Novel materials for organic light emitting devices

Abstract

The present invention relates to novel materials and electronic devices, in particular organic electronic devices such as OLEDs (organic light emitting diodes) containing these materials, for example as electron transport materials, hole blocking materials or matrix materials. The invention also relates to mixtures that contain these novel materials.

Description

[0001] Foreignfiling text P24-260

[0002] -1-

[0003] Novel materials for organic light emitting devices

[0004] The present invention relates to novel materials and electronic devices, in particular organic electronic devices such as OLEDs (organic light emitting diodes) containing these materials, for example as electron transport materials,

[0005] 5 hole blocking materials or matrix materials. The invention also relates to mixtures that contain these novel materials.

[0006] Electronic devices according to the present application are understood to be organic electronic devices, which contain organic semiconductor materials as

[0007] 10 functional materials. In particular, the electronic devices are organic electroluminescent devices (OLEDs). OLEDs, in the sense of the present application, are understood to be electronic devices which contain one or more layers of organic compounds, and which emit light if an electrical voltage is applied. The structure as well as the basic operating mode of OLEDs, as well as

[0008] 15 methods for the preparation of OLEDs, are known to the skilled person.

[0009] In electronic devices, in particular OLEDs, performance data like lifetime, efficiency and operating voltage of devices are important. A great influence on these performance data can be attributed to layers like emitting layers, hole

[0010] 20 blocking layers or electron transporting layers.

[0011] In the prior art, triazine derivatives are known to be suitable for use in layers with electron-transporting function. Triazine derivatives with many different structural elements such as fluorene or spirobifluorene groups are known.

[0012] 25

[0013] WO 2005 / 053055 A1 discloses a 9,9'-bis(triazinyl) fluorene compound having two phenyl groups as substituents of each triazine group as hole blocking material in phosphorescent electroluminescent devices.

[0014] 30 WO 2009 / 124627 A1 and WO 2010 / 136109 A1 each shows bis(triazinyl)- indenocarbazole compounds wherein both triazine groups are identically substituted with aryl groups. These compounds can be used as electron transport material in electroluminescent devices.

[0015] KR 20140099082 A relates to heteroaromatic compounds amongst which are

[0016] 35 compounds having N-containing heteroaryl groups like pyridine, pyrimidine or Foreignfiling text P24-260

[0017] -2- triazine as substituents. These compounds can be used as matrix material in organic electroluminescent devices.

[0018] In general terms, in the case of these materials, e. g. for use as electron-transport materials, hole blocking materials or as matrix materials, there is still need for

[0019] 5 improvement in performance of the device, particularly in relation to the efficiency, operating voltage and lifetime of said device.

[0020] It is therefore an object of the present invention to provide compounds suitable for use in an electronic device, especially an organic electroluminescent device,

[0021] 10 preferably a phosphorescent or fluorescent OLED, as electron-transport material, hole blocking material and / or as matrix material. More particularly, it is an object of the present invention to provide compounds that lead to a long lifetime, good efficiency and low operating voltage when used in an electronic device such as an OLED.

[0022] 15

[0023] Surprisingly, it has been found that these objects are solved by a compound according to Formula (I) where the symbols and indices used are as follows:

[0024] 30

[0025] X is the same at each instance, and is N or CR;

[0026] Ar is the same at each instance, and is an aromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be identically substituted by

[0027] 35 one or more radicals R1or a heteroaromatic ring system having 5 to 40 Foreignfiling text P24-260

[0028] -3- aromatic ring atoms, which may in each case be identically sub-'stituted by one or more radicals R1;

[0029] Ar1is the same at each instance, and is an aromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be identically substituted by

[0030] 5 one or more radicals R2or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2;

[0031] Ra, Rb

[0032] 10 is independently from each other selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 30 C-atoms, an alkenyl or alkynyl group having 2 to 20 C atoms, wherein each of the straight chain

[0033] 15 alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi or polycyclic alkyl groups may be substituted by one or more radhcals R3, where in each case one or more non-adjacent CH2 groups may be replaced by -R3C=CR3-, -C=C-, Si(R3)2, C=O, C=S, C=NR3, -C(=O)O-, -C(=O)NR3-, NR3, P(=O)(R3), -O-, -S-, SO or SO2and

[0034] 20 where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or an aliphatic polycyclic ring system having at least 3 rings, which may be substituted by one or more radicals R3, or an aryloxy or heteroaryloxy group having 5 to 40

[0035] 25 aromatic ring atoms, which may be substituted by one or more radicals R3, or an aralkyl group having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R3; at the same time two or more, preferably adjacent radicals Raand / or Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which

[0036] 30 may be substituted by one or more radicals R3;

[0037] R is the same at each instance and is selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a mono- , bi- or polycyclic alkyl group

[0038] 35 each having 3 to 30 C-atoms, an alkenyl or alkynyl group having 2 to 20 C Foreignfiling text P24-260

[0039] -4- atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R4, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R4; at the

[0040] 5 same time two radicals R, or two or more radicals R and R1or two or more radicals R and R2may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R4;

[0041] 10 R1, R2, R6is the same or different at each instance and is H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a mono-, bi-or polycyclic alkyl group each having 3 to 20 C-atoms, an alkenyl or alkynyl group having 2 to 20 C atoms wherein each of the straight

[0042] 15 chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5where one or more nonadjacent CH2 groups may be replaced by -R5C=CR5-, -C=C-, Si(R5)2, C=O, C=S, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO2and

[0043] 20 where one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R5radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R5radicals, or an aralkyl or heteroaralkyl

[0044] 25 group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R5radicals; at the same time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent radicals R2or two or more, preferably adjacent radicals R6, together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be substituted

[0045] 30 by one or more radicals R5;

[0046] R3, R4, R5is the same or different at each instance and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, Foreignfiling text P24-260

[0047] -5- having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN;

[0048] Ar2is is the same or different at each instance, and is an aromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be substituted by

[0049] 5 one or more radicals R6or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R6; m, n

[0050] 10 is independently from each other 0, 1 , 2, 3 or 4, preferably 0, 1 , 2 or 3, more preferably 0, 1 or 2, even more preferably 0 or 1 with the proviso that at least one of m or n is at least 1 and with the proviso that ring system A and ring system B is different and

[0051] 15 wherein the following compounds are excluded:

[0052] 25

[0053] It is to be understood, that if an index is 0 all free positions at the benzene ring are

[0054] 35 substituted with hydrogen or deuterium. Foreignfiling text P24-260

[0055] The term “ring system A and ring system B is different” means that the benzene rings are not identically substituted; for example, different substituent(s) may be used for the two benzene rings or identical substituent(s) are linked to different positions of the benzole ring.

[0056] 5

[0057] Adjacent carbon atoms in the context of the present invention are carbon atoms bonded directly to one another. In addition, "adjacent radicals" in the definition of the radicals means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply correspondingly, inter alia, to the

[0058] 10 terms "adjacent groups" and "adjacent substituents".

[0059] The wording that two or more radicals together may form a ring, in the context of the present description, shall be understood to mean, inter alia, that the two radicals are joined to one another by a chemical bond with formal elimination of

[0060] 15 two hydrogen atoms. This is illustrated by the following scheme:

[0061] 20

[0062] In addition, however, the abovementioned wording shall also be understood to mean that, if one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This shall be illustrated by the following scheme:

[0063] 25

[0064] A fused aryl group in the context of the present invention is a group in which two

[0065] 30 or more aromatic groups are fused, i.e. annealed, to one another along a common edge, such that, for example, two carbon atoms belong to the at least two aromatic or heteroaromatic rings, as, for example, in naphthalene. By contrast, for example, fluorene is not a fused aryl group in the context of the present invention, since the two aromatic groups in fluorene do not have a common edge. Foreignfiling text P24-260

[0066] -7-

[0067] Corresponding definitions apply to heteroaryl groups and to fused ring systems which may but need not also contain heteroatoms.

[0068] According to the present invention “D” or “D-atom” stands for deuterium.

[0069] 5 An aryl group in the context of this invention contains 6 to 40 ring atoms, preferably carbon atoms; a heteroaryl group in the context of this invention contains 5 to 40 ring atoms comprising carbon atoms and at least one heteroatom, with the proviso that the total sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl

[0070] 10 group or heteroaryl group is understood here to mean either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, furane, thiophene, etc., or a fused aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. An aromatic ring system in the context of this invention contains 6 to 40 ring

[0071] 15 atoms, preferably 6 to 30 ring atoms, more preferably 6 to 25 ring atoms, even more preferably 6 to 18 ring atoms, most preferably 6 to 12 ring atoms, in the ring system wherein the ring atoms are preferably C-atoms. A heteroaromatic ring system in the context of this invention contains 1 to 40 carbon atoms, preferably 4 to 30 carbon atoms, more preferably 4 to 25 carbon atoms, even more preferably

[0072] 20 4 to 19 carbon atoms, most preferably 4 to 12 carbon atoms and at least one heteroatom in the ring system, with the proviso that the total sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of this invention shall be understood to mean a system which does not necessarily

[0073] 25 contain only aryl or heteroaryl groups, but in which it is also possible for two or more aryl or heteroaryl groups to be interrupted by a nonaromatic unit (preferably less than 10% of the atoms other than H), for example a carbon, nitrogen or oxygen atom or a carbonyl group. For example, systems such as 9,9’- spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc. shall

[0074] 30 also be regarded as aromatic ring systems in the context of this invention, and likewise systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. In addition, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, shall likewise be regarded as an

[0075] 35 aromatic or heteroaromatic ring system. Foreignfiling text P24-260

[0076] -8-

[0077] An aromatic ring system which has 6 to 40 aromatic ring atoms or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms which can be linked via any position on the aromatic or heteroaromatic ring system is understood to mean, for example, groups derived from benzene, which may be joined to the aromatic or heteroaromatic system via any desired positions

[0078] 5 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-

[0079] 10 dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,

[0080] 15 phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1 ,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1 ,5-diazaanthracene,

[0081] 20 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, 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-

[0082] 25 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.

[0083] In the context of the present invention, a straight-chain alkyl group having 1 to 20

[0084] 30 C-atoms, preferably having 1 to 10 C-atoms, more preferably having 1 to 6 C- atoms, a branched alkyl group having 3 to 20 C-atoms, preferably having 3 to 10 C-atoms, more preferably having 3 to 6 C-atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 30 C-atoms, preferably having 3 to 20 C-Atoms, more preferably having 3 to 12 C-atoms, in which individual hydrogen atoms or CH2

[0085] 35 groups may also be substituted by the abovementioned groups is understood to Foreignfiling text P24-260

[0086] -9- mean, for example, the 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,

[0087] 5 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-

[0088] 10 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. An alkenyl group having 2 to 20 C-atoms, preferably having 2 to 10 C-atoms,

[0089] 15 more preferably having 2 to 6 C-atoms, is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. An alkynyl group having 2 to 20 C-atoms, preferably having 2 to 10 C-atoms, more preferably having 2 to 6 C-atoms, is understood to mean, for example, ethynyl, propynyl,

[0090] 20 butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0091] In a preferred embodiment of the present invention, both symbols X are N.

[0092] In a further preferred embodiment of the present invention, the radicals

[0093] 25 Raand Rbare independently from each other selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 20 C-atoms, an alkenyl or alkynyl group having 2 to 10 C atoms wherein each of the straight chain alkyl groups,

[0094] 30 each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono- or polycyclic alkyl groups may be substituted by one or more radhcals R3, where in each case one or more non-adjacent CH2groups may be replaced by - -O- or -S-, and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms,

[0095] 35 which may in each case be substituted by one or more radicals R3, or an Foreignfiling text P24-260

[0096] -10- aliphatic polycyclic ring system having at least 3 rings, which may be substituted by one or more radicals R3; at the same time two or more, preferably adjacent radicals Raand / or Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3.

[0097] 5

[0098] More preferably, the radicals Raand Rbare independently from each other selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 6 C atoms, a branched alkyl group having 3 to 8 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 10

[0099] 10 C-atoms, an alkenyl group having 2 to 8 C atoms where in each case one or more non-adjacent CH2 groups may be replaced by - -O- or -S-, and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be sub-'stituted by one or more radicals R3, or an aliphatic polycyclic ring system

[0100] 15 having at least 3 rings, which may be substituted by one or more radicals R3; at the same time two or more, preferably adjacent radicals Raand / or two ore more, preferably adjacent radicals Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3.

[0101] 20

[0102] Even more preferably, the radicals Raand Rbare the same or different at each instance, and and are selected from the group consisting of H, D, F, CN, -OH, - SH, - N(Ar2)2, a straight-chain alkyl group having 1 to 6 C atoms, a branched alkyl group having 3 to 8 C atoms, a mono- , bi- or polycyclic alkyl group each having 3

[0103] 25 to 10 C-atoms, an alkenyl group having 2 to 8 C atoms where in each case one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which may in each case be sub^stituted by one or more radicals R3, or an aliphatic polycyclic ring system having at least 3 rings, which may be substituted by one or more radicals R3; at

[0104] 30 the same time two or more, preferably adjacent radicals Raand / or Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3.

[0105] In a further preferred embodiment of the present invention, the symbol Ar is the

[0106] 35 same at each instance and is an aromatic ring system having 6 to 30 aromatic Foreignfiling text P24-260

[0107] -11 - ring atoms, more preferably 6 to 25 aromatic ring atoms, even more preferably 6 to 18 aromatic ring atoms, most preferably 6 to 12 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R1, or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, more preferably 5 to 25 aromatic ring atoms, even more preferably 5 to 18 aromatic ring atoms,

[0108] 5 most preferably 5 to 13 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R1, and the symbol Ar1is the same at each instance and is an aromatic ring system having 6 to 30 aromatic ring atoms, more preferably 6 to 25 aromatic ring atoms, even more preferably 6 to 18 aromatic ring atoms, most preferably 6 to 12 aromatic ring atoms, which may in

[0109] 10 each case be identically substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, more preferably 5 to 25 aromatic ring atoms, even more preferably 5 to 18 aromatic ring atoms, most preferably 5 to 13 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2, , where R1and R2have the

[0110] 15 definition as mentioned above.

[0111] Suitable examples for the symbols Ar or Ar1can independently from each other be selected from the following (Ar-1) to (Ar-264) which may in each case be substituted by one or more radicals R1or R2, where R1or R2has the above-

[0112] 20 mentioned definition:

[0113] 25

[0114] 30

[0115] 35 Foreignfiling text P24-260

[0116] 5

[0117] 10

[0118] 15

[0119] 20

[0120] 25

[0121] 30

[0122] 35 Foreignfiling text P24-260

[0123] 5

[0124] 10

[0125] 15

[0126] 20

[0127] 25

[0128] 30

[0129] 35 Foreignfiling text P24-260

[0130] 5

[0131] 10

[0132] 15

[0133] 20

[0134] 25

[0135] 30

[0136] 35 Foreignfiling text P24-260

[0137] 5

[0138] 10

[0139] 15

[0140] 20

[0141] 25

[0142] 30

[0143] 35 Foreignfiling text P24-260

[0144] 5

[0145] 10

[0146] 15

[0147] 20

[0148] 25

[0149] 30

[0150] 35 Foreignfiling text P24-260

[0151] 5

[0152] 10

[0153] 15

[0154] 20

[0155] 25

[0156] 30

[0157] 35 Foreignfiling text P24-260

[0158] 5

[0159] 10

[0160] 15

[0161] 20

[0162] 25

[0163] 30

[0164] 35 Foreignfiling text P24-260

[0165] 5

[0166] 10

[0167] 15

[0168] 20

[0169] 25

[0170] 30

[0171] 35 Foreignfiling text P24-260

[0172] 5

[0173] 10

[0174] 15

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[0177] 30

[0178] 35 Foreignfiling text P24-260

[0179] 5

[0180] 10

[0181] 15

[0182] 20

[0183] 25

[0184] 30

[0185] 35 Foreignfiling text P24-260

[0186] -22-

[0187] 5

[0188] 10

[0189] 15

[0190] 20

[0191] 25

[0192] 30

[0193] 35 Foreignfiling text P24-260

[0194] 5

[0195] 10

[0196] 15

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[0200] 35 Foreignfiling text P24-260

[0201] 5

[0202] 10

[0203] 15

[0204] 20

[0205] 25

[0206] 30

[0207] 35 Foreignfiling text P24-260

[0208] -25-

[0209] 5

[0210] 10

[0211] 15

[0212] 20

[0213] 25

[0214] 30

[0215] 35 Foreignfiling text P24-260

[0216] 5

[0217] 10

[0218] 15

[0219] 20

[0220] 25

[0221] 30

[0222] 35 Foreignfiling text P24-260

[0223] 5

[0224] 10

[0225] 15

[0226] 20

[0227] 25

[0228] 30

[0229] 35 Foreignfiling text P24-260

[0230] 5 where the dotted bond marks the attachment position.

[0231] 10

[0232] It is further preferred, that for the symbols Ar or Ar1an aromatic ring system having 6 to 30 aromatic ring atoms is selected from the group consisting of phenyl, ortho-, meta- or para biphenyl, ortho-, meta, para- or branched terphenyl, ortho-, meta- , para- or branched quaterphenyl, napthalene, anthracene,

[0233] 15 phenanthrene, triphenylene, fluoranthene, benzofluoranthene, 1-, 2-, 3- or 4- fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, which may in each case be identically substituted by one or more radicals R1or which may in each case be identically substituted by one or more radicals R2and the heteroaromatic ring system having 5 to 30 aromatic ring atoms is selected from the group consisting of 1-, 2-, 3- or 4-

[0234] 20 dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl or N- carbazolyl, which may in each case be identically substituted by one or more radicals R1or which may in each case be identically substituted by one or more radicals R2, where the radicals R1and R2have the definition as mentioned above.

[0235] 25 The radical R is the same or different at each instance and is preferably selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, an alkenyl having 2 to 10 C atoms, a mono-, bi- or polycyclic alkyl group having each having 3 to 12 C-atoms, wherein each of the straight chain alkyl groups, each of the branched

[0236] 30 alkyl groups, each of the alkenyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R4, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R4; at the same time two or more, preferably adjacent radicals R may form a mono- or polycyclic, aliphatic or

[0237] 35 aromatic or heteroaromatic ring system with one another, which may be Foreignfiling text P24-260

[0238] -29- substituted by one or more radicals R4. More preferably, the radical R is independently from each other selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 6 C atoms, a branched alkyl group having 3 to 6 C atoms, a mono-, bi- or polycyclic alkyl group having each having 3 to 10 C-atoms, wherein each of the straight chain alkyl groups, each of the branched

[0239] 5 alkyl groups, each of the alkenyl groups or each of the mono- or polycyclic alkyl groups may be substituted by one or more radhcals R4, or an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R4; at the same time two or more, preferably adjacent radicals R may form a mono- or polycyclic, aliphatic or

[0240] 10 aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R4. Even more preferably, the radical R is independently from each other selected from the group consisting of H, D, F, CN, or an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R4; at the same

[0241] 15 time two or more, preferably adjacent radicals R may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R4.

[0242] Preferably, the radicals R1, R2and R6are the same or different at each instance

[0243] 20 and are selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a mono-, bi-or polycyclic alkyl group each having 3 to 10 C-atoms, an alkenyl or alkynyl group having 2 to 10 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or

[0244] 25 each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5where one or more nonadjacent CH2 groups may be replaced by -O- or -S-, and where one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R5radicals, at the same

[0245] 30 time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent radicals R2or two or more, preferably adjacent radicals R6together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R5. More preferably, the radicals R1, R2and R6are the same or different at each instance and are

[0246] 35 selected from the group consisting of H, D, F, CN, a straight-chain alkyl group Foreignfiling text P24-260

[0247] -30- having 1 to 6 C atoms, a branched alkyl group having 3 to 8 C atoms, a mono-, bi- or polycyclic alkyl group each having 3 to 8 C-atoms, an alkenyl or alkynyl group having 2 to 8 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5

[0248] 5 where one or more nonadjacent CH2 groups may be replaced by -O- or -S-, and where one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 18 aromatic ring atoms, each of which may be substituted by one or more R5radicals, at the same time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent

[0249] 10 radicals R2or two or more, preferably adjacent radicals R6together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R5. Even more preferably, the radicals R1, R2and R6are the same or different at each instance and are selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 6 C

[0250] 15 atoms, a branched alkyl group having 3 to 8 C atoms, a mono-, bi-or polycyclic alkyl group each having 3 to 8 C-atoms, an alkenyl group having 2 to 8 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5where one or more

[0251] 20 hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 13 aromatic ring atoms, each of which may be substituted by one or more R5radicals, at the same time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent radicals R2or two or more, preferably adjacent radicals R6together may also form a mono- or

[0252] 25 polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R5.

[0253] It is further preferred, that the radicals R3, R4, R5are the same or different at each instance and are selected from the group consisting of H, D, F, CN or an aliphatic,

[0254] 30 aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 18 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN. It is even more preferred, that the radicals R3, R4, R5are the same or different at each instance and are selected from the group consisting of H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical,

[0255] 35 Foreignfiling text P24-260

[0256] -31 - especially a hydrocarbyl radical, having 1 to 13 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN.

[0257] Compounds according to formula (I) have a molecular weight of not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, especially preferably not more than 2000 g / mol and most

[0258] 5 preferably not more than 1200 g / mol. In addition, it is a feature of preferred compounds of the invention that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0259] Examples of suitable compounds according to the invention are listed below in

[0260] 10 Table 1.

[0261] Table 1 :

[0262] 15

[0263] 20

[0264] 25

[0265] 30

[0266] 35 Foreignfilingjext P24-260

[0267] -32-

[0268] 35 Foreignfilingjext P24-260

[0269] -33-

[0270] 35 Foreignfiling text P24-260

[0271] 5

[0272] 10

[0273] 15

[0274] 20

[0275] 25

[0276] 30

[0277] 35 Foreignfilingjext P24-260

[0278] -35- Foreignfiling_text P24-260

[0279] -36-

[0280] 5

[0281] 10

[0282] 15

[0283] 20

[0284] 25

[0285] 30 Foreignfiling text P24-260

[0286] 5

[0287] 10

[0288] 15

[0289] 20

[0290] 25

[0291] 30

[0292] 35 Foreignfiling text P24-260

[0293] 5

[0294] 10

[0295] 15

[0296] 20

[0297] 25

[0298] Preferred embodiments of compounds of the invention are detailed specifically in the examples, these compounds being usable alone or in combination with further

[0299] 30 compounds for all purposes of the invention.

[0300] Provided that the conditions specified in Claim 1 are complied with, the abovementioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the

[0301] 35 abovementioned preferred embodiments apply simultaneously. Foreignfiling text P24-260

[0302] -39-

[0303] The compounds of the invention are preparable in principle by various processes. However, the process described hereinafter has been found to be particularly suitable.

[0304] 5 Suitable compounds having an electron-transporting group are in many cases commercially available, and the starting compounds detailed in the examples are obtainable by known processes, and so reference is made thereto.

[0305] These compounds can be reacted with further aryl or heteroaryl compounds by

[0306] 10 known coupling reactions, the necessary conditions for this purpose being known to the person skilled in the art, and detailed specifications in the examples give support to the person skilled in the art in conducting these reactions.

[0307] In all the synthesis schemes which follow, the compounds are shown with a small

[0308] 15 number of substituents to simplify the structures. This does not rule out the presence of any desired further substituents in the processes.

[0309] An illustrative implementation is given by the scheme which follows, without any intention that this should impose a restriction.

[0310] 20

[0311] The process shown for synthesis of the compounds of the invention should be understood by way of example. The person skilled in the art will be able to develop alternative synthesis routes within the scope of his common knowledge in the art.

[0312] 25

[0313] The compounds according to the invention can be obtained starting from fluorenes (1) well known in the literature by deprotonation with a base, such as n-butyllithium, sodium or potassium tert-butylate, lithium-di-iso-propylamide, lithium-tetramethyl piperidide or preferably lithium bis-trimethylsilylamide

[0314] 30 (LHMDS) and coupling with a chlorotriazine (2) to give the product (3), see Scheme 1. Suitable reaction media are preferably dipolar-aprotic solvents, preferably aliphatic and / or cyclic ethers, such as diethyl ether, di-n-butyl ether, tetra hydrofuran, 2-methyltetrahydrofuran or dioxane.

[0315] 35 Scheme 1: Foreignfiling text P24-260 wherein the symbols Ra, Rb, Ar, Ar1, Ar3, and X and the indices m and n have the definition as given above.

[0316] 10

[0317] It is possible by these processes, if necessary followed by purification, for example recrystallization or sublimation, to obtain the compounds of the invention according to Formula (I) and preferred embodiments of these structures in high purity, preferably more than 99% (determined by means of1H NMR and / or

[0318] 15 HPLC).

[0319] Further compounds which can be used as electron transport material and / or matrix material are the following ones:

[0320] 20

[0321] 25

[0322] 30

[0323] 35 Foreignfiling text P24-260

[0324] -41-

[0325] Compound ETM-1 can be prepared according to procedures disclosed in WO 2010 / 072300 A1 or WO 2023 / 099543 A1 in connection with known deuteration methods. Deuteration methods are known to the skilled person and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651, and WO2018 / 110887, or in the Bulletin of the Chemical Society of Japan, 2021 ,

[0326] 5 94(2), 600-605, or the Asian Journal of Organic Chemistry, 2017, 6(8), 1063- 1071.

[0327] A suitable method for the deuteration of a compound by the exchange of one or more H atoms for D atoms is a treatment of the compound to be deuterated in the

[0328] 10 presence of a platinum catalyst or palladium catalyst and a deuterium source. The term "deuterium source" means any compound that contains one or more D atoms and can release them under suitable conditions.

[0329] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry

[0330] 15 platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol- d4, or toluene-d8. A preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is

[0331] 20 the combination of D2O with a fully deuterated organic solvent, where the fully deuterated solvent is not limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably at temperatures between 100 °C and 200 °C.

[0332] 25 Furthermore, the reaction is preferably carried out under pressure.

[0333] If available, commercially available deuterated intermediate can be employed to synthesize these compounds.

[0334] 30 Compound ETM-2 can be prepared in accordance with the procedures disclosed in WO 2010 / 015306 A1 and compound ETM-3 can be prepared in accordance with the procedures disclosed in WO2017 / 178311 A1.

[0335] The compounds of the invention may also be mixed with a polymer. It is likewise

[0336] 35 possible to incorporate these compounds covalently into a polymer. This is Foreignfiling text P24-260

[0337] -42- especially possible with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, or by reactive polymerizable groups such as olefins or oxetanes. These may find use as monomers for production of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably effected via the halogen

[0338] 5 functionality or the boronic acid functionality or via the polymerizable group. It is additionally possible to crosslink the polymers via groups of this kind. The compounds of the invention and polymers may be used in the form of a crosslinked or uncrosslinked layer.

[0339] 10 The invention therefore further provides oligomers, polymers or dendrimers containing one or more of the above-detailed structures of the Formula (I) and preferred embodiments of these structures or compounds of the invention, wherein one or more bonds in the compounds of the invention or in the structures of the Formula (I) and preferred embodiments of these structures to the polymer,

[0340] 15 oligomer or dendrimer are present. According to the linkage of the structures of the Formula (I) and preferred embodiments of these structures or of the compounds, these therefore form a side chain of the oligomer or polymer or are bonded within the main chain. The polymers, oligomers or dendrimers may be conjugated, partly conjugated or nonconjugated. The oligomers or polymers may

[0341] 20 be linear, branched or dendritic. For the repeat units of the compounds of the invention in oligomers, dendrimers and polymers, the same preferences apply as described above.

[0342] For preparation of the oligomers or polymers, the monomers of the invention are

[0343] 25 homopolymerized or copolymerized with further monomers. Preference is given to copolymers wherein the units of Formula (I) or the preferred embodiments recited above and hereinafter are present to an extent of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, more preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer base skeleton are chosen from fluorenes (for example

[0344] 30 according to EP 842208 or WO 2000 / 022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylenes (for example according to WO 92 / 18552), carbazoles (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (for example according to WO 2005 / 014689),

[0345] 35 cis- and trans-indenofluorenes (for example according to WO 2004 / 041901 or WO Foreignfiling text P24-260

[0346] -43-

[0347] 2004 / 113412), ketones (for example according to WO 2005 / 040302), phenanthrenes (for example according to WO 2005 / 104264 or WO 2007 / 017066) or else a plurality of these units. The polymers, oligomers and dendrimers may contain still further units, for example hole transport units, especially those based on triarylamines, and / or electron transport units.

[0348] 5

[0349] Additionally of particular interest are compounds of the invention which feature a high glass transition temperature. In this connection, preference is given especially to compounds of the invention comprising structures of the general Formula (I) or the preferred embodiments recited above and hereinafter which

[0350] 10 have a glass transition temperature of at least 70 °C, more preferably of at least 110 °C, even more preferably of at least 125 °C, still even more preferably of at least 140 °C, and especially preferably of at least 150 °C, determined in accordance with DIN EN ISO 11357-2 (2014).

[0351] 15 For the processing of the compounds of the invention from the liquid phase, for example by spin-coating or by printing methods, formulations of the compounds of the invention are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. Suitable and preferred solvents are, for example,

[0352] 20 toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1, 2,4,5- tetramethyl benzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2- phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-

[0353] 25 dimethylanisole, 3,5-dimethylanisole, acetophenone, a-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

[0354] 30 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.

[0355] 35 Foreignfiling text P24-260

[0356] -44-

[0357] The present invention therefore further provides a formulation comprising at least one compound of the invention and at least one solvent, especially one of the abovementioned solvents or a mixture of these solvents. It is also possible that the formulation may alternatively be at least one further organic or inorganic compound which is likewise used in the electronic device, for example an emitting

[0358] 5 compound, especially a phosphorescent dopant, and / or a further matrix material.

[0359] The present invention also provides a composition comprising at least one compound of the invention and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF emitters,

[0360] 10 host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, n-dopants, wide band gap materials, electron blocking materials and hole blocking materials. This composition may also comprise at least one solvent as mentioned above.

[0361] 15 The present invention therefore also relates to a composition comprising at least one compound according to Formula (I) or the preferred embodiments recited hereinand at least one further matrix material as further compound. According to a particular aspect of the present invention, the further matrix material has holetransporting properties.

[0362] 20

[0363] The present invention further provides a composition comprising at least one compound according to Formula (I) or the preferred embodiments recited above and hereinafter and at least one wide band gap material, a wide band gap material being understood to mean a material in the sense of the disclosure of US

[0364] 25 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

[0365] Preferably, the additional compound may have a band gap of 2.5 eV or more, preferably 3.0 eV or more, very preferably of 3.5 eV or more. One way of

[0366] 30 calculating the band gap is via the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0367] Molecular orbitals, especially also the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), the energy levels thereof

[0368] 35 and the energy of the lowest triplet state Ti and that of the lowest excited singlet Foreignfiling text P24-260

[0369] -45- state Si of the materials are determined via quantum-chemical calculations. For calculation of organic substances without metals, an optimization of geometry is first conducted by the "Ground State / Semi-empirical / Default Spin / AM1 / Charge 0 / Spin Singlet" method. Subsequently, an energy calculation is effected on the basis of the optimized geometry. This is done using the "TD-SCF / DFT / Default

[0370] 5 Spin / B3PW91" method with the "6-31 G(d)" basis set (charge 0, spin singlet). For metal-containing compounds, the geometry is optimized via the "Ground State / Hartree-Fock / Default Spin / LanL2MB / Charge 0 / Spin Singlet" method. The energy calculation is effected analogously to the above-described method for the organic substances, except that the "LanL2DZ" basis set is used for the metal atom and

[0371] 10 the "6-31G(d)" basis set for the ligands. The HOMO energy level HEh or LIIMO energy level LEh is obtained from the energy calculation in Hartree units. This is used to determine the HOMO and LIIMO energy levels in electron volts, calibrated by cyclic voltammetry measurements, as follows:

[0372] 15 HOMO(eV) = ((HEh*27.212)-0.9899) / 1.1206

[0373] LUMO(eV) = ((LEh*27.212)-2.0041) / 1.385

[0374] These values are to be regarded as HOMO and LIIMO energy levels of the materials in the context of this application.

[0375] 20

[0376] The lowest triplet state Ti is defined as the energy of the triplet state having the lowest energy, which is apparent from the quantum-chemical calculation described.

[0377] 25 The lowest excited singlet state Si is defined as the energy of the excited singlet state having the lowest energy, which is apparent from the quantum-chemical calculation described.

[0378] The method described herein is independent of the software package used and

[0379] 30 always gives the same results. Examples of frequently utilized programs for this purpose are “GaussianO9W” (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

[0380] The present invention also relates to a composition comprising at least one compound according to Formula (I) or the preferred embodiments recited above

[0381] 35 and hereinafter and at least one phosphorescent emitter, the term Foreignfiling text P24-260

[0382] -46-

[0383] "phosphorescent emitter" also being understood to mean phosphorescent dopants.

[0384] A dopant in a system comprising a matrix material and a dopant is understood to mean that component having the smaller proportion in the mixture.

[0385] 5

[0386] Correspondingly, a matrix material in a system comprising a matrix material and a dopant is understood to mean that component having the greater proportion in the mixture.

[0387] 10 Preferred phosphorescent dopants for use in matrix systems, preferably mixed matrix systems, are the preferred phosphorescent dopants specified hereinafter.

[0388] The term "phosphorescent dopants" typically encompasses compounds where the emission of light is effected through a spin-forbidden transition, for example a

[0389] 15 transition from an excited triplet state or a state having a higher spin quantum number, for example a quintet state.

[0390] Suitable phosphorescent compounds (= triplet emitters) are especially compounds which, when suitably excited, emit light, preferably in the visible

[0391] 20 region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum,

[0392] 25 silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the abovementioned metals are regarded as phosphorescent compounds.

[0393] Preferred examples of phosphorescent emitters are described in WO2019 / 007867

[0394] 30 on pages 120 to 126 in table 5, and on pages 127 to 129 in table 6. The emitters are incorporated into the description by this reference.

[0395] Particularly preferred examples of phosphorescent emitters are listed in table 2 below.

[0396] 35 Foreignfilingjext P24-260

[0397] -47-

[0398] Table 2:

[0399] 35 Foreignfiling_text P24-260

[0400] -48-

[0401] 5

[0402] 10

[0403] 15

[0404] 20

[0405] 25

[0406] 30

[0407] 35 Foreignfiling text P24-260

[0408] 5

[0409] 10

[0410] 15

[0411] 20

[0412] 25

[0413] 30

[0414] The above-described compound according to Formula (I) or the above-detailed preferred embodiments can preferably be used as active component in an electronic device. An electronic device is understood to mean any device comprising anode, cathode and at least one layer between anode and cathode,

[0415] 35 said layer comprising at least one organic or organometallic compound. The Foreignfiling text P24-260

[0416] -50- electronic device of the invention thus comprises anode, cathode and at least one layer in between containing at least one compound according to Formula (I). Preferred electronic devices here are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-

[0417] 5 TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices (D. M. Koller et al., Nature Photonics 2008, 1-4), preferably organic electroluminescent

[0418] 10 devices (OLEDs, PLEDs), especially phosphorescent OLEDs, containing at least one compound according to Formula (I) in at least one layer. Particular preference is given to organic electroluminescent devices. Active components are generally the organic or inorganic materials introduced between the anode and cathode, for example charge injection, charge transport or charge blocking materials, but

[0419] 15 especially emission materials and matrix materials.

[0420] The present invention further provides the use of a compound of the invention in an electronic device, preferably as a matrix material, a hole blocking material, an electron injection material and / or an electron transport material, more preferably

[0421] 20 as a hole blocking material and / or an electron transport material. The use of a composition comprising at least one compound according to the invention and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor

[0422] 25 materials, hole injection materials, n-dopants, wide band gap materials, electron blocking materials and hole blocking materials or the use of a formulation comprising at least one compound according to the invention and at least one solvent in an electronic device, preferably as matrix material, a hole blocking material, an electron injection material and / or an electron transport material, more

[0423] 30 preferably as hole blocking material and / or an electron transport material is also provided by the present invention.

[0424] A preferred embodiment of the invention relates to organic electroluminescent devices. The organic electroluminescent device comprises cathode, anode and at least one emitting layer. Apart from these layers, it may comprise still further

[0425] 35 layers, for example in each case one or more hole injection layers, hole transport Foreignfiling text P24-260

[0426] -51 - layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n junctions. At the same time, it is possible that one or more hole transport layers are p-doped, for example with metal oxides such as MoOa or WO3 or with (per)fluorinated electron-deficient aromatic systems, and / or

[0427] 5 that one or more electron transport layers are n-doped. It is likewise possible for interlayers to be introduced between two emitting layers, these having, for example, an exciton-blocking function and / or controlling the charge balance in the electroluminescent device. However, it should be pointed out that not necessarily every one of these layers need be present.

[0428] 10

[0429] In this case, it is possible for the organic electroluminescent device to contain an emitting layer, or for it to contain a plurality of emitting layers. If a plurality of emission layers are present, these preferably have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white

[0430] 15 emission; in other words, various emitting compounds which may fluoresce or phosphoresce are used in the emitting layers. Especially preferred are three-layer systems where the three layers exhibit blue, green and orange or red emission (for the basic construction see, for example, WO 2005 / 011013), or systems having more than three emitting layers. The system may also be a hybrid system

[0431] 20 wherein one or more layers fluoresce and one or more other layers phosphoresce.

[0432] In a preferred embodiment of the invention, the organic electroluminescent device contains the compound of the invention according to Formula (I) or the above¬

[0433] 25 detailed preferred embodiments as matrix material, preferably as electron transport matrix material, in one or more emitting layers, preferably in combination with a further matrix material, preferably a hole transport matrix material. In a further preferred embodiment of the invention, the further matrix material is an electron-transporting compound. In yet a further preferred embodiment, the

[0434] 30 further matrix material is a compound having a large band gap which is not involved to a significant degree, if at all, in the hole and electron transport in the layer. An emitting layer comprises at least one emitting compound.

[0435] Suitable matrix materials which can be used in combination with the compounds

[0436] 35 of Formula (I) or according to the preferred embodiments are aromatic ketones, Foreignfiling text P24-260

[0437] -52- aromatic phosphine oxides or aromatic sulphoxides or sulphones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, especially monoamines, for example according to WO 2014 / 015935, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP

[0438] 5 2004 / 288381, EP 1205527 or WO 2008 / 086851 , indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, for example according to WO 2010 / 136109 and WO 2011 / 000455, azacarbazole derivatives, for example according to EP 1617710, EP 1617711 , EP 1731584, JP 2005 / 347160, bipolar matrix materials, for example according to WO

[0439] 10 2007 / 137725, silanes, for example according to WO 005 / 111172, azaboroles or boronic esters, for example according to WO 2006 / 117052, triazine derivatives, for example according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, for example according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, for example according to

[0440] 15 WO 2010 / 054729, diazaphosphole derivatives, for example according to WO 2010 / 054730, bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, triphenylene derivatives, for example according to WO 2012 / 048781, lactams, for example according to WO 2011 / 116865, WO

[0441] 20 2011 / 137951 or WO 2013 / 064206, or 4-spirocarbazole derivatives, for example according to WO 2014 / 094963 or the as yet unpublished application EP 14002104.9. It is likewise possible for a further phosphorescent emitter which emits at a shorter wavelength than the actual emitter to be present as co-host in the mixture.

[0442] 25

[0443] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams and carbazole derivatives.

[0444] 30 It may also be preferable to use a plurality of different matrix materials as a mixture, especially at least one electron transport matrix material and at least one hole transport matrix material. Preference is likewise given to the use of a mixture of a charge-transporting matrix material and an electrically inert matrix material having no significant involvement, if any, in the charge transport, as described, for

[0445] 35 example, in WO 2010 / 108579. Foreignfiling text P24-260

[0446] -53-

[0447] It is further preferable to use a mixture of two or more triplet emitters together with a matrix. In this case, the triplet emitter having the shorter-wave emission spectrum serves as co-matrix for the triplet emitter having the longer-wave emission spectrum.

[0448] 5 More preferably, a compound of the invention according to Formula (I), in a preferred embodiment, can be used as matrix material in an emission layer of an organic electronic device, especially in an organic electroluminescent device, for example in an OLED or OLEC. In this case, the matrix material containing compound according to Formula (I) or the preferred embodiments recited above

[0449] 10 and hereinafter is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

[0450] Here, the concentration of an compound according to formula (I), as previously described or preferably described, in the mixture according to the invention or in

[0451] 15 the light-emitting layer of the device according to the invention is usually in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, still more preferably in the range from 20 wt.% to 70 wt.%, most preferably in the range from 40 wt.% to 80 wt.%. % by weight, more preferably in the range from 15 % to 80 % by weight,

[0452] 20 even more preferably in the range from 20 % to 70 % by weight, most preferably in the range from 40 % to 80 % by weight and most preferably in the range from 50 % to 70 % by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0453] 25 The concentration of the phosphorescent emitter as described hereinafter or described as preferred in the mixture of the invention or in the light-emitting layer of the device of the invention is in the range from 1% by weight to 30% by weight, preferably in the range from 2% by weight to 20% by weight, more preferably in the range from 4% by weight to 15% by weight, even more preferably in the range

[0454] 30 from 8% by weight to 12% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0455] It is also possible for fluorescent emitters to be present in the light-emitting layer of the device of the invention.

[0456] 35 Foreignfiling text P24-260

[0457] -54-

[0458] Preferred fluorescent emitters are selected from the class of the arylamines. An arylamine or an aromatic amine in the context of this invention is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system,

[0459] 5 more preferably having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines or aromatic chrysenediamines. What is meant by an aromatic anthraceneamine is a compound in which a diarylamino group is bonded directly to an anthracene

[0460] 10 group, preferably in the 9 position. What is meant by an aromatic anthracenediamine is a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 positions. Aromatic pyreneamines, pyrenediamines, chryseneamines and chrysenediamines are defined analogously, where the diarylamino groups are bonded to the pyrene

[0461] 15 preferably in the 1 position or 1,6 positions. Further preferred fluorescent emitters are indenofluoreneamines or -diamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluoreneamines or -diamines, for example according to WO 2008 / 006449, and dibenzoindenofluoreneamines or - diamines, for example according to WO 2007 / 140847, and the indenofluorene

[0462] 20 derivatives having fused aryl groups disclosed in WO 2010 / 012328.

[0463] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device, as well as the compounds according to formula (I) as described above or described as preferred, may

[0464] 25 comprise further host materials or matrix materials, called mixed matrix systems. The mixed matrix systems preferably comprise three or four different matrix materials, more preferably three different matrix materials (in other words, one further matrix component in addition to the compounds according to formula (I) as described above). Particularly suitable matrix materials which can be used in

[0465] 30 combination as matrix component in a mixed matrix system are selected from wide-band gap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM).

[0466] 35 Foreignfiling text P24-260

[0467] -55-

[0468] The present invention further provides an electronic device, preferably an organic electroluminescent device, comprising one or more compounds of the invention and in one or more electron transport layers, as electron transport compound.

[0469] The present invention further provides an electronic device, preferably an organic

[0470] 5 electroluminescent device, comprising one or more compounds of the invention in one or more hole-blocking layers, as hole-blocking compound.

[0471] The electronic device preferably comprises an electron transport region. The electron transport region may comprise one or more layers conducting electrons,

[0472] 10 such as hole-blocking layers, electron transport layers and / or electron injection layers. All of the layers of the electron transport region may comprise one or more compounds of the invention. In addition thereto, all of the layers of the electron transport region may consist of one or more compounds of the invention. In a further embodiment of the invention, one layer of the electron transport region

[0473] 15 may comprise one or more compounds of the invention and another layer of the electron transport region does not comprise a compound of the invention, preferably.

[0474] Preferred cathodes are metals having a low work function, metal alloys or

[0475] 20 multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is

[0476] 25 also possible to use further metals having a relatively high work function, for example Ag, in which case combinations of the metals such as Mg / Ag, Ca / Ag or Ba / Ag, for example, are generally used. It may also be preferable to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of useful materials for this

[0477] 30 purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. Li F, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Likewise useful for this purpose are organic alkali metal complexes, e.g. Liq (lithium quinolinate). The layer thickness of this layer is preferably between 0.5 and 5 nm.

[0478] 35 Foreignfiling text P24-260

[0479] -56-

[0480] Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. AI / Ni / NiOx, AI / PtOx) may also be preferred. For some applications, at least one of the electrodes has to be

[0481] 5 transparent or partly transparent in order to enable either the irradiation of the organic material (O-SC) or the emission of light (OLED / PLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is further given to conductive doped organic materials, especially conductive doped

[0482] 10 polymers, for example PEDOT, PAN I or derivatives of these polymers. It is further preferable when a p-doped hole transport material is applied to the anode as hole injection layer, in which case suitable p-dopants are metal oxides, for example MoOa or WO3, or (perfluorinated electron-deficient aromatic systems. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the

[0483] 15 compound NPD9 from Novaled. Such a layer simplifies hole injection into materials having a low HOMO, i.e. a large HOMO in terms of magnitude. In the further layers, it is generally possible to use any materials as used according to the prior art for the layers, and the person skilled in the art is able, without exercising inventive skill, to combine any of these materials with the

[0484] 20 materials of the invention in an electronic device.

[0485] The device is correspondingly (according to the application) structured, contact- connected and finally hermetically sealed, since the lifetime of such devices is severely shortened in the presence of water and / or air.

[0486] 25

[0487] Additionally preferred is an electronic device, especially an organic electroluminescent device, which is characterized in that one or more layers are coated by a sublimation process. In this case, the materials are applied by vapour deposition in vacuum sublimation systems at an initial pressure of typically less

[0488] 30 than 10-5mbar, preferably less than 10'6mbar. It is also possible that the initial pressure is even lower or even higher, for example less than 10'7mbar.

[0489] Preference is likewise given to an electronic device, especially an organic electroluminescent device, which is characterized in that one or more layers are

[0490] 35 coated by the OVPD (organic vapour phase deposition) method or with the aid of Foreignfiling text P24-260

[0491] -57- a carrier gas sublimation. In this case, the materials are applied at a pressure between 10'5mbar and 1 bar. A special case of this method is the OVJP (organic vapour jet printing) method, in which the materials are applied directly by a nozzle and thus structured (for example, M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0492] 5

[0493] Preference is additionally given to an electronic device, especially an organic electroluminescent device, which is characterized in that one or more layers are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, offset printing or nozzle printing,

[0494] 10 but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds are needed, which are obtained, for example, through suitable substitution.

[0495] The electronic device, especially the organic electroluminescent device can also

[0496] 15 be produced as a hybrid system by applying one or more layers from solution and applying one or more other layers by vapour deposition. For example, it is thus possible to apply an emitting layer comprising a compound of the invention comprising compounds of formula (I) and a matrix material from solution, and to apply a hole blocking layer and / or an electron transport layer thereto by vapour

[0497] 20 deposition under reduced pressure.

[0498] These methods are known in general terms to those skilled in the art and can be applied without difficulty to electronic devices, especially organic electroluminescent devices comprising compounds of the invention comprising

[0499] 25 compounds of Formula (I) or the above-detailed preferred embodiments.

[0500] The inventive compounds and mixtures are suitable for use in an electronic device. An electronic device is understood to mean a device containing at least one layer containing at least one organic compound. This component may also

[0501] 30 comprise inorganic materials or else layers formed entirely from inorganic materials.

[0502] The present invention therefore further provides for the use of the inventive compounds or mixtures in an electronic device, especially in an organic

[0503] 35 electroluminescent device. Foreignfiling text P24-260

[0504] -58-

[0505] The present invention still further provides for the use of a compound of the invention in an electronic device as matrix material, hole blocking material, electron injection material and / or electron transport material.

[0506] The present invention still further provides an electronic device comprising at least

[0507] 5 one of the above-detailed inventive compounds or mixtures. In this case, the preferences detailed above for the compound also apply to the electronic devices.

[0508] In a further embodiment of the invention, the organic electroluminescent device of the invention does not contain any separate hole injection layer and / or hole

[0509] 10 transport layer and / or hole blocking layer and / or electron transport layer, meaning that the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. It is additionally possible to use a metal complex identical or similar to the metal

[0510] 15 complex in the emitting layer as hole transport or hole injection material directly adjoining the emitting layer, as described, for example, in WO 2009 / 030981.

[0511] In the further layers of the organic electroluminescent device of the invention, it is possible to use any materials as typically used according to the prior art. The

[0512] 20 person skilled in the art is therefore able, without exercising inventive skill, to use any materials known for organic electroluminescent devices in combination with the inventive compounds of Formula (I) or according to the preferred embodiments.

[0513] 25 The compounds of the invention generally have very good properties on use in organic electroluminescent devices. Especially in the case of use of the compounds of the invention in organic electroluminescent devices, the lifetime is significantly better compared to similar compounds according to the prior art. At the same time, the further properties of the organic electroluminescent device,

[0514] 30 especially the efficiency and voltage, are likewise better or at least comparable.

[0515] It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be

[0516] 35 exchanged for alternative features which serve the same purpose or an Foreignfiling text P24-260

[0517] -59- equivalent or similar purpose. Thus, any feature disclosed in the present invention, unless stated otherwise, should be considered as an example of a generic series or as an equivalent or similar feature.

[0518] All features of the present invention may be combined with one another in any

[0519] 5 manner, unless particular features and / or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

[0520] It should also be pointed out that many of the features, and especially those of the

[0521] 10 preferred embodiments of the present invention, are themselves inventive and should not be regarded merely as some of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.

[0522] 15 The technical teaching disclosed with the present invention may be abstracted and combined with other examples.

[0523] The invention is illustrated in detail by the examples which follow, without any intention of restricting it thereby.

[0524] 20

[0525] The person skilled in the art will be able to use the details given, without exercising inventive skill, to produce further electronic devices of the invention and hence to execute the invention over the entire scope claimed.

[0526] 25

[0527] A) Synthesis examples

[0528] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are

[0529] 30 additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can display multiple tautomeric forms,

[0530] 35 one tautomeric form is shown representatively. Foreignfiling text P24-260

[0531] -60-

[0532] Synthons LS well known in literature:

[0533] 5

[0534] 10

[0535] 15

[0536] 20

[0537] 25

[0538] 30

[0539] 35 Foreignfiling text P24-260

[0540] -61 -

[0541] 5

[0542] 10

[0543] 15

[0544] 20

[0545] 25

[0546] 30

[0547] 35 Foreignfiling text P24-260

[0548] 5

[0549] 10

[0550] 15

[0551] 20

[0552] 25

[0553] 30

[0554] 35 Foreignfiling text P24-260

[0555] 5

[0556] 10

[0557] 20

[0558] To a well-stirred solution of 21.6 g (100 mmol) LS1 and 53,6 g (200 mmol) 2- Chloro-4,6-diphenyl-1,3,5-triazine [3842-55-5] in 700 ml of THF 200 ml (200 mmol) of a lithium bis-trimethylsilylamide solution (LHMDS, 1 M in THF) is added dropwise during 20 min and stirring is continued for 20 h at 50 °C. The reaction mixture is

[0559] 25 then allowed to cool, 200 ml of water is carefully added, before 500 ml toluene are added, and the aqueous phase is separated. The organic phase is washed three times with 200 ml water each, once with 200 ml saturated sodium chloride solution and then it is concentrated to dryness. The residue is stirred hot with 300 ml ethyl acetate (EE).

[0560] 30

[0561] Further purification of the crude product is carried out by chromatography and / or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, in the ratio of 1:3 to 3:1 vv) and fractional sublimation or tempering in a high vacuum.

[0562] 35 Foreignfiling text P24-260

[0563] -64-

[0564] Yield: 44.6 g (66 mmol) 66 %; purity: approx. 99.9 % acc. HPLC.

[0565] The following bases can be used as an alternative to lithium bis-trimethylsilylamide: n-butyllitium, sodium and potassium tert-butanolate, lithium di-iso-propylamide, lithium tetramethyl piperidide, etc..

[0566] 5

[0567] In an analogous manner, it is possible to prepare the following compounds:

[0568] 10

[0569] 15

[0570] 20

[0571] 25

[0572] 30

[0573] 35 Foreignfiling text P24-260

[0574] 5

[0575] 10

[0576] 15

[0577] 20

[0578] 25

[0579] 30

[0580] 35 Foreignfiling_text P24-260

[0581] -66-

[0582] 5

[0583] 10

[0584] 15

[0585] 20

[0586] 25

[0587] 30

[0588] 35 Foreignfiling text P24-260

[0589] 5

[0590] 10

[0591] 15

[0592] 20

[0593] 25

[0594] 30

[0595] 35 Foreignfilingjext P24-260

[0596] -68-

[0597] 35 Foreignfilingjext P24-260

[0598] -69-

[0599] 35 Foreignfiling text P24-260

[0600] 5

[0601] 10

[0602] 15

[0603] 20

[0604] 25

[0605] 30

[0606] 35 Foreignfilingjext P24-260

[0607] -71- Foreignfilingjext P24-260

[0608] -72-

[0609] 35 Foreignfiling_text P24-260

[0610] -73-

[0611] 35 Foreignfiling_text P24-260

[0612] 35 Foreignfiling text P24-260

[0613] -75-

[0614] 5

[0615] 10

[0616] 15

[0617] 20

[0618] 25

[0619] 30

[0620] 35 Foreignfiling text P24-260

[0621] 5

[0622] 10

[0623] B) Device examples

[0624] In the following examples V1 to V3 and Ex1 to Ex12 (see Tables 5 and 6), the data of various OLEDs are presented. Examples Ex1 to Ex12 show data of

[0625] 15 OLEDs according to the invention, examples V1 to V3 show the respective corresponding comparative examples according to the state of the art.

[0626] 1) General production process for the OLEDs and characterization of the OLEDs

[0627] 20

[0628] Cleaned glass plates (cleaned in Miele laboratory dishwasher, Merck Extran cleaner) coated with structured ITO (indium tin oxide) of 500A thickness are pretreated with UV ozone for 25 minutes (UV ozone generator PR-100 from UVP company). These coated glass plates form the substrates to which the OLEDs are

[0629] 25 applied.

[0630] In principle, OLEDs have the layer structure as shown in Table 3.

[0631] Table 3:

[0632] 30

[0633] 35 Foreignfiling text P24-260

[0634] 5 wherein ET stands for the electron transport material which is either a reference

[0635] 10 material R or a material B according to the invention.

[0636] Table 4 shows the materials which are used for the production of the OLEDs.

[0637] Table 4: Materials for the OLEDs

[0638] 15

[0639] 20

[0640] 25

[0641] 30

[0642] 35 Foreignfiling text P24-260

[0643] 5

[0644] 10

[0645] 15

[0646] 20

[0647] 25

[0648] 30

[0649] 35 Foreignfiling text P24-260

[0650] 5

[0651] 10

[0652] 15

[0653] 20

[0654] 25

[0655] 30

[0656] 35 Foreignfiling text P24-260

[0657] 5

[0658] 10

[0659] 15

[0660] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer consists of at least one matrix material (host material) and an emitting dopant (dotand, emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in

[0661] 20 such a form as BH:BE (97:3) mean here that the material BH is present in the layer in a proportion by volume of 97 % as host material and the material BE in a proportion of 3 % as emitter. Analogously, the hole injection layer (HIL) and the electron transport layer may also consist of a mixture of at least two materials.

[0662] 25 The materials which are used for the ETL in the various OLEDs are listed in below table 5.

[0663] Table 5:

[0664] 30

[0665] 35 Foreignfiling text P24-260

[0666] -81 -

[0667] 5

[0668] 10

[0669] 15

[0670] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and the current-voltage-luminance characteristics

[0671] 20 (lUL-characteristics); the EQE (external quantum efficiency) is calculated therefrom. The calculation is based on the assumption of a Lambertian emission characteristic. The electroluminescence spectra are determined at a luminance of 1000 cd / m2, and the CIE 1931 x and y colour coordinates are calculated therefrom.

[0672] 25

[0673] The parameter U12 in Table 6 refers to the voltage which is required for a current density of 12 mA / cm2. EQE12 denotes the external quantum efficiency at a current density of 12 mA / cm2.

[0674] 30 For each example, the relative EQE and the relative voltage are calculated in comparison to the corresponding reference example: rel. rel.

[0675] 35 Foreignfiling text P24-260

[0676] -82-

[0677] The lifetime LT80 is defined as the time after which the luminance drops from a starting luminance LO (in cd / m2) to 80 % of this starting luminance in the course of operation at a constant current density jo in mA / cm2. in the course of operation with a constant current. In the examples shown herein, the current density used is 70 mA / cm2.

[0678] 5

[0679] For each example the relative LT is calculated in comparison to the corresponding reference example: rel. LT (Ex) = LT80(Ex) I LT80(V).

[0680] 10

[0681] The data for the various OLEDs are collated in table 6.

[0682] Table 6: Data of OLEDs

[0683] 15

[0684] 20

[0685] 25

[0686] 30

[0687] 35 Foreignfiling text P24-260

[0688] 5

[0689] When comparing the examples according to the invention with the corresponding reference examples, it can be clearly seen that the examples according to the

[0690] 10 invention each shows a clear advantage in the device voltage, i.e. a reduced voltage without a noticeable change in efficiency, lifetime and color.

[0691] The materials according to the invention can also be used in the emission layer as a matrix material or in the hole blocking layer of OLEDs.

[0692] 15

[0693] 20

[0694] 25

[0695] 30

[0696] 35

Claims

Foreignfiling text P24-260-84-Claims1. Compound according to formula (I)Formula (I)15 where the symbols and indices used are as follows:X is the same at each instance, and is N or CR;Ar is the same at each instance, and is an aromatic ring system having 6 to20 40 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R1or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R1;25Ar1is the same at each instance, and is an aromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2;30Ra, Rbis independently from each other selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C35 atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 30 C-Foreignfiling text P24-260-85- atoms, an alkenyl or alkynyl group having 2 to 20 C atoms, wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi or polycyclic alkyl groups may be substituted by one or more radhcals R3, where in each case one or more non-adjacent CH2 groups may be replaced by -5 R3C=CR3-, -C=C-, Si(R3)2, C=O, C=S, C=NR3, -C(=O)O-, -C(=O)NR3-, NR3, P(=O)(R3), -O-, -S-, SO or SO2 and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be sub-'stituted by one or more radicals R3, or an aliphatic polycyclic ring10 system having at least 3 rings, which may be substituted by one or more radicals R3, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R3, or an aralkyl group having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R3; at the same time two or15 more, preferably adjacent radicals Raor Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3;R is the same at each instance and is selected from the group consisting of20 H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 30 C-atoms, an alkenyl or alkynyl group having 2 to 20 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups25 or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R4, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be sub^stituted by one or more radicals R4; at the same time two radicals R, or two or more radicals R and R1or two or more radicals R and R2may30 form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R4;R1, R2, R635Foreignfiling text P24-260-86- is the same or different at each instance and is H, D, F, CN, a straightchain alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a mono-, bi-or polycyclic alkyl group each having 3 to 20 C-atoms, an alkenyl or alkynyl group having 2 to 20 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl5 groups, each of the alkenyl or alkinyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5where one or more nonadjacent CH2 groups may be replaced by - R5C=CR5-, -C=C-, Si(R5)2, C=O, C=S, C=NR5, -C(=O)O-, -C(=O)NR5-, NR5, P(=O)(R5), -O-, -S-, SO or SO2 and where one or more hydrogen10 atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R5radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R5radicals, or an aralkyl or heteroaralkyl group which has 515 to 40 aromatic ring atoms and may be substituted by one or more R5radicals; at the same time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent radicals R2or two or more, preferably adjacent radicals R6together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be20 substituted by one or more radicals R5;R3, R4, R5is the same or different at each instance and is selected from the group consisting H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic25 radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN;Ar2is is the same or different at each instance, and is an aromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be30 substituted by one or more radicals R6or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be sub-'stituted by one or more radicals R6; m, n35 is independently from each other 0, 1 , 2, 3 or 4Foreignfiling text P24-260 with the proviso that at least one of m or n is at least 1 and with the proviso that ring system A and ring system B is different and wherein the following compounds are excluded:

202. Compound according to claim 1 , wherein both X are N.

3. Compound according to claim 1 or 2, wherein Raand Rbis independently selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 10 C atoms, a25 branched alkyl group having 3 to 10 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 20 C-atoms, an alkenyl or alkynyl group having 2 to 10 C atoms wherein each of the straight chain alkyl groups, each of the branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono- or polycyclic alkyl groups may be substituted by one or more radhcals30 R3, where in each case one or more non-adjacent CH2 groups may be replaced by - -O- or -S-, and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or an aliphatic polycyclic ring system having at least 3 rings,35 which may be substituted by one or more radicals R3; at the same time two orForeignfiling text P24-260-88- more, preferably adjacent radicals Raor Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3.

4. Compound according to any one of claims 1 to 3, wherein Raand Rbis the5 same or different at each instance, and is independently from each other selected from the group consisting of H, D, F, CN, -OH, -SH, -S(O)2R3, N(Ar2)2, Si(R3)3, a straight-chain alkyl group having 1 to 6 C atoms, a branched alkyl group having 3 to 8 C atoms, a mono- , bi- or polycyclic alkyl group each having 3 to 10 C-atoms, an alkenyl group having 2 to 8 C atoms10 where in each case one or more non-adjacent CH2 groups may be replaced by - -O- or -S-, and where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or an aliphatic polycyclic ring system having at least 3 rings, which may15 be substituted by one or more radicals R3; at the same time two or more, preferably adjacent radicals Raor Rbmay form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R3.20 5. Compound according to any one of claims 1 to 4, wherein Ar is the same at each instance, and is an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R1or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be identically substituted by one or more25 radicals R1and wherein Ar1is the same at each instance, and is an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be identically substituted by one or more radicals R2.

306. Compound according to claim 5, wherein wherein the aromatic ring system having 6 to 30 aromatic ring atoms is selected from the group consisting of phenyl, ortho-, meta- or para biphenyl, ortho-, meta, para- or branched terphenyl, ortho-, meta- , para- or branched quaterphenyl, napthalene,35 anthracene, phenanthrene, triphenylene, fluoranthene, benzofluoranthene 1-,Foreignfiling text P24-260-89-2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, which may in each case be may in each case be identically sub-'stituted by one or more radicals R1or which may in each case be identically substituted by one or more radicals R2and the heteroaromatic ring system having 5 to 30 aromatic ring atoms is selected from the group consisting of 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3-5 or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl or N-carbazolyl , which may in each case be identically substituted by one or more radicals R1or which may in each case be identically substituted by one or more radicals R2.

7. Compound according to any one of claims 1 to 6, wherein R1, R2and R6is10 the same or different at each instance and is selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a mono-, bi-or polycyclic alkyl group each having 3 to 10 C-atoms, an alkenyl or alkynyl group having 2 to 10 C atoms wherein each of the straight chain alkyl groups, each of the15 branched alkyl groups, each of the alkenyl or alkinyl groups or each of the mono-, bi- or polycyclic alkyl groups may be substituted by one or more radhcals R5where one or more nonadjacent CH2 groups may be replaced by -O- or -S-, and where one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 5 to 3020 aromatic ring atoms, each of which may be substituted by one or more R5radicals, at the same time, two or more, preferably adjacent radicals R1or two or more, preferably adjacent radicals R2or two or more, preferably adjacent radicals R6together may also form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system, which may be substituted by one or25 more radicals R5.

8. Compound according to any one of claims 1 to 7, wherein the compound according to formula (I) is selected from the following compounds:30Foreignfiling text P24-2605101520253035Foreignfilingjext P24-260-91-35Foreignfiling text P24-2605101520253035Foreignfiling text P24-260-93-5101520253035Foreignfiling_text P24-260-94-5101520253035Foreignfilingjext P24-260-95-35Foreignfiling text P24-2605101520253035Foreignfiling text P24-260-97-5101520253035Foreignfilingjext P24-260-98-35Foreignfiling text P24-2605101520253035Foreignfiling text P24-260-100-510152025309. Composition comprising at least one compound according to one or more of Claims 1 to 8 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF emitters, host materials, matrix materials, electron transport materials, electron35 injection materials, hole conductor materials, hole injection materials, n-Foreignfiling text P24-260-101- dopants, wide band gap materials, electron blocking materials and hole blocking materials.

10. Formulation comprising at least one compound according to one or more of Claims 1 to 8, and / or at least one composition according to Claim 9 and at5 least one solvent.

11. Use of a compound according to one or more of Claims 1 to 8, or of a composition according to Claim 9 or of a formulation according to claim 10 in an electronic device as a hole blocking material, electron injection material,10 matrix material and / or electron transport material.

12. An electronic device comprising at least one compound according to one or more of Claims 1 to 8, or a composition according to claim 9 or a formulation according to claim 10 wherein the electronic device is selected from the15 group consisting organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.2013. An electronic device according to claim 12, wherein the device is an electroluminescent device and contains at least one electron-injecting layer, one hole blocking layer, one emission layer or one electron-transporting layer comprising at least compound according to one or more of Claims 1 to 8, or25 the composition according to claim 9 or the formulation according to claim 11.3035

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