Materials for organic electroluminescent devices

Abstract

The present invention relates to diazadibenzofuran derivatives and diazadibenzothiophene derivatives and to electronic devices containing these compounds, in particular organic electroluminescent devices containing these compounds in the form of matrix materials, optionally in combination with a further matrix material and suitable phosphorescent emitters, and suitable mixtures and formulations of said compounds.

Description

[0001] Materials for organic electroluminescent devices

[0002] Technical area

[0003] The present invention relates to diazadibenzofuran or diazadibenzothiophene derivatives and electronic devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as matrix materials, optionally in combination with a further matrix material and suitable phosphorescent emitters, suitable mixtures and formulations.

[0004] State of the art

[0005] Phosphorescent organometallic complexes are frequently used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, for example, with regard to efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are determined not only by the triplet emitters used. The other materials used, such as matrix materials, are also particularly important. Improvements to these materials can therefore also lead to significant improvements in OLED properties.

[0006] According to the state of the art, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters.

[0007] In US20150207082 AA, WO15169412 A1 , KR20170005637 A and CN 115385922 A, special diazadibenzofuran or diazadibenzothiophene derivatives are described as matrix materials.

[0008] WO19017731 A1 and WO19098765 A1 describe specific diazadibenzofuran and diazadibenzothiophene derivatives, respectively, suitable for use in organic electronic devices.

[0009] In CN114560864 A and CN114621240 A, special diazadibenzofuran and diazadibenzothiophene derivatives are described as electron transport materials.

[0010] In general, there is still room for improvement in these materials for use as matrix materials. The object of the present invention is to provide compounds which are particularly suitable for use as matrix materials in a phosphorescent OLED. In particular, the object of the present invention is to provide matrix materials which lead to an improved lifetime. This applies in particular to the use of a low to medium

[0011] Emitter concentration, ie emitter concentrations in the order of 3 to 20%, in particular 3 to 15%, since the device lifetime is particularly limited here.

[0012] It has now been found that electroluminescent devices containing compounds according to the following formulas (1a) and (1b) exhibit improvements over the prior art, in particular when using the compounds as matrix material for phosphorescent dopants.

[0013] It has further been found that the combination of at least one compound of formula (1a) or formula (1b) as first host material and at least one hole-transporting compound, for example in combination with one or more compounds of formulas (6), (7), (8), (9), (10) or (11), as further host material / further host materials in a light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, solves this problem and eliminates the disadvantages of the prior art.

[0014] A first aspect of the present invention is a compound according to formula (1a) or formula (1b), Formula (1b), where the symbols and indices used are:

[0015] V is independently O or S at each occurrence; Li is a linker selected from L-1 to L-26, which may be partially or fully deuterated, or a combination of linkers L-1 to L-26, where linkers L-1 to L-26 may be partially or fully deuterated,

[0016] Vi is O or S; the dashed lines indicate the bond to Rx and the residue of formula (1a) or formula (1b);

[0017] * denotes the bond to Li ,

[0018] R 1 is at each occurrence independently H, D, or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0019] Ar, An are, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R;

[0020] Ar2, Ars are, identically or differently at each occurrence, an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 9 to 40 ring atoms, which may be substituted by one or more radicals R;

[0021] R is, on each occurrence, identical or different, selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where 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; R# is, on each occurrence, D, F or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0022] [L] is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D; b, b1 are each independently 0 or 1 . b2 are each independently 0, 1 , 2 or 3, with the condition for compounds of formula (1a), if Li is a linker L-3 or L-8 which is not deuterated, then Li-Rx is only bonded to the remainder of formula (1a) in positions 6, 7 or 9.

[0023] The invention further relates to a mixture comprising at least one compound of formula (1a) or of formula (1b) as described above or preferably described later and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0024] The invention further relates to a formulation comprising at least one compound of formula (1a) or of formula (1b) as described above or preferably described later, or a mixture as described above, and at least one solvent.

[0025] A further subject matter of the invention is an organic electronic, preferably electroluminescent, device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (1a) or of formula (1b) as described above or preferably described later.

[0026] A further subject of the invention is a method for producing an organic electronic, preferably electroluminescent, device, as described above or preferably described below, characterized in that the organic layer is applied by vapor deposition.

[0027] In the present patent application, "D" or "D atom" denotes deuterium. An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline.An aryl group with 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl, or triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted. The aryl or heteroaryl group within the meaning of this invention can bear one or more radicals, with the suitable radical being described below. If no such radical is described, the aryl group or heteroaryl group is unsubstituted.

[0028] An aromatic ring system within the meaning of this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system also includes aryl groups, as described above.

[0029] An aromatic ring system with 6 to 18 C atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0030] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0031] An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such asBiphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

[0032] An aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-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, phenothiazine, phenoxazine,Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenan- thrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1 ,5-Diaza- anthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diaza- pyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4- Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4- Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0033] The abbreviations Ar and An mean, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R, where the radical R or the substituents R have / have a meaning as described above or below.

[0034] A preferred meaning of Ar and An is described below. The abbreviations Ar2 and Ars, identically or differently at each occurrence, mean an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be substituted by one or more radicals R, where the radical R or the substituents R have a meaning as described above or below. A preferred meaning of Ar2 and Ars is described below.

[0035] The abbreviation Ars stands, the same or different at each occurrence, for an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is substituted with one or more radicals R 7 may be substituted, where the radical R 7 or the substituents R 7 has / have a meaning as described above or below. A preferred meaning of Ars is described below.

[0036] A cyclic alkyl, alkoxy or thioalkyl group in the sense of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0037] Im Rahmen der vorliegenden Erfindung werden unter einer geradkettigen, verzweigten oder cyclischen Ci- bis C2o-Alkylgruppe beispielsweise die Reste 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, neo-Pentyl, Cyclopentyl, n-Hexyl, s-Hexyl, t-Hexyl, 2-Hexyl, 3- Hexyl, neo-Hexyl, Cyclohexyl, 1-Methylcyclopentyl, 2-Methylpentyl, n-Heptyl, 2-Heptyl, 3- Heptyl, 4-Heptyl, Cycloheptyl, 1-Methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1- Bicyclo[2,2,2]octyl, 2-Bicyclo[2,2,2]octyl, 2-(2,6-Dimethyl)octyl, 3-(3,7-Dimethyl)octyl, Adamantyl, Trifluormethyl, Pentafluorethyl, 2,2,2-Trifluorethyl, 1 ,1-Dimethyl-n-hex-1-yl-,

[0038] 1.1-Dimethyl-n-hept-1-yl-, 1 ,1-Dimethyl-n-oct-1-yl-, 1 ,1-Dimethyl-n-dec-1-yl-, 1 ,1-Dimethyl- n-dodec-1-yl-, 1 ,1-Dimethyl-n-tetradec-1-yl-, 1 ,1-Dimethyl-n-hexadec-1-yl-, 1 ,1-Dimethyl- n-octadec-1-yl-, 1 , 1-Diethyl-n-hex-1-yl-, 1 , 1-Diethyl-n-hept-1 -yl-, 1 , 1-Diethyl-n-oct-1 -yl-,

[0039] 1.1-Diethyl-n-dec-1-yl-, 1 ,1-Diethyl-n-dodec-1-yl-, 1 ,1-Diethyl-n-tetradec-1-yl-, 1 ,1- Diethyln-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- und 1-(n- Decyl)-cyclohex-1-yl- verstanden.

[0040] The phrase "two or more residues can form a ring system" refers to the formation of an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system. For the purposes of this description, it is understood, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0041] In education

[0042] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0043] The compounds of formulas (1a) and (1b) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture according to the invention, the formulation according to the invention, and the organic electronic or electroluminescent device according to the invention.

[0044] In formulas (1-2) to (1-5) R 1 preferred for H or D.

[0045] In compounds of formulas (1a) and (1b), Rx preferably represents formula (1-2).

[0046] In compounds of formula (1a), Rx is preferably bonded in position 6 or 9, particularly preferably in position 9, of the diazadibenzofuran or diazadibenzothiophene. Compounds of formula (1a) are a preferred embodiment of the invention.

[0047] In compounds of formula (1b), Rx is preferably bonded in position 5, 6 or 7, particularly preferably in position 5 or 6, most particularly preferably in position 5, of the diazadibenzofuran or diazadibenzothiophene.

[0048] The numbering of the positions is shown below using the example of the diazadibenzofuran skeleton:

[0049] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), V is preferably O.

[0050] In one embodiment of the compounds of formulas (1a) and (1b) or the preferred compounds of formulas (1a) and (1b), Li is preferably selected from the group of linkers L-14 to L-26, which may be partially or completely deuterated.

[0051] In linkers L-14 to L-26, Vi preferentially represents O.

[0052] Particularly preferred linkers from the group L-1 to L-13 are linkers L-1 to L-7, which can be partially or fully deuterated. Linker L-2, which can be partially or fully deuterated, is especially preferred.

[0053] Particularly preferred linkers from the group L-14 to L-26 are linkers L-15, L-16, L-18, L-19, L-23, and L-26, which may be partially or fully deuterated. Linker L-16, which may be partially or fully deuterated, is especially preferred.

[0054] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Li is preferably selected from the preferred group of linkers, as described above. In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Li is preferably selected from the preferred group of linkers, as described above, which are partially or fully deuterated.

[0055] In one embodiment of the compounds of formulas (1a) and (1b) or the preferred compounds of formulas (1a) and (1b), Li is preferably selected from the combination of linkers L-1 to L-26, wherein linkers L-1 to L-26 may be partially or completely deuterated.

[0056] Preferred combinations of linkers L-1 to L-26 are the combinations of linkers L-2 or L-3, which may be partially or fully deuterated, with linkers L-14, L-15, L-16, L-17, L-18, L-22, L-23, L-25, or L-26, which may be partially or fully deuterated and in which V1 has a previously stated or preferred meaning. The order of the combination is not restricted, and two of the dashed lines together form the connection of the linkers, and the two remaining dashed lines indicate the connection to Rx and the residue of formula (1a) or formula (1b).

[0057] Particularly preferred linker combinations for Li are: can be completely deuterated.

[0058] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Li is preferably selected from the preferred combination of linkers as described above. In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Li is preferably selected from the preferred combination of linkers as described above, which are partially or fully deuterated.

[0059] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), R# preferably represents D, F or non-deuterated or partially or fully deuterated phenyl, particularly preferably D or F, very particularly preferably D. In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), b2 preferably represents 3 and R# represents D.

[0060] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), b2 preferably represents 0 or 1 if R# has a meaning previously mentioned or preferably mentioned.

[0061] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), the symbol [L] as a linker represents an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D.

[0062] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), the symbol [L], when occurring, independently preferably represents a linker selected from the group L-1 to L-13 and [L-14] to [L-34], which may be unsubstituted or partially or fully substituted by D,

[0063] [L-14] [L-15] [L-16] [L-17]

[0064]

[0065] [ L ' 33 l , [L -34 ! , where V2 are each independent

[0066] denotes O, S or N-aryl, the dashed lines denote the bond to Ar2 or Ars and to the radical of formula (1a) or (1b), and the abbreviation “aryl” denotes an aromatic or heteroaromatic ring system having 5 to 30 ring atoms which may be substituted by one or more radicals R. “Aryl” is preferably phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl or dibenzothiophenyl, where these radicals may be unsubstituted or partially or fully substituted by D.

[0067] V2 is preferably O or N-aryl. V2 is particularly preferred.

[0068] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), the symbol [L] when occurring independently particularly preferably represents linkers selected from the group L-2, L-3, L-4, L-5, [L-21] to [L-34], as previously described or preferably described, which may be partially or fully substituted by D.

[0069] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), b is preferably 0.

[0070] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), b1 is preferably 0.

[0071] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Ar and An are preferably different from each other.

