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.

Claims

1.-15. (canceled)

16. A compound of formula (1a) or formula (1b): ##STR00658## wherein: V at each instance is independently O or S; L.sub.1 is a linker selected from L-1 to L26 that may be partly or fully deuterated, or a combination of the linkers L-1 to L-26, where the linkers L-1 to L-26 may be partly or fully deuterated, ##STR00659## ##STR00660## V.sub.1 is O or S; the dashed lines denote the attachment to Rx and the remainder of the formula (1a) or of the formula (1b); Rx conforms to one of the formulae (1-2), (1-3), (1-4) and (1-5) ##STR00661## * denotes the attachment to L.sub.1, R.sup.1 at each instance is independently H, D, or undeuterated or partly or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; Ar, Ar.sub.1 are the same or different at each instance and are an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sub.2, Ar.sub.3 are the same or different at each instance and are an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, each of which may be substituted by one or more R.sup.2 radicals; R.sup.2 is the same or different at each instance and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where one or more nonadjacent CH.sub.2 groups may be replaced by O or S and where one or more hydrogen atoms may be replaced by D, F, or CN; R #where it occurs is D, F or undeuterated or partly or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; [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 partly 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 the formula (1a) that, when L.sub.1 is an undeuterated linker L-3 or L-8, L.sub.1-Rx is bound to the remainder of the formula (1a) only in position 6, 7 or 9.

17. A compound as claimed in claim 16, where Rx conforms to the formula (1-2).

18. A compound as claimed in claim 16, where Vis O.

19. A compound as claimed in claim 16, where Li is selected from the group of linkers L-14 to L-26.

20. A mixture comprising at least one compound as claimed in claim 16 and at least one further compound selected from the group of the matrix materials, phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence).

21. A formulation comprising at least one compound as claimed in claim 16 and at least one solvent.

22. An organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one compound as claimed in claim 16.

23. The organic electronic device as claimed in claim 22, wherein the electronic device is an electroluminescent device.

24. The organic electronic device as claimed in claim 22, wherein the organic layer contains at least one light-emitting layer containing the compounds.

25. The organic electronic device as claimed in claim 22, wherein the light-emitting layer contains a further matrix material.

26. The organic electroluminescent device as claimed in claim 25, wherein the further matrix material corresponds to a compound of the formulae (6), (7), (8), (9), (10) or (11) ##STR00662## wherein: A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, O or S; L is a bond, O, S, C(R.sup.7).sub.2 or NR.sup.7; A at each instance is independently a group of the formula (3) or (4), ##STR00663## X.sub.2 is the same or different at each instance and is CH, CR.sup.6 or N, where not more than two symbols X.sub.2 can be N; * indicates the binding site to the formula (9); U.sup.1, U.sup.2 where they occur are a bond, O, S, C(R.sup.7).sub.2 or NR.sup.7; R.sup.6 is the same or different at each instance and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.7 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, CO, NR.sup.7, O, S or CONR.sup.7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be substituted in each case by one or more R.sup.7 radicals; it is also possible here for two R.sup.6 radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar.sub.5 is the same or different at each instance and is independently an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.7 radicals; R.sup.7 is the same or different at each instance and is D, F, Cl, Br, I, N(R.sup.8).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(O) R.sup.8, P(O)(R.sup.8).sub.2, S(O) R.sup.8, S(O).sub.2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.8 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, CO, NR.sup.8, O, S or CONR.sup.8, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted in each case by one or more R.sup.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, the R.sup.7 radicals do not form any such ring system; R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; c, c1, c2 at each instance are each independently 0 or 1, where the sum total of the indices at each instance c+c1+c2=1; d, d1, d2 at each instance are each independently 0 or 1, where the sum total of the indices at each instance d+d1+d2=1; q, q1, q2 at each instance are each independently 0 or 1; S is the same or different at each instance and is 0, 1, 2, 3 or 4; t is the same or different at each instance and is 0, 1, 2 or 3; u is the same or different at each instance and is 0, 1 or 2; u1, u2 at each instance are each independently 0 or 1, where the sum total u1+u2=1; and v is 0 or 1.

27. The organic electronic device as claimed in claim 22, wherein the light-emitting layer contains a phosphorescent emitter.

28. The organic electronic device as claimed in claim 22, wherein it is an electroluminescent device selected from 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).

29. A process for producing a device as claimed in claim 22, wherein the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formula (1a) or (1b) is deposited from the gas phase together with the further materials that form the light-emitting layer, successively or simultaneously from at least two material sources.

30. A process for producing a device as claimed in claim 22, wherein the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formula (1a) or (1b) is deposited from the gas phase together with at least one further matrix material as premix, successively or simultaneously with the light-emitting materials selected from the group of the phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence).

Description

DESCRIPTION OF THE INVENTION

[0031] In the present patent application, D or D atom means deuterium.

[0032] An aