded to the corresponding carbon atom instead of R 1 or R 3 .

[0023] In a preferred embodiment, X is O.

[0024] In a further preferred embodiment, Y is CR2.

[0025] In a further preferred embodiment, X is O and Y is CR2.

[0026] In a further preferred embodiment of the present invention, when the compound of formula (1) is optionally substituted carbazole with R 1 or R 2 substituents, through those two positions, this carbazole is not bonded.

[0027] In a further embodiment of the present invention, the compound is of formula (1-1) or formula (1-2)

[0028]

Chemical formula

[0029] (wherein the symbols correspond to the symbols of formula (1)) selected from the compounds of

[0030] In a further preferred embodiment of the present invention, Ar is, in each case, the same or different and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R radicals, but is preferably unsubstituted, where Ar contains only aryl or heteroaryl groups having a maximum of 15 aromatic ring atoms, does not contain a carbazolyl group, and does not contain a 9,9'-spirobifluorene group. Examples of suitable Ar groups are phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, and 1-, 2-, 3- or 4-dibenzothienyl, each of which may be substituted by one or more R radicals, but is preferably unsubstituted.

[0031] In a preferred embodiment of the present invention, Ar is of the formula (Ar-1) to (Ar-16):

[0032]

Chemical formula

[0033]

Chemical formula

[0034] selected from the structures of where the symbols correspond to the symbols of formula (1) and, in addition, Q is, in each case, the same or different and is CR 4 or N, with no more than 3 Q symbols per ring being N; E is, in each case, the same or different and is C(R 4 )2, O, S or C=O; where two Rs 4 do not form an aromatic or heteroaromatic ring system; G is, in each case, NR 4 , C(R 4 )2, O, S or C=O; and * represents a bond to a nitrogen atom.

[0035] Preferably, none of the Qs is N.

[0036] In a further preferred embodiment, the Ar group in each case is selected from groups having the structures of formulas (Ar-1) to (Ar-16), where these general formulas are replaced by the particularly preferred respective embodiments of the following formulas (Ar-1-1) to (Ar-16-6) (for example, formula (Ar-1) is replaced by one of formulas (Ar-1-1) to (Ar-1-9)),

[0037]

Chemical formula

[0038]

Chemical formula

[0039]

Chemical formula

[0040]

Chemical formula

[0041]

Chemical formula

[0042]

Chemical formula

[0043] Here, the symbols correspond to the symbols in formulas (Ar-1) to (Ar-16). The formulas are in free positions and may be substituted by R 4 as appropriate.

[0044] In a further aspect of the present invention, R 2 is, in each case, the same or different, and in the case of an aromatic or heteroaromatic ring system, the structure of formulas (Ar-1) to (Ar-16), or preferred embodiments thereof, and formulas (Ar-17) and (Ar-18):

[0045]

Chemical formula

[0046] selected from the structures of where the symbols correspond to the symbols of formula (1), and further, in formulas (Ar-17) and (Ar-18): Q is, in each case, the same or different, CR 4 or N, and not more than 3 Q symbols per ring are N; E is, in each case, the same or different, NR 4 , C(R 4 )2, O, S or C=O, where two R 4 do not form an aromatic or heteroaromatic ring system; G is, in each case, NR 4 , C(R 4 )2, O, S or C=O; and * indicates a bond to an aromatic ring system.

[0047] Preferably, none of the Qs is N.

[0048] In a further preferred embodiment, R in each case 2The base, in the case of an aromatic or heteroaromatic ring system, is selected from groups having the structures of formulas (Ar-1) to (Ar-18), where these general formulas are replaced by their respective particularly preferred embodiments of the following formulas (Ar-1-1) to (Ar-16-6) (for example, formula (Ar-1) is replaced by one of formulas (Ar-1-1) to (Ar-1-9)), and further, the following formulas:

[0049]

Chemical formula

[0050] are preferred, where the symbols correspond to the symbols of formula (1).

[0051] In one embodiment of the present invention, the compound has the structure of formula (2) or formula (3):

[0052]

Chemical formula

[0053] where the symbols correspond to the symbols of formula (1), and where one R bonded to a carbon atom and one R 2 are replaced by a single bond, and in formula (2), in the case of R 4 , preferably, it is in a 6-membered ring not bonded to a nitrogen atom. 2 In a preferred embodiment of the present invention, the carbazole is not bonded through its two positions.

[0054] In a further preferred embodiment of the present invention, the compound has the structures of formulas (2-1) and (2-2):

[0055] In a further preferred embodiment of the present invention, the compound has the structures of formulas (2-1) and (2-2):

[0056]

Chemical formula

[0057] One compound of the structure, where the symbols correspond to the symbols of formula (2), where one R in formula (2-1) 2 and one R attached to the carbon atom in formula (2-2) 4 is replaced by a single bond (in the case of formula (2-2), on the 6-membered ring not attached to the nitrogen atom).

[0058] In a further preferred embodiment of the present invention, the compound is of formula (2-3):

[0059]

Chemical formula

[0060] a compound of where the symbols correspond to the symbols of formula (2).

[0061] In a further preferred embodiment of the present invention, the compound is of formula (3-1) and (3-2):

[0062]

Chemical formula

[0063] one compound of the structure, where the symbols correspond to the symbols of formula (3), where one R in formula (3-1) 2 and one R attached to the carbon atom in formula (3-2) 4 is replaced by a single bond (in the case of formula (3-2), on the 6-membered ring attached to the nitrogen atom).

[0064] In a further preferred embodiment of the present invention, the compound is of formula (3-3):

[0065]

Chemical formula

[0066] a compound of Here, the symbols correspond to the symbols of formula (3).

[0067] In a further aspect of the present invention, the compound is of formula (2-1a), (2-1b), (2-2a), (2-2b):

[0068]

Chemical formula

[0069]

Chemical formula

[0070] and is a compound of where the symbols correspond to the symbols of formula (2).

[0071] In a further aspect of the present invention, the compound is of formula (3-1a), (3-1b), (3-2a) or (3-2b):

[0072]

Chemical formula

[0073]

Chemical formula

[0074] and is a compound of where the symbols correspond to the symbols of formula (3).

[0075] In a further preferred aspect of the present invention, the compound is of formula (2-3a) or (2-3b):

[0076]

Chemical formula

[0077] and is a compound of Here, the symbols correspond to the symbols in formula (2-3).

[0078] In a further preferred embodiment of the present invention, the compound is of formula (3-3a) or (3-3b):

[0079]

Chemical formula

[0080] wherein the symbols correspond to the symbols in formula (3-3). Here, the symbols correspond to the symbols in formula (3-3).

[0081] In a further embodiment of the present invention, R 1 and R 3 are, in each case, the same or different and, in the case of an aromatic or heteroaromatic ring system, are selected from one of formulas (Ar-1) to (Ar-16), where the definitions of the symbols correspond to the symbols defining Ar, * is a bond to the aromatic ring system.

[0082] Preferably, the R substituents attached to Ar are H, D, F, CN, N(Ar 1 )2, a linear alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (the alkyl group or alkenyl group may, in each case, be substituted by one or more R 4 radicals, but is preferably unsubstituted), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms (each of these may, in each case, be substituted by one or more R 4 radicals, but is preferably unsubstituted), and is selected from the group consisting of; simultaneously, two R substituents attached to adjacent carbon atoms are one or more R 4It may be substituted by a radical, but is preferably unsubstituted, and may optionally form a monocyclic or polycyclic aliphatic ring system.

[0083] When Y is CR2, the R radicals bonded to this carbon atom are the same or different in each case, and are a linear alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (each alkyl or alkenyl group may be substituted by one or more R 4 radicals, where one or more non-adjacent CH2 groups may be replaced by O, and one or more hydrogen atoms may be replaced by D or F), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms (each of these may be substituted by one or more R 4 radicals), and preferably; at the same time, the two R substituents may be substituted by one or more R 4 radicals and may optionally form a monocyclic or polycyclic, aliphatic ring system. The ring formation between the two R substituents forms a spiro system.

[0084] Preferably, the R 1 substituent is H, D, F, CN, N(Ar 1 )2, a linear alkyl group having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms (the alkyl or alkenyl group is substituted by one or more R in each case 4which may be substituted by a radical, but is preferably unsubstituted), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms (each of these is one or more R 4 which may be substituted by a radical, but is preferably unsubstituted) and is selected from the group consisting of; simultaneously, two R 1 substituents or two R 1 and R 3 substituents may optionally form a monocyclic or polycyclic aliphatic ring system which may be substituted by one or more R 4 radicals, but is preferably unsubstituted).

[0085] Preferably, the R 2 substituent is H, D, F, CN, N(Ar 1 )2, a linear alkyl group having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably having 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms (the alkyl group or alkenyl group may, in each case, be substituted by one or more R 4 radicals, but is preferably unsubstituted), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms (each of these is one or more R 4 radicals, but is preferably unsubstituted) and is selected from the group consisting of; simultaneously, two R 2 substituents may optionally form a monocyclic or polycyclic aliphatic ring system which may be substituted by one or more R 4 radicals, but is preferably unsubstituted).

[0086] Preferably, R 3 substituent is H, D, F, CN, N(Ar 1 )2, a linear alkyl group having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably having 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms (the alkyl or alkenyl group may be substituted by one or more R 4 radicals in each case, but is preferably unsubstituted), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms (each of these may be substituted by one or more R 4 radicals in each case, but is preferably unsubstituted), selected from the group consisting of; simultaneously, two R 3 and R 1 substituents bonded to the same carbon atom or adjacent carbon atoms may be substituted by one or more R 4 radicals in each case, but is preferably unsubstituted, and may optionally form a monocyclic or polycyclic aliphatic ring system.

[0087] Preferably, R 4 substituent is H, D, F, CN, N(Ar 1 )2, N(R 5 )2, a linear alkyl group having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 8 carbon atoms, preferably having 3, 4, 5 or 6 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon atoms (the alkyl group or alkenyl group may be substituted by one or more R 4Optionally substituted by radicals, but preferably unsubstituted), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms (each of these is one or more non-aromatic R 5 Optionally substituted by radicals, but preferably unsubstituted), and is selected from the group consisting of; simultaneously, two Rs bonded to the same carbon atom or adjacent carbon atoms 4 The substituent is one or more Rs 5 Optionally, it may form a monocyclic or polycyclic, aliphatic ring system that is optionally substituted by radicals, but is preferably unsubstituted.

[0088] When E or G is NR 4 In this case, the Rs bonded to this nitrogen atom 4 Radicals are the same or different in each case, and have 5 to 24 aromatic ring atoms, and in each case, one or more Rs 5 Optionally substituted by radicals, aromatic or heteroaromatic ring system, more preferably having 6 to 18 aromatic ring atoms, and one or more Rs 5 Optionally substituted by radicals, preferably an aromatic or heteroaromatic ring system. Examples of suitable Rs 4 Substituents are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1,3,5-triazinyl, 4,6-diphenyl-1,3,5-triazinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, and 1-, 2-, 3- or 4-carbazolyl, where the carbazolyl group is substituted by an R other than H or D at the nitrogen atom 5 Radicals. These groups may each be optionally substituted by one or more Rs 5 Radicals, but are preferably unsubstituted.

[0089] In a further aspect of the present invention, the compound does not contain any additional uncrosslinked amines except for the central nitrogen atom. This means, for example, that no radical is N(Ar 1 )2 or N(R 4 )2.

[0090] In a further aspect of the present invention, at least one of R, R 1 , R 2 or R 3 in formula (1) is a heteroaryl group.

[0091] In a further aspect of the present invention, Ar is not a group of formula (Ar-10-2), for example, a 2-fluoroenyl group.

[0092] The above preferences can occur individually or together. The case where the above preferences occur together is preferred.

[0093] Examples of suitable compounds of the present invention are the structures shown below.

[0094] [Table 1-1]

[0095] [Table 1-2]

[0096] [Table 1-3]

[0097] [Table 1-4]

[0098] [Table 1-5]

[0099]

Table 1-6

[0100]

Table 1-7

[0101]

Table 1-8

[0102]

Table 1-9

[0103]

Table 1-10

[0104]

Table 1-11

[0105]

Table 1-12

[0106]

Table 1-13

[0107]

Table 1-14

[0108]

Table 1-15

[0109]

Table 1-16

[0110] The compounds of the present invention can be prepared by synthetic processes known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. An appropriate synthetic method is generally shown in Scheme 1 below.

[0111]

Chemical formula

[0112] The compound of formula (2) is shown in the following Scheme (2):

[0113]

Chemical formula

[0114] can be obtained by.

[0115] In this scheme, R is, according to formula (1) or (2), R, R 1 , R 2 or R 3 . Rather than a fluorene derivative, correspondingly, it is also possible to use a dibenzofuran derivative or a dibenzothiophene derivative.

[0116] For example, formulations of the compounds of the present invention are required for the processing of the compounds of the present invention from the liquid phase, by spin coating or by a printing method. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular, 3-phenoxytoluene, (-)-fencon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane, or mixtures of these solvents.

[0117] Therefore, the present invention further provides a formulation comprising a compound of the present invention and at least one further compound. The further compound can be, for example, a solvent, in particular one of the above solvents or a mixture of these solvents. Alternatively, the further compound can likewise be at least one further organic or inorganic compound used in an electronic device, for example a luminescent compound, in particular a phosphorescent dopant, and / or a further matrix material. Suitable luminescent compounds and further matrix materials are listed at the end in connection with organic electroluminescence devices. This further compound can also be a polymer.

[0118] The compounds and mixtures of the present invention are suitable for use in electronic devices. An electronic device is understood to mean a device comprising at least one layer containing at least one organic compound. This component can also include inorganic materials or, alternatively, layers formed entirely of inorganic materials.

[0119] Accordingly, the present invention further provides the use of a compound or mixture of the present invention in an electronic device, in particular in an organic electroluminescence device.

[0120] The present invention further provides an electronic device comprising at least one compound or mixture of the present invention as detailed above. In this case, the preferences detailed above for the compound also apply to the electronic device.

[0121] The electronic device is preferably selected from the group consisting of an organic electroluminescence device (OLED, PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitized solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light emitting electrochemical cell (LEC), an organic laser diode (O-laser), and an organic plasmonic light emitting device, preferably an organic electroluminescence device (OLED, PLED), particularly a phosphorescent OLED.

[0122] The organic electroluminescence device includes a cathode, an anode, and at least one light emitting layer. In addition to these layers, it may also include additional layers, for example, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. Similarly, an intermediate layer having an exciton blocking function can also be introduced, for example, between two light emitting layers. However, it should be pointed out that the presence of any of these layers is not necessarily required. In this case, the organic electroluminescence device can include one light emitting layer or it can include a plurality of light emitting layers. If a plurality of light emitting layers are present, they preferably have several emission maxima in the range of 380 nm to 750 nm, and as a result, the overall result is white light emission. In other words, various luminescent compounds that can emit fluorescence or phosphorescence are used in the light emitting layer. One aspect of the present invention relates to a system having three light emitting layers, where the three layers exhibit blue, green, and orange or red light emission. These can be multiple layers of fluorescent or phosphorescent emission, or alternatively, a hybrid system in which fluorescent and phosphorescent emission layers are combined with each other. A further aspect of the present invention relates to a tandem OLED. The white light emitting electroluminescence device can be used, for example, for lighting applications, but can also be used in a full-color display in combination with a color filter.

[0123] Depending on the exact structure, the compounds of the present invention according to the embodiments detailed above can be used in various layers. Depending on the exact substitution, the compounds of formula (1) or those shown as preferred embodiments can be used for fluorescent or phosphorescent emitters, or for emitters showing TADF (thermally activated delayed fluorescence), especially for phosphorescent emitters, and / or as matrix materials in electron transport layers and / or electron blocking layers or exciton blocking layers and / or hole transport layers and / or hole injection layers in organic electroluminescence devices. In this context, the preferred embodiments detailed above also apply to the use of materials in organic electronic devices.

[0124] In a preferred embodiment of the present invention, the compound of formula (1) or according to a preferred embodiment is used as a matrix material for a fluorescent or phosphorescent compound in the emission layer. In this case, the organic electroluminescence device may comprise one emission layer, or it may comprise a plurality of emission layers, in which case at least one emission layer contains at least one compound of the present invention as a matrix material.

[0125] When the compound of formula (1) or according to a preferred embodiment is used as a matrix material for a luminescent compound in the emission layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the context of the present invention is understood to mean luminescence from an excited state with a spin multiplicity > 1, especially from an excited triplet state. In the context of this application, all transition metal complexes showing luminescence and all lanthanide complexes showing luminescence, especially all complexes of iridium, platinum and copper, are of course regarded as phosphorescent compounds.

[0126] The mixture of the compound according to formula (1) or a preferred embodiment and the luminescent compound contains 99 to 1% by volume, preferably 98 to 10% by volume, more preferably 97 to 60% by volume, particularly 95 to 80% by volume of the compound according to formula (1) or a preferred embodiment, based on the total mixture of the emitter and the matrix material. Correspondingly, the mixture contains 1 to 99% by volume, preferably 2 to 90% by volume, more preferably 3 to 40% by volume, particularly 5 to 20% by volume of the emitter, based on the total mixture of the emitter and the matrix material. When the compound is processed by a solution, it is preferred to use the corresponding amount by weight rather than the amount by volume specified above.

[0127] Suitable phosphorescent compounds (= triplet emitters) emit light, particularly when appropriately excited, preferably in the visible region, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. In particular, they are compounds containing a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, particularly compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the above metals are considered phosphorescent compounds.

[0128] Examples of such light emitters can be found in applications WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307, WO2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709, WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023377, WO2014 / 094961, WO2014 / 094960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, and WO2016 / 124304. In general, all phosphorescent complexes used in prior art phosphorescent OLEDs and known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art could use additional phosphorescent complexes without exercising the skill corresponding to the invention.

[0129] A further preferred embodiment of the present invention is the use of a compound of formula (1) or a preferred embodiment as a matrix material for a phosphorescent emitter in combination with a further matrix material. In a preferred embodiment of the present invention, the further matrix material is a hole transporting compound. In a further preferred embodiment of the present invention, the further matrix material is an electron transporting compound. In a further preferred embodiment, the further matrix material is a compound having a large band gap that is not significantly involved in the transport of holes and electrons in the layer.

[0130] Suitable matrix materials that can be used in combination with the compound according to formula (1) or the preferred embodiment are, for example, aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones according to WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or 2010 / 006680, for example, triarylamines according to WO2014 / 015935, especially monoamines, carbazole derivatives, such as CBP(N,(N-biscarbazolylbiphenyl), or a carbazole derivative disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527 or WO2008 / 086851, for example, an indolocarbazole derivative according to WO2007 / 063754 or WO2008 / 056746, for example, an indenocarbazole derivative according to WO2010 / 136109 and WO2011 / 000455, for example, an azacarbazole derivative according to EP1617710, EP1617711, EP1731584, JP2005 / 347160, for example, a bipolar matrix material according to WO2007 / 137725, for example, a silane according to WO2006 / 117052, for example, an azaborole or boronic ester according to WO2010 / 015306, WO2007 / 063754 or WO2008 / 056746, for example, a triazine derivative according to EP652273 or WO2009 / 062578, for example, a zinc complex according to WO2010 / 054729, for example, a diazasilole or tetraazasilole derivative according to WO2010 / 054730, for example, a diazaphosphole derivative according to US2009 / 0136779, WO2010 / 050778, WO2011 / 042107, WO2011 / 088877 or WO2012 / 143080, for example, a bridged carbazole derivative according to WO2012 / 048781, for example, a triphenylene derivative according to WO2011 / 116865, WO2011 / 137951 or WO2013 / 064206, a lactam, or, for example, a 4-spirocarbazole derivative according to WO2014 / 094963 or WO2015 / 192939. Additionally, additional phosphorescent emitters that emit at wavelengths shorter than the actual emitter can also be present as co-hosts in the mixture.,

[0131] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams and carbazole derivatives.

[0132] In a further aspect of the invention, the organic electroluminescence device of the invention does not include any independent hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that, as described in, for example, WO2005 / 053051, the light-emitting layer is directly in contact with the hole injection layer or the anode, and / or the light-emitting layer is directly in contact with the electron transport layer or the electron injection layer or the cathode. Further, as described in, for example, WO2009 / 030981, it is possible to use the same or a similar metal complex as the metal complex in the light-emitting layer as a hole transport or hole injection material directly in contact with the light-emitting layer.

[0133] Furthermore, the compound of the invention can be used in a hole transport or electron blocking layer.

[0134] In a further layer of the organic electroluminescence device of the invention, it is possible to use any material commonly used in the prior art. Therefore, a person skilled in the art can use any material known in organic electroluminescence devices in combination with the compound of the invention according to formula (1) or the preferred embodiments without exercising the skill corresponding to the invention.

[0135] In addition, preferably, the organic electroluminescence device is characterized in that one or more layers are coated by a sublimation method. In this case, the material is deposited by evaporation at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar in a vacuum sublimation apparatus. It is also possible for the initial pressure to be even lower or higher, for example less than 10 -7 mbar.

[0136] Similarly, an organic electroluminescence device is also preferred, wherein one or more layers are coated by an OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. In this case, the material is applied at a pressure of 10 -5 mbar to 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly by a nozzle, thus giving a structure. (For example, M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301) In addition, an organic electroluminescence device is preferred, wherein one or more layers are produced from a solution, for example, by spin coating or by any printing method, such as inkjet printing, LITI (light-induced thermal imaging, thermal transfer printing), screen printing, flexographic printing, offset printing or nozzle printing. For this purpose, soluble compounds are required, which can be obtained, for example, through appropriate substitution.

[0137] The compounds of the present invention have improved oxidation stability, especially in solution, compared to the diamines commonly used. This is particularly important in printing methods. The compounds of the present invention are also characterized by high thermal stability, so that they can be vapor deposited without decomposition under high vacuum. The thermal stability also increases the operating life of the compounds.

[0138] Furthermore, a hybrid method is possible, in which, for example, one or more layers are applied from a solution and one or more further layers are applied by vapor deposition. For example, it is possible to apply a light-emitting layer from a solution and an electron transport layer by vapor deposition.

[0139] These methods are generally known to those skilled in the art, and those skilled in the art can apply them to organic electroluminescence devices containing the compounds of the present invention without exercising inventive skills.

[0140] When the compounds of the present invention are used in organic electroluminescence devices, they generally have very good properties. In particular, when the compounds of the present invention are used in organic electroluminescence devices, the lifetime is significantly better compared to similar compounds according to the prior art. At the same time, further properties of the organic electroluminescence devices, especially efficiency and voltage, are likewise better or at least equivalent.

[0141] The present invention will now be illustrated in detail by the following examples, without any intention of limiting the invention thereby.

[0142] [Examples] The following syntheses are carried out in a dry solvent under a protective gas atmosphere, unless otherwise stated. Solvents and reagents can be purchased, for example, from Sigma - ALDRICH or ABCR. For compounds known from the literature, the corresponding CAS numbers are also reported in each case.

[0143] [Synthesis Examples] a) 4 - Bromo - 9 - methyl - 9 - phenyl - 9H - fluorene

[0144] [Chemical Formula]

[0145] Dissolve 30 g (94 mmol) of 2,2'-dibromobiphenyl in 200 ml of dry THF in a baked-out flask. Cool the reaction mixture to -78 °C. At this temperature, slowly add dropwise (over about 1 hour) 37.7 ml of a 2.5 M hexane solution of n-butyllithium (94 mmol). Stir the mixture at -70 °C for an additional 1 hour. Next, dissolve 11.1 ml of acetophenone (94 mmol) in 100 ml of THF and add dropwise at -70 °C. After the addition is complete, warm the reaction mixture slowly to room temperature, quench with NH4Cl, and then concentrate on a rotary evaporator. Carefully add 300 ml of acetic acid to the concentrated solution, and then add 50 ml of fuming HCl. Heat the mixture at 75 °C for 6 hours. During this time, a white solid precipitates. Cool the mixture to room temperature, filter off the precipitated solid by suction, and wash with methanol. Dry the residue under reduced pressure at 40 °C. The yield is 25.3 g (75 mmol) (80% of theory).

[0146] b) 4-Bromo-9,9-diphenyl-9H-fluorene

[0147] [Chemical formula]

[0148] Dissolve 37 g (152 mmol) of 2,2'-dibromobiphenyl in 300 mL of dry THF in a baked-out flask. Cool the reaction mixture to -78 °C. At this temperature, slowly add dropwise (over about 1 hour) 75 mL of a 15% hexane solution of n-butyllithium (119 mmol). Stir the mixture at -70 °C for an additional 1 hour. Next, dissolve 21.8 g of benzophenone (119 mmol) in 100 mL of THF and add it dropwise at -70 °C. After the addition is complete, warm the reaction mixture slowly to room temperature, quench it with NH4Cl, and then concentrate it on a rotary evaporator. Carefully add 510 mL of acetic acid to the concentrated solution, and then add 100 mL of fuming HCl. Heat the mixture at 75 °C for 4 hours. During this time, a white solid precipitates. Cool the mixture to room temperature, filter off the precipitated solid by suction, and wash it with methanol. Dry the residue under reduced pressure at 40 °C. The yield is 33.2 g (83 mmol) (70% of theory).

[0149] The following brominated compounds are prepared in the same manner:

[0150] [Table 2]

[0151] c) 6-Bromo-2-fluoro-2'-methoxybiphenyl

[0152] [Chemical formula]

[0153] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid, and 137.5 g (997 mmol) of sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of water, degassed, and 9.3 g (13.3 mmol) of bis(triphenylphosphino)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is then stirred at 70 °C for 48 h under a protective gas atmosphere. Toluene is added to the cooled solution, washed repeatedly with water, dried, and concentrated. The product is purified by column chromatography on silica gel with toluene / heptane (1:2). Yield: 155 g (553 mmol), 83% of theory.

[0154] The following compounds are prepared in the same manner.

[0155] [Table 3]

[0156] d) 6’-bromo-2’-fluorobiphenyl-2-ol

[0157] [Chemical formula]

[0158] 112 g (418 mmol) of 6-bromo-2-fluoro-2’-methoxybiphenyl are dissolved in 2 L of dichloromethane and cooled to 5 °C. To this solution, 41.0 ml (431 mmol) of boron tribromide are added dropwise within 90 min, and the mixture is stirred overnight. The mixture is then gradually mixed with water, the organic phase is washed three times with water, dried over Na2SO4, concentrated by rotary evaporator, and purified by chromatography. Yield: 104 g (397 mmol), 98% of theory.

[0159] The following compounds are prepared in the same manner.

[0160]

Table 4

[0161] e) 1-Bromodibenzofuran

[0162]

Chem.

[0163] Dissolve 111 g (416 mmol) of 6'-bromo-2'-fluorobiphenyl-2-ol in 2 L of DMF (max. H2O 0.003%) SeccoSolv® and cool to 5 °C. To this solution, add portionwise 20 g (449 ml) of sodium hydride (60% suspension in paraffin). Once the addition is complete, stir the mixture for 20 minutes and then heat the mixture to 100 °C for 45 minutes. After cooling, add 500 ml of ethanol gradually to the mixture, concentrate by rotary evaporator and then purify by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

[0164] The following compounds are prepared in the same manner.

[0165]

Table 5

[0166] f) Biphenyl-4-yl dibenzofuran-1-ylamine

[0167]

Chem.

[0168] 30.0 g (177 mmol, 1.0 eq) of 4-aminobiphenyl was initially charged into 600 ml of anhydrous toluene together with 43.7 g (177 mmol, 1.0 eq) of 1-bromodibenzofuran and 2.4 g (212 mmol, 1.20 eq) of sodium tert-pentoxide [14593-46-5], and degassed for 30 minutes. Next, 398 mg (1.77 mmol, 0.01 eq) of palladium(II) acetate [3375-31-3] and 1.46 g (3.56 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPHOS) [657408-07-6] were added, and the mixture was heated to reflux overnight. After completion of the reaction, the mixture was cooled to room temperature and extracted with 500 ml of water. Next, the aqueous phase was washed three times with toluene, the combined organic layers were dried over sodium sulfate, and the solvent was removed by rotary evaporator. The brown residue was dissolved in approximately 200 ml of toluene and filtered through silica gel. For further purification, recrystallization from toluene / heptane was performed. Yield: 44 g (133 mmol), 76% of theory.

[0169] The following compounds are prepared in the same manner.

[0170] [Table 6-1]

[0171] [Table 6-2]

[0172] [Table 6-3]

[0173] [Table 6-4]

[0174] g) Dibenzofuran-1-yl-(4-dibenzofuran-4-ylphenyl)-(9,9-dimethyl-9H-fluoren-4-yl)amine

[0175]

Chem.

[0176] A mixture of 13.6 g (50 mmol) of 4-bromo-9,9-dimethyl-9H-fluorene, 25.5 g (60 mmol) of dibenzofuran-1-yl-(4-dibenzofuran-4-ylphenyl)amine, 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate, and 300 ml of mesitylene is heated to reflux for 24 h. After cooling, 200 ml of water is added, the mixture is stirred for a further 30 min, the organic phase is removed, the organic phase is filtered through a short bed of celite, and then the solvent is removed under reduced pressure. The residue is recrystallized 5 times from DMF and finally sublimed twice (p is about 10 -6 mbar, T = 340 - 350 °C). Yield: 23 g (37 mmol), 75% of theory: 99.9% by HPLC.

[0177] The following compounds are obtained in the same way:

[0178]

Table 7-1

[0179]

Table 7-2

[0180]

Table 7-3

[0181]

Table 7-4

[0182]

Table 7-5

[0183] h) 1-Bromo-8-iododibenzofuran

[0184]

Chem.

[0185] 20 g (80 mmol) of dibenzofuran-1-boronic acid, 2.06 g (40.1 mmol) of iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid, and 5 ml of sulfuric acid, and 5 ml of water, and 2 ml of chloroform are stirred at 65 °C for 3 hours. After cooling, the mixture is mixed with water, and the precipitated solid is separated by suction filtration and washed three times with water. The residue is recrystallized from toluene and also from dichloromethane / heptane. The yield is 25.6 g (68 mmol), corresponding to 85% of the theoretical value.

[0186] The following compounds are prepared in the same manner.

[0187]

Table 8

[0188] i) 3-(9-Bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole

[0189]

Chem.

[0190] 58 g (156 mmol) of 1-bromo-8-iododibenzofuran, 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol dimethyl ether and 280 ml of water. To this suspension, 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) is added and the reaction mixture is heated to reflux for 16 hours. After cooling, the organic layer is taken out, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The yield is 48 g (89 mmol), corresponding to 64% of the theoretical value.

[0191] The following compounds are prepared in the same manner.

[0192]

Table 9-1

[0193]

Table 9-2

[0194]

Table 9-3

[0195]

Table 9-4

[0196] j) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-[8-(9-phenyl-9H-carbazol-3-yl)dibenzofuran-1-yl]amine

[0197]

Chemical formula

[0198] A mixture of 9.3 g (26 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)amine, 12 g (26 mmol) of 3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole, 7.7 g (80 mmol) of sodium tert-butoxide, 2.6 ml (78 mmol) of tri-tert-butylphosphine (1 M, toluene), 224 mg (2.6 mmol) of palladium(II) acetate, and 300 ml of mesitylene is heated to reflux for 24 hours. After cooling, 200 ml of water is added, the mixture is stirred for an additional 30 minutes, the organic phase is removed, the organic phase is filtered through a short bed of celite, and then the solvent is removed under reduced pressure. The residue is recrystallized 5 times from DMF and finally sublimed twice (p is about 10 -6 mbar, T = 340 - 350 °C). Yield: 13 g (17 mmol), 68% of theory: 99.9% by HPLC.

[0199] The following compounds are prepared in the same manner.

[0200]

Table 10-1

[0201]

Table 10-2

[0202]

Table 10-3

[0203]

Table 10-4

[0204]

Table 10-5

[0205]

Table 10-6

[0206]

Table 10-7

[0207]

Table 10-8

[0208] Manufacture of OLED In the following Examples C1 to I9 (see Tables 1 and 2), data of various OLEDs are shown.

[0209] Pretreatment in Examples C1 to I9: A glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm is coated with 20 nm of PEDOT:PSS (purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH, Germany and spin-on from an aqueous solution of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonic acid)) for improved processing. These coated glass plates form the substrates on which the OLEDs are deposited.

[0210] The OLED basically has the following layer structure: substrate / hole transport layer (HTL) / optional intermediate layer (IL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally the cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The exact structure of the OLED can be found in Table 1. The materials required for the manufacture of the OLED are shown in Table 3.

[0211] All materials are deposited by thermal evaporation in a vacuum chamber. In this case, the light-emitting layer always consists of at least one matrix material (host material) and a luminescent dopant (luminescent substance) added to the matrix material(s) in a specific volume ratio by co-evaporation. Details described in the form of IC5:IC3:TEG1 (45%:45%:10%) 30 nm here mean that in the layer, material IC5 is present in a ratio of 45% by volume, IC3 is present in a ratio of 45% by volume, and TEG1 is present in a ratio of 10% by volume. Similarly, the electron transport layer also consists of a mixture of two materials.

[0212] OLEDs are characterized in a standard way. For this purpose, the electroluminescence spectrum, voltage, and external quantum efficiency (EQE, measured as a percentage) are determined as a function of luminance and lifetime calculated from the current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics. The electroluminescence spectrum is determined at a luminance of 1000 cd / m 2 The parameter U1000 in Table 2 here represents the voltage required for a luminance of 1000 cd / m 2 EQE1000 represents the external quantum efficiency at an operating luminance of 1000 cd / m 2 The lifetime LT is defined as the time during operation at a constant current when the luminance drops from the starting luminance to a certain ratio L1. The numerical values L0;j0 = 4000 cd / m 2 and L1 = 70% in Table 2 mean that the lifetime reported in the LT column corresponds to the time when the starting luminance of 4000 cd / m 2 ~2800 cd / m 2 Similarly, L0;j0 = 20 mA / cm 2 and L1 = 80% mean that during operation at 20 mA / cm 2 the luminance drops to 80% of its starting value after time LT.

[0213] Data for various OLEDs are collected in Table 2. Examples C1 - C8 are comparative examples according to the prior art; examples I1 - I9 show data for the OLEDs of the present invention.

[0214] Some examples are disclosed in detail below to illustrate the advantages of the OLEDs of the present invention.

[0215] Use of the mixtures of the present invention in the light-emitting layer of phosphorescent OLEDs The materials of the present invention, when used in the light-emitting layer (EML) of phosphorescent light-emitting OLEDs and also in the electron blocking layer (EBL), result in a significant improvement over the prior art, particularly with regard to the lifetime of the OLED components. By using the compounds INV-1 to INV-3 of the present invention in combination with IC5 and the green dopant TEG1, an increase in lifetime of more than 40% can be observed compared to the prior art VG-1 to VG-4 (comparison with I1 to I3 in Examples C1 to C4). By using the compounds INV-1 to INV-3 of the present invention in the EBL, an increase in lifetime of more than 25% can be observed compared to the prior art VG-1 to VG-4 (comparison with I4 to I6 in Examples C5 to C8).

[0216] [Table 11-1]

[0217] [Table 11-2]

[0218] [Table 11-3]

[0219] [Table 12]

[0220] [Table 13-1]

[0221] [Table 13-2]

[0222]