[0072] Ar and An are each independently preferred from the following groups Ar-

[0073] 1 to Ar-19 selected:

[0074] Ar-19 where R' at each occurrence is selected, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Aro)2, NH2, N(R 2)2, C(=O)Aro, C(=O)H, C(=O)R , P(=O)(Aro)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, where one or more non-adjacent CH2 groups are substituted by HC=CH, R 2 C=CR 2 , C=C, Si(R 2 )2, Ge(R 2 )2, Sn(R 2 )2, C=O, C=S, C=Se, C=NR 2 , P(=O)(R 2 ), SO, SO2, NH, NR 2 , O, S, CONH or CONR and where one or more H atoms may be replaced by F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic

[0075] 2 ring system with 5 to 40 ring atoms, each of which may be substituted by one or more radicals R, an aryloxy or heteroaryloxy group with 5 to 40 ring atoms, which may be substituted by one or more radicals R, or a combination of these systems, where optionally two or more adjacent substituents R' are a monocyclic or polycyclic, aliphatic, aromatic or hetero-

[0076] 2 aromatic ring system which may be substituted by one or more radicals R; and

[0077] Aro is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; one or more R' may also be directly bonded to a C atom of Aro.

[0078] The dashed line indicates the binding site to the rest of formulas (1-2), (1-3), (1-4) and (1-5).

[0079] Particularly preferably, Ar or An each independently represents Ar-1, Ar-2, Ar-6, Ar-11 and Ar-17, where R' has a meaning given above or preferably given below.

[0080] R' in substituents of the formulas Ar-1 to Ar-17, as described above, is preferably selected independently from the group consisting of H, D, CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R. R' in substituents of the formulas Ar-1 to Ar-17, as described above, is particularly preferably selected from the group consisting of H or D.

[0081] Aro in substituents of the formulas Ar-13 to Ar-16, as described above, is preferably phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which may optionally be partially or completely deuterated.

[0082] In compounds of formulas (1a) and (1b) or preferably described compounds of formulas (1a) and (1b), Ar2 and Ars each independently represent an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be substituted by one or more radicals R.

[0083] In compounds of formulas (1a) and (1b) or preferred compounds of formulas (1a) and (1b), Ar2 and Ars are preferably different from each other.

[0084] Ar2 and Ars are each independently preferably selected from the groups Ar-1 to Ar-17 as previously described or preferably described, wherein the dashed line indicates the binding site to [L] or the residue of formulas (1a) and (1b).

[0085] In compounds of formulas (1a) and (1b) or preferably described compounds of formulas (1a) and (1b), Ar2 and Ars each independently of one another particularly preferably denote phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, indenocarbazol-N-yl, N-arylindolocarbazol-N-yl, carbazol-N-yl or aryl-N-carbazolyl, which may be substituted by one or more radicals R, where aryl has a meaning given above and R has a meaning given above or below. If the substituent Ar2 or Ars is substituted by one or more radicals R, as described above, R is preferably selected in each case independently from the group D, F or CN, particularly preferably as D.

[0086] In compounds of formulas (1a) and (1b) or in preferred compounds of formulas (1a) and (1b), Ar2 and Ars each independently of one another very particularly preferably represent phenyl, 1-4-biphenyl, carbazol-N-yl, or dibenzofuranyl, which may be partially or fully deuterated. The dibenzofuranyl can be attached in any position.

[0087] In a preferred embodiment of the compounds of formulas (1a) and (1b), these compounds are partially or completely deuterated, particularly preferably completely deuterated.

[0088] Examples of suitable host materials of formulas (1a) and (1b), as previously described or preferably described, are the structures listed below in Table 1.

[0089] Table 1 :

[0090] oo C\lo co

[0091] ro ro cn o

[0092]

[0093] oo C\lo co

[0094]

[0095] Particularly suitable compounds of formulas (1a) and (1b), as described above or preferably described, are compounds E1 to E36 of Table 2.

[0096] Table 2:

[0097]

[0098] The compounds according to the invention can be prepared by synthesis steps known to the person skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig

[0099] Buchwald coupling, etc., can be represented.

[0100] Suitable compounds containing a diazadibenzofuran or diazadibenzothiophene group can often be obtained commercially. The starting compounds presented in the examples are obtainable by known processes, so reference is made to this. In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any other substituents in the processes. The processes shown for the synthesis of the compounds according to the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge.

[0101] Scheme 1: Scheme 2:

[0102] Scheme 3: Ar and Ar' correspond to Ar2 and Ars in compounds of formulas (1a) and

[0103] (1b)

[0104] Scheme 4: Ar and Ar' correspond to Ar2 and Ars in compounds of formulas (1a) and

[0105] (1b) Scheme 5: Ar and Ar' correspond to Ar2 and Ars in compounds of formulas (1a) and

[0106] (1b) Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0107] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds of formula (1a) or formula (1b) can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0108] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention or mixtures of compounds of the invention with other functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF, are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a- Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1 ,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Tri- ethylenglycolbutylmethylether, Diethylenglycoldibutylether, T riethylenglycoldimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetraethylenglycoldi- methylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1 ,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbiphenyl, 1- Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure-diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0109] The compounds of the formulas (1a) and (1b) according to the invention, as described above or preferably described, are suitable for use in an organic electroluminescent device, in particular as a matrix material. When the compound of the invention is used as a matrix material or, synonymously, host material in an emitting layer, it is preferably used in combination with another compound.

[0110] The invention therefore further provides a mixture comprising at least one compound of the formulas (1a) or (1b) or at least one preferred compound of one of the formulas (1a) and (1b) or a compound of Table 1 or one of the compounds E1 to E36 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture according to the invention are described below.

[0111] The present invention also further provides a formulation comprising at least one compound according to the invention, as described above, or a mixture according to the invention, as described above, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0112] The present invention further provides an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound of the formulas (1a) or (1b) or at least one preferred compound of one of the formulas (1a) and (1b) or a compound of Table 1 or one of the compounds E1 to E36.

[0113] The organic electronic device can be selected, for example, from organic integrated circuits (OLCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, organic photoreceptors.

[0114] Preferably, the organic electronic device is an organic electroluminescent device.

[0115] The organic electroluminescent device according to the invention (synonymously referred to as organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0116] The organic layer of the device according to the invention preferably contains, in addition to a light-emitting layer (EML), a hole-injection layer (HIL), a hole-transport layer (HTL), a hole-blocking layer (HBL), an electron-transport layer (ETL), an electron-injection layer (EIL), an exciton-blocking layer, an electron-blocking layer, and / or charge-generation layers. The device according to the invention can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Interlayers, which, for example, have an exciton-blocking function, can also be introduced between two emitting layers.

[0117] If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e. different emitting compounds which can fluoresce or phosphoresce are used in the emitting layers. A plurality of fluorescent and / or phosphorescent compounds can also be present in one emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

[0118] The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0119] It is not difficult for a person skilled in the art to draw on a multitude of materials known in the prior art to select suitable materials for use in the layers of the organic electroluminescent device described above. In doing so, the person skilled in the art will consider common considerations regarding the chemical and physical properties of the materials, as they are aware that the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, as well as other material properties.

[0120] The compound according to the invention of the formulas (1a) or (1b), as described above or preferably described, can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (1a) or formula (1b) or the preferred embodiments described above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters or for emitters which display TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in an electron transport layer and / or in a hole transport layer and / or in an exciton blocking layer and / or in a hole blocking layer. The compound according to the invention is particularly preferably used as a matrix material in a light-emitting layer or as an electron transport orHole blocking material used in an electron transport or hole blocking layer.

[0121] A further subject matter of the present invention is an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formulas (1a) or (1b) or which contains at least one preferred compound of one of the formulas (1a) and (1b) or a compound of Table 1 or one of the compounds E1 to E36.

[0122] In one embodiment of the invention, a further matrix material is selected for the device according to the invention in the light-emitting layer, which is used with compounds of the formulas (1a) or (1b), as described above or preferably described, or with the compounds of Table 1 or the compounds E1 to E36.

[0123] A further subject matter of the present invention is accordingly an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formulas (1a) or (1b) or the at least one preferred compound of one of the formulas (1a) and (1b) or a compound of Table 1 or one of the compounds E1 to E36 and a further matrix material.

[0124] Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter that emits at a shorter wavelength than the actual emitter can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, such as a wide-band-gap compound.

[0125] A wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the distance between the HOMO and LUMO energy of a material.

[0126] Particularly suitable matrix materials which are advantageously combined with compounds of formula (1a) or formula (1b), as previously described or preferably described, in a mixed matrix system can be selected from the compounds of formulas (6), (7), (8), (9), (10) or (11), as described below.

[0127] A further subject of the invention is therefore an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of formula (1a) or formula (1b) as matrix material 1, as described above or described as preferred, and at least one compound of formulas (6), (7), (8), (9), (10) or (11) as matrix material 2,

[0128] , where the symbols and indices used are:

[0129] A 1 is C(R 7 )2, NR 7 , O or S;

[0130] L is a bond, O, S, C(R 7 )2 or NR 7 ;

[0131] A is at each occurrence independently a group of formula (3) or

[0132] (4),

[0133] X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of

[0134] 2 symbols X2 can mean N;

[0135] * indicates the binding site to formula (9);

[0136] U 1 , U 2 are a bond, O, S, C(R 7 )2 or NR 7 ;

[0137] R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other;

[0138] Ars, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted;

[0139] R 7 is the same or different at each occurrence D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system;

[0140] R 8is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently denote 0 or 1 on each occurrence, where the sum of the indices on each occurrence is c+c1+c2 = 1; d, d1, d2 each independently denote 0 or 1 on each occurrence, where the sum of the indices on each occurrence is d+d1+d2 = 1; q, q1, q2 each independently denote 0 or 1 on each occurrence; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; t is, on each occurrence, the same or different, 0, 1, 2 or 3; u is the same or different at each occurrence: 0, 1, or 2; u1, u2 each independently mean 0 or 1 at each occurrence, where the sum u1 + u2 = 1; and v is 0 or 1.

[0141] In compounds of formulas (6), (7), (8), (10) or (11), s is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0142] In compounds of formulas (6), (7) or (8), t is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0143] In compounds of formulas (6), (7), (8) or (10), u is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0144] The sum of the indices s, t and u in compounds of the formulas (6), (7), (8), (10) or (11) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2. This preferably applies when R 6is different from D. In compounds of formula (9), c, c1, c2 each independently represent 0 or 1 at each occurrence, where the sum of the indices c+c1+c2 represents 1 at each occurrence. Preferably, c2 represents 1.

[0145] In compounds of formula (9), L is preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferably L is a single bond.

[0146] In formula (4), U or U when occurring are preferably a single bond or C(R )2, where R 7 has a meaning mentioned above, particularly preferred are U 1 or U 2 when a single bond occurs.

[0147] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10) or (11), which can be combined according to the invention with compounds of formula (1a) or formula (1b), as described above, R 6identically or differently on each occurrence selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 7 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, each substituted by one or more radicals R 7 can be substituted.

[0148] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10) or (11), which can be combined according to the invention with compounds of formula (1a) or formula (1b), as described above, R 6 identically or differently on each occurrence selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which is reacted with one or more radicals R7 can be substituted.

[0149] Preferably, Ars in compounds of formulas (6), (7), (8), (10) or (11) is selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which can be substituted via the 1-,

[0150] 2-, 3- or 4-position, spirobifluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-,

[0151] 3- or 4-position, dibenzothiophene, which can be linked via the 1-, 2-, 3- or

[0152] 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is linked to one or more radicals R 7 may be substituted. Preferably, Ars is unsubstituted.

[0153] If A 1 in formula (7) or (8) or (11) for NR 7 the substituent R 7 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 In a particularly preferred embodiment, this substituent R 7 identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms. Preferred embodiments for R 7are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, as well as radicals derived from triazine, pyrimidine and quinazoline, which are substituted by one or more radicals R 8 can be substituted.

[0154] If A 1 in formula (7) or (8) or (11) for C(R 7 )2, the substituents R 7 which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 R is particularly preferably 7 represents a methyl group or a phenyl group. The radicals R 7 also form a ring system with each other, which leads to a spiro system.

[0155] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10) and (11), these compounds are partially or completely deuterated, particularly preferably completely deuterated.

[0156] The preparation of the compounds of formulas (6), (7), (8), (9), (10) and (11) are generally known and some of the compounds are commercially available.

[0157] Compounds of formula (9) are disclosed, for example, in WO2021 / 180614, pages 110 to 119, in particular as examples on pages 120 to 127. Their preparation is disclosed in WO2021 / 180614 on page 128 and in the synthesis examples on pages 214 to 218. The preparation of the triarylamines of formula (11) is known to the person skilled in the art, and some of the compounds are commercially available.