Table 13-3

Claims

1. Formula (1) 【Chemical 1】 [wherein the symbols used are as follows: X is O or S; Y is O, S or CR 2 and; Ar is selected from the structures of formulas (Ar-2) to (Ar-5), (Ar-8), (Ar-9), (Ar-11) and (Ar-16), where Ar contains only aryl or heteroaryl groups having a maximum of 15 aromatic ring atoms, (wherein in addition to containing aryl or heteroaryl groups having a maximum of 15 aromatic ring atoms, Ar allows for the intervention of non-aromatic units.) and does not contain a carbazolyl group as a heteroaryl group and does not contain a 9,9'-spirobifluorene group; 【Chemical 2】 wherein Q is the same or different in each case, CR 4 and is; however, when Q is in formulas (Ar-2), (Ar-5) and (Ar-8) directly bonded to the N atom specified in formula (1), Q is C, and when Q is in formulas (Ar-3), (Ar-4), (Ar-11) and (Ar-16) directly bonded to a further Q via a single bond, Q is C; E is C(R 4 ), O or S; 2 wherein; * indicates a bond to a nitrogen atom; R is, in each case, the same or different and is H, D, a linear alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms (one or more hydrogen atoms of the alkyl group may be replaced by D or F), an aromatic ring system having 6 to 13 aromatic ring atoms and, in each case, one or more R 4 radicals, which is selected from the group consisting of aromatic ring systems, where the aromatic ring system is defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other; R 1 is, in each case, the same or different and is H, D, F, CN, N(Ar １ ), a linear alkyl group having 2, 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms (one or more hydrogen atoms of the alkyl group may be replaced by D or F), an aromatic ring system having 6 to 13 aromatic ring atoms, and in each case is selected from the group consisting of aromatic ring systems which may be substituted by one or more R 4 radicals, where the aromatic ring system is defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other; R 2 is, in each case, the same or different and is H, D, F, CN, N(Ar １ ), a linear alkyl group having 2, 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms, where one or more hydrogen atoms of the alkyl group may be replaced by D or F), an aromatic ring system having 6 to 13 aromatic ring atoms and, in each case, optionally substituted by one or more R 4 radicals, and is selected from the group consisting of aromatic or heteroaromatic ring systems, where the aromatic ring system is defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other, and where the heteroaromatic ring system is defined as a heteroaryl group or a group in which a heteroaryl group is directly bonded to one or more further aryl or heteroaryl groups; R 3 which, in each case, is the same or different and is H, D, F, CN, a linear alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 carbon atoms (one or more hydrogen atoms of the alkyl group may be replaced by D or F), an aromatic ring system having 6 to 13 aromatic ring atoms, and in each case, one or more R 4 radicals may be selected from the group consisting of aromatic ring systems which are defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other; Ar 1 is, in each case, the same or different and has 6 to 30 aromatic ring atoms and is, in each case, the same or different, an aromatic ring system optionally substituted by one or more radicals selected from the group consisting of H, D, an alkyl group having 1 carbon atom (one or more hydrogen atoms of the alkyl group may be replaced by D), where the aromatic ring system is defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other; R 4 which, in each case, is the same or different and is selected from the group consisting of H, D, an alkyl group having 1 carbon atom (one or more hydrogen atoms of the alkyl group may be replaced by D), an aromatic ring system having 6 aromatic ring atoms and which, in each case, may be substituted by one or more 5 R radicals, where the aromatic ring system is defined as an aryl group or a group in which two or more aryl groups are directly bonded to each other; R 5 is, in each case, the same or different and is selected from H or D; Here, the nitrogen atom is bonded to the corresponding carbon atom instead of R 1 or R 3 and where the nitrogen atom specified in formula (1) is bonded to the corresponding carbon atom instead of R 3 Y in the case where it is bonded is not CR 2 and cannot be a compound of; however, the following compounds are excluded. [Chemical Formula 3]

2. The compound according to claim 1, wherein X is O.

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

4. The compound according to any one of claims 1 to 3, wherein the compound is of formula (1-1) or formula (1-2) 【Chemical Formula 4】 (wherein the symbols have the definitions given in claim 1). The compound according to any one of claims 1 to 3, wherein the compound is of formula (1-1) or formula (1-2)

5. The compound according to any one of claims 1 to 4, wherein the compound is of formula (2) 【Chemical Formula 5】 (wherein the symbol has the definition given in claim 1, and wherein one R bonded to a carbon atom 2 and one R 4 are replaced by a single bond) The compound according to any one of claims 1 to 4, wherein the compound is of formula (2)

6. The compound according to any one of claims 1 to 5, wherein the compound is one of formulas (2-1) and (2-2) 【Chemical Formula 6】 (Here, the symbol has the definition given in claim 1, and here, one R of formula (2-2) 2 and one R bonded to the carbon atom of formula (2-1) 4 is replaced by a single bond) The compound according to any one of claims 1 to 5, wherein the compound is one of formulas (2-1) and (2-2)

7. In formula (2-2), R replaced by a single bond 2 The compound according to claim 6, wherein is not located on the 6-membered ring bonded to the nitrogen atom.

8. A mixture comprising at least one compound according to any one of claims 1 to 7, at least one further compound and / or at least one solvent.

9. Use of a compound according to any one of claims 1 to 7 or a mixture according to claim 8 in an electronic device.

10. An electronic device comprising at least one compound according to any one of claims 1 to 7 or a mixture according to claim 8.

11. The electronic device according to claim 10, which is an organic electroluminescence device.

12. The electronic device according to claim 11, wherein the compound according to any one of claims 1 to 7 or the mixture according to claim 8 is used in the light-emitting layer, or in the hole transport layer, or in the electron blocking layer.

13. The electronic device according to claim 11, wherein the compound according to any one of claims 1 to 7 or the mixture according to claim 8 is used in the light-emitting layer, or in the hole transport layer, or in the electron blocking layer, in combination with a phosphorescent dopant and optionally one or more further matrix materials.

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