[0158] If the additional matrix material is a deuterated compound, it is possible that the additional matrix material is a mixture of deuterated compounds with the same basic chemical structure, which differ only in the degree of deuteration.

[0159] In a preferred embodiment of the further matrix material, this is a mixture of deuterated compounds of the formulas (6), (7), (8), (9), (10), or (11), as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. The data are in mol%. Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651, and WO2018 / 110887 or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605, or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0160] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0161] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry 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 the combination of D2O with a fully deuterated organic solvent, whereby 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 with heating, more preferably with heating to temperatures between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure. Examples of suitable further matrix materials for combination with compounds of formula (1a) or formula (1b), as previously described or preferably described, are the compounds described in WO2019 / 229011, Table 3, pages 137 to 203, which may also be partially or fully deuterated.

[0162] Examples of suitable further matrix materials for a combination with compounds of formula (1a) or formula (1b), as previously described or preferably described, are the compounds described in WO2011 / 088877, table page 30, compounds 1 to 166, which may also be partially or completely deuterated.

[0163] Examples of suitable further matrix materials for a combination with compounds of formula (1a) or formula (1b), as previously described or preferably described, are the compounds described in WO2011 / 128017, table page 23, compounds 1 to 151, which may also be partially or completely deuterated.

[0164] For a combination with a compound of formula (1a) or formula (1b), as described above or preferably described, compounds of formula (6) are particularly suitable in which at least one group Ars represents a heteroaromatic ring system having 5 to 40 ring atoms, which with one or more radicals R 7 may be substituted or compounds of formula (9) or (10).

[0165] For a combination with a compound of formula (1a) or formula (1b), as described above or preferably described, compounds of formula (9) or (10) are very particularly suitable.

[0166] For a combination with a compound of formula (1a) or formula (1b), as described above or preferably described, compounds of formula (10) are very particularly preferably suitable.

[0167] Further examples of suitable host materials of formulas (6), (7), (8), (9), (10) and (11) for combination with compounds of formulas (1a) or (1b), as previously described or preferably described, are the structures listed below in Table 3 and Table 4. Table 3:

[0168]

[0169] Particularly suitable compounds of formulas (6), (7), (8), (9), (10) or (11), which are selected according to the invention and are preferably used in combination with at least one compound of formula (1a) or formula (1b) in the electroluminescent device according to the invention, are the compounds of Table 4.

[0170]

[0171] The above-mentioned host materials of formulas (1a) and (1b) and their preferred embodiments or the compounds of Table 1 and the compounds E1 to E36 can be combined as desired in the device according to the invention with the above-mentioned matrix materials / host materials, the matrix materials / host materials of formulas (6), (7), (8), (9), (10) or (11) and their preferred embodiments of Table 3 or the compounds H1 to H27.

[0172] The invention further relates to a mixture containing at least one compound according to formula (1a) or formula (1b), where the symbols and indices used are:

[0173] V is O or S independently at each occurrence;

[0174] Li is a linker selected from L-1 to L-26, which may be partially or fully deuterated, or a combination of the linkers L-1 to L-26, where the linkers L-1 to L-26 may be partially or fully deuterated,

[0175] Vi is O or S; the dashed lines indicate the bond to Rx and the remainder of formula (1a) or formula (1b);

[0176] * denotes the bond to Li ,

[0177] R 1 is at each occurrence independently H, D, or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0178] Ar, An are, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R;

[0179] Ar2, Ars are, identically or differently at each occurrence, an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 9 to 40 ring atoms, which may be substituted by one or more radicals R;

[0180] R is selected, identically or differently at each occurrence, from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where 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;

[0181] R# is, when occurring, D, or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0182] [L] is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted by D; b, b1 are each independently 0 or 1. b2 are each independently 0, 1, 2 or 3, with the condition for compounds of formula (1a), if Li is a linker L-3 or L-8 which is not deuterated, then Li-Rx is bonded to the remainder of formula (1a) only in positions 6, 7 or 9, and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0183] Very particularly preferred mixtures of the compounds of formulas (1a) and (1b) with the host materials of formulas (6), (7), (8), (9), (10) or (11) for the device according to the invention are obtained by combining the compounds E1 to E36 with the compounds H1 to H27 as shown below in Table 5. The first mixture M1, for example, is a combination of the compound E1 with H1.

[0184] Table 5: The concentration of the host material of formula (1a) or formula (1b), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0185] The concentration of the host material of one of the formulas (6), (7), (8), (9), (10) or (11), as described above or described as preferred, in the mixture according to the invention or in 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.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0186] The present invention also relates to a mixture which, in addition to the above-mentioned host materials of the formula (1a) or the formula (1b), hereinafter referred to as host material 1, and the host material of one of the formulas (6), (7), (8), (9), (10) or (11), hereinafter referred to as host material 2, as described above or preferably described, in particular mixtures M1 to M972, contains at least one phosphorescent emitter.

[0187] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter in addition to the above-mentioned host materials of the formulas (1a) or (1b) and one of the formulas (6), (7), (8), (9), (10) or (11), as described above or preferably described, in particular the material combinations M1 to M972.

[0188] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0189] Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that, upon suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.

[0190] In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

[0191] Preferred phosphorescent emitters according to the present invention correspond to the formula (IIIa), Formula (Illa), where the symbols and indices for this formula (Illa) have the meaning: n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0192] X is the same or different at each occurrence, N or CR,

[0193] R is, identically or differently on each occurrence, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms, which may be partially or fully substituted with deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may be partially or fully substituted with deuterium. The invention accordingly further provides an organic electroluminescent device, as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the formula (IIIa), as described above.

[0194] In emitters of formula (IIIa), n is preferably 1 and m is preferably 2.

[0195] In emitters of the formula (IIIa), one X is preferably selected from N and the other Xs are CR or all Xs, identical or different at each occurrence, are CR.

[0196] In emitters of formula (IIIa) at least one R is preferably different from H. In

[0197] Emitters of the formula (IIIa) are preferably two R different from H and have one of the meanings otherwise previously given for the emitters of the formula (IIIa).

[0198] Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V), where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the meaning:

[0199] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium. Preferred phosphorescent emitters according to the present invention correspond to the formulas (VI), (VII) or (VIII), where the symbols and indices for these formulas (VI), (VII) and (VIII) have the meaning:

[0200] Ri is H or D, R2 is H, D, F, CN, or a branched or linear alkyl group having 1 to 10 C atoms, or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms, or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium. Preferred examples of phosphorescent emitters are described in WO2019 / 007867 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.

[0201] Particularly preferred examples of phosphorescent emitters are listed in Table 6 below.

[0202] Table 6: 

[0203] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture selected from the sum of the mixtures M1 to M972 is preferably combined with a compound of the formula (IIIa) or a compound of the formulas (I) to (VIII) or a compound from Table 6.

[0204] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.

[0205] A yellow-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 600 to 750 nm.

[0206] A green-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 490 to 540 nm. A blue-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host materials of formulas (1a) or (1b) and one of formulas (6), (7), (8), (9), (10) or (11) and the corresponding emitter.

[0207] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0208] The photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free, 10 molar solution. The measurement is performed at room temperature, and any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is performed using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0209] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T-| is preferably between ~2.3 eV and ~2.1 eV.

[0210] Preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T 1 is preferably between ~2.5 eV and ~2.3 eV.

[0211] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, as previously described, whose triplet energy T-| is preferably between ~2.5 eV and ~2.3 eV.

[0212] Very particular preference is given to selecting green emitters, preferably of the formula (IIIa), the formulas (I) to (VIII) or from Table 6, as described above, for the mixture according to the invention or the emitting layer according to the invention.

[0213] Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably with at least 14 ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which one diarylamino group is bonded directly to one anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to one anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan units or thiophene units. Furthermore, the light-emitting device or the mixture according to the invention can also contain materials that exhibit TADF (thermally activated delayed fluorescence).

[0214] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can comprise, in addition to the host materials 1 and 2, as described above or described as preferred, further host materials or matrix materials, so-called mixed-matrix systems. The mixed-matrix systems preferably comprise three or four different matrix materials, particularly preferably three different matrix materials (i.e., a further matrix component in addition to the host materials 1 and 2, as described above). Particularly suitable matrix materials, which can be used in combination as a matrix component of a mixed-matrix system, are selected from wide-band gap materials, bipolar host materials, electron transport materials (ETMs), and hole transport materials (HTMs).

[0215] Preferably, the mixed matrix system is optimized for an emitter of formula (IIIa), formulas (I) to (VIII) or from Table 6.

[0216] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, apart from the constituents of the host material of formula (1a) or formula (1b) and the host material 2, as described above. These are material mixtures used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This enables the vapor deposition of a layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0217] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (1a) or formula (1b) and the host material 2, as described above, a phosphorescent emitter, as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source, as described above.

[0218] The components or constituents of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0219] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material made of at least one compound of formula (1a) or formula (1b) and at least one compound of one of formulas (6), (7), (8), (9), (10) or (11) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.%, very particularly preferably between 3 and 20 vol.-% of the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt.% are preferred instead of the above-mentioned amounts in vol.%.

[0220] The present invention also relates to an organic electroluminescent

[0221] Device as described above or preferably described, wherein the organic

[0222] Layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL), whose hole injecting material and hole transporting material belong to the class of arylamines.

[0223] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0224] Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0225] This sequence of layers is a preferred sequence.

[0226] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0227] All materials used in the electron-transport layer according to the state of the art can be used as electron-transport materials. Particularly suitable are aluminum complexes, for example, Alq3; zirconium complexes, for example, Zrq4; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0228] Suitable cathodes for the device according to the invention are metals with a low work function, metal alloys or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals can be used which have a relatively high work function, such as Ag or Al, in which case combinations of the metals, such as Ca / Ag, Mg / Ag or Ba / Ag, are generally used. It may also be preferable to have a thin intermediate layer of a material with a high work function between a metallic cathode and the organic semiconductor.

[0229] Dielectric constant. Examples of suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g.

[0230] B. LiF, Ü2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm. Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. On the other hand, metal / metal oxide electrodes (e.g. Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, 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). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0231] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly (depending on the application) during production, since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0232] The production of the device according to the invention is not restricted in this regard. It is possible for one or more organic layers, including the light-emitting layer, to be coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'6 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10'7 mbar.

[0233] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10'5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0234] Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0235] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0236] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0237] A further subject of the invention is therefore a method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0238] When manufactured by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premixed" systems) and the mixture placed in a single material source, from which it is then vaporized ("premix evaporation"). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0239] A further subject matter of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1a) or formula (1b) together with the further materials forming the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0240] In a preferred embodiment of the present invention, the light-emitting layer is applied by vapor deposition, wherein the components of the composition are premixed and evaporated from a single material source.

[0241] A further subject of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1a) or formula (1b) together with at least one further matrix material as a premix, successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence), are deposited from the gas phase.

[0242] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0243] 1. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (1a) or formula (1b) or the preferred embodiments set out above and below, in particular as matrix material, have a very good lifetime. In particular, these compounds bring about low roll-off, i.e. a low drop in the power efficiency of the device at high luminance levels. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (1a) or formula (1b) or the preferred embodiments set out above and below as matrix materials, have excellent efficiency. In particular, compounds of the invention according to formula (1a) or formula (1b) or the preferred embodiments set out above and below bring about a low operating voltage when used in electronic devices.The compounds according to the invention of formula (1a) or formula (1b) or the preferred embodiments described above and below exhibit very high stability and longevity. Compounds according to formula (1a) or formula (1b) or the preferred embodiments described above and below can prevent the formation of optical loss channels in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants. The use of compounds according to formula (1a) or formula (1b) or the preferred embodiments described above and below in layers of electronic devices, particularly organic electroluminescent devices, leads to high mobility of the electron-conductor structures.Compounds according to formula (1a) or formula (1b), or the preferred embodiments described above and below, exhibit excellent glass film formation. Compounds according to formula (1a) or formula (1b), or the preferred embodiments described above and below, form very good films from solutions. The compounds according to formula (1a) or formula (1b), or the preferred embodiments described above and below, exhibit a triplet Ti level, which can, for example, be in the range of 2.50 eV - 2.90 eV. These aforementioned advantages are not accompanied by an excessive deterioration in other electronic properties.

[0244] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0245] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0246] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0247] The invention is explained in more detail by the following examples, without intending to limit it thereby.

[0248] Examples

[0249] General methods:

[0250] The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​are determined at the B3LYP / 6-31G(d) level for the ground-state energy optimized with B3LYP / 6-31G(d). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground-state geometry. The default settings for SCF and gradient convergence are used.

[0251] From the energy calculation, the HOMO is determined as the last orbital occupied by two electrons (alpha occupancy eigenvalues) and the LUMO as the first unoccupied orbital (alpha virtual eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. From this, the HOMO and LUMO values ​​in electronvolts, calibrated using cyclic voltammetry measurements, are determined as follows:

[0252] HOMOcorr = 0.90603 * HOMO - 0.84836

[0253] LUMOcorr = 0.99687 * LUMO - 0.72445

[0254] The triplet level T1 of a material is defined as the relative excitation energy (in eV) of the lowest energy triplet state resulting from quantum chemical energy calculations.

[0255] The singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state with the second lowest energy, which results from the quantum chemical energy calculation.

[0256] The lowest energy singlet state is called SO.

[0257] The method described here is independent of the software package used and always produces the same results. Examples of commonly used programs for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this case, the program package "Gaussian16 (Rev. B.01)" is used to calculate the energies.

[0258] Synthesis examples

[0259] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared using synthesis methods known to those skilled in the art. a) (3-Amino-4-chloro-2-benzofuranyl)phenylmethanone

[0260] [73289-85-7]

[0261] To a solution of 99 g (489 mmol) of 2-bromo-6-hydroxy-benzonitrile and 99.5 g (489 mmol) of bromoacetophenone in 790 ml of acetone, 319 g (979 mmol) of cesium carbonate are added portionwise under argon at room temperature.

[0262] The reaction mixture is heated to 60°C for 2 hours. The mixture is then cooled to room temperature, filtered, and then concentrated to dryness under reduced pressure and recrystallized from heptane.

[0263] The yield is 107 g (316 mmol), corresponding to 69% of theory. The following brominated compounds are prepared analogously: b) 6-Bromo-2-cyanophenyl benzoate

[0264] [73289-85-7]

[0265] A solution of 10 g (50 mmol) of 2-bromo-6-hydroxybenzonitrile, 10.4 ml (75 mmol) of triethylamine, and 61 mg (0.5 mmol) of 4-N,N-dimethylaminopyridine in 200 ml of CH2Cl2 is initially charged, cooled to 0°C, and then 10.5 g (75 mmol) of benzoyl chloride is added. The mixture is stirred at room temperature for 3 h. The reaction mixture is poured into 20 ml of sodium chloride solution and extracted three times with Et2O. The combined organic phase is dried over MgSO4. The organic solvent is removed under reduced pressure, and the residue is subjected to flash column chromatography on silica gel (hexane / AcOEt = 20 / 1-7 / 1).

[0266] Yield: 10.4 g (33 mmol), 70% of theory. c) S-(2-cyano-3-bromophenyl)-benzenecarbothionate

[0267] [1245648-93-4]

[0268] In a baked-out flask under argon, 8 g (25 mmol) of 2-bromo-6-iodobenzonitrile, 0.47 g (10 mol%, 2.5 mmol) of Cul, 0.9 g (20 mol%, 5 mmol) of 1,10-phenanthroline, and 5.1 g (37.5 mmol) of thiobenzoic acid were added to 20 ml of degassed toluene under nitrogen and stirred at 100 °C for 24 h. The reaction mixture was cooled to room temperature. Diethyl ether (1000 ml) and saturated sodium chloride solution (1000 ml) were added, and the mixture was stirred. The organic phase was separated, and the aqueous phase was extracted with diethyl ether (2 x 1000 ml). The combined organic phases were dried over NaSO4, and the product was isolated by column chromatography.

[0269] Yield: 5.3 g (16.2 mmol), 65% of theory d) 2-Amino-4-Bromo-3-benzofuranyl)phenylmethanone

[0270] In a heated flask under argon, 0.67 g (30 mmol) of Pd(OAc)2, 1.69 g (6 mmol) of PCys (tricyclohexylphosphine), 1.96 g (30 mmol) of zinc powder, and 3 g of 4 Å molecular sieve (MS4A) are placed in 1200 ml of DMF. After stirring at room temperature for 20 min, 9.4 g (30 mmol) of bromo-2-cyanophenyl benzoate is added, and the mixture is stirred overnight at 100°C. Saturated NaCl solution is then added to the mixture, and the aqueous phase is quenched with Et2. <D (100 ml x 3) extrahiert. Die vereinigten organischen Phasen werden über MgSCU getrocknet und filtriert. Das organische Lösungsmittel wird im Vakuum entfernt und der Rückstand wird einer Flash-Säulenchromatographie an Kieselgel (Hexan / AcOEt = 7 / 1 - 2 / 1) gereinigt. Ausbeute: 6,2 g (20 mmol), 67 % der Theorie.

[0271] Analogously, the following brominated compounds are prepared: e) 9-Bromo-2,4-diphenylbenzofuro[3,2-cf]pyrimidine Under argon, 107 g (316 mmol) of (3-amino-4-chloro-2-benzofuranyl)phenylmethanone and 104 g (1015 mmol) of benzonitrile are placed in 1000 ml of o-xylene, and 56 g (677 mmol) of sodium 2-methylpropan-2-olate are added. The mixture is stirred for 5 hours at 140°C. 30 ml of water is removed via a water separator, then a small amount of acetone is added and the mixture is stirred for another hour. After cooling, the mixture is quenched with one liter of water. The organic phase is separated, washed three times with 300 ml of water, dried over MgSO , filtered, and the solvent is removed in vacuo. The residue is purified by column chromatography.

[0272] The yield is 64 g (160 mmol), corresponding to 48% of theory.

[0273] Analogously, the following connections are made:

[0274] f) 2,9-Dichloro-4-phenyl-benzofuro[3,2-d]pyrimidine

[0275] 13 g (110.0 mmol) of phenylboronic acid, 15.1 g (56 mmol) of 2,4,9-trichlorobenzofuro[3,2-dipyrimidine], and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, and then evaporated to dryness. The residue is recrystallized from toluene and dichloromethane / heptane. Yield: 13.1 g (42 mmol), 75% of theory.

[0276] Analogously, the following connections are made:

[0277]

[0278] Production of OLEDs

[0279] In the following examples V1 to V11 and B1 to B40 (see Tables 7 and 8) the data of different OLEDs are presented.

[0280] Examples B1 to B40 show data from OLEDs according to the invention. The substrates used for the OLEDs in Table 7 are glass plates coated with a 50 nm thick patterned ITO (indium tin oxide).

[0281] The exact structure of the OLEDs can be found in Table 7. The materials required to manufacture the OLEDs are shown in Table 9, unless previously described.

[0282] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (also called host material) and an emitting dopant (dopant, emitter), which is mixed with the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as SdT1:H2:TEG1 (33%:60%:7%) 30nm means that the material SdT1 is present in a volume fraction of 33% as host material 1, the compound H2 as host material 2 in a volume fraction of 60%, and TEG1 in a volume fraction of 7% in a 30nm-thick layer. Analogously, the electron-transport layer can also consist of a mixture of two materials. OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured, from which the EQE is calculated.The calculation assumes a Lambertian radiation pattern. The electroluminescence spectra are measured at a luminance of 1000 cd / m. 2 and from this the CIE 1931 x and y color coordinates are calculated. The value U1000 in Table 8 refers to the voltage required for a luminance of 1000 cd / m 2 is required. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd / m 2 .

[0283] The lifetime LT is defined as the time after which the luminance in mA / cm 2 from a starting luminance LO (in cd / m 2 ) to a certain proportion L1 (in cd / m 2 ). A value of L1 / L0 = 80% in Table 8 means that the lifetime given in column LT corresponds to the time (in hours) after which the luminance drops to 80% of its initial value (LO).

[0284] Use of mixtures according to the invention in OLEDs

[0285] The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0286] The data for the various OLEDs are summarized in Table 8. Examples C1 to C11 are comparative examples according to the prior art, while Examples B1 to B40 show data for OLEDs according to the invention. The inventive examples demonstrate a significant advantage in the device's lifetime.

[0287] Table 7: Structure of the OLEDs Table 8:

[0288] Table 9: Materials used, unless previously described

[0289]

Claims

Patent claims Compound according to formula (1a) or formula (1b), where the symbols and indices used are: V is O or S independently at each occurrence; Li is a linker selected from L-1 to L-26, which may be partially or fully deuterated, or a combination of the linkers L-1 to L-26, where the linkers L-1 to L-26 may be partially or fully deuterated, Vi is O or S; the dashed lines indicate the bond to Rx and the rest of the formula (1a) or the formula (1b); Rx corresponds to one of the formulas (1-2), (1-3), (1-4) or (1-5) denotes the bond to Li , R 1 is at each occurrence independently H, D, or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; Ar, An are, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; Ar2, Ars are, identically or differently at each occurrence, an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 9 to 40 ring atoms, which may be substituted by one or more radicals R; R is selected, identically or differently at each occurrence, from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where 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; R# is, when occurring, D, F or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; [L] is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 9 to 40 ring atoms, which may be unsubstituted or partially or fully substituted with D; b, b1 are each independently 0 or 1. b2 are each independently 0, 1, 2 or 3, with the condition for compounds of formula (1a) when Li is a linker L-3 or L- 8, which is not deuterated, then Li-Rx is bonded to the residue of formula (1a) only in positions 6, 7, or 9. A compound according to claim 1, wherein Rx corresponds to formula (1-2). A compound according to claim 1 or 2, wherein VO denotes. A compound according to one or more of claims 1 to 3, wherein Li is selected from the group of linkers L-14 to L-26.

5. A mixture comprising at least one compound according to one or more of claims 1 to 4 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

6. Formulation comprising at least one compound according to one or more of claims 1 to 4 or a mixture according to claim 5 and at least one solvent.

7. An organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound according to one or more of claims 1 to 4.

8. The organic electronic device of claim 7, wherein the electronic device is an electroluminescent device.

9. The organic electronic device according to claim 7 or 8, wherein the organic layer contains at least one light-emitting layer containing the compounds according to any one of claims 1 to 4.

10. Organic electronic device according to one or more of claims 7 to 9, characterized in that the light-emitting layer contains a further matrix material.

11. Organic electroluminescent device according to claim 10, characterized in that the further matrix material corresponds to a compound of formulas (6), (7), (8), (9), (10) or (11), Ċ where the symbols and indices used are: A 1 is C(R 7 )2, NR 7 , O or S; L is a bond, O, S, C(R 7 )2 or NR 7 ; A is, at each occurrence independently, a group of the formula (3) or (4), X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols X2 can mean N; * indicates the binding site to formula (9); U 1 , U 2 are a bond, O, S, C(R 7 )2 or NR 7 ; R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other; Ars, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted; R 7 is the same or different at each occurrence D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; Q R is, identical or different at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently at each occurrence is 0 or 1, where the sum of the indices at each occurrence is c+c1+c2 = 1; d, d1, d2 each independently at each occurrence is 0 or 1, where the sum of the indices at each occurrence is d+d1+d2 = 1; q, q1, q2 each independently at each occurrence is 0 or 1; s is, identical or different at each occurrence, 0, 1, 2, 3 or 4; t is, identical or different at each occurrence, 0, 1, 2 or 3; u is the same or different at each occurrence: 0, 1, or 2; u1, u2 each independently mean 0 or 1 at each occurrence, where the sum u1 + u2 = 1; and v is 0 or 1.Organic electronic device according to one or more of claims 7 to 11, characterized in that the light-emitting layer contains a phosphorescent emitter.

13. The organic electronic device according to one or more of claims 7 to 12, characterized in that it is an electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

14. The method for producing a device according to one or more of claims 7 to 13, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formula (1a) or (1b) together with the other materials forming the light-emitting layer are deposited successively or simultaneously from at least two material sources from the vapor phase.Method for producing a device according to one or more of claims 7 to 13, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1a) or (1b) together with at least one further matrix material as a premix, are deposited from the gas phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

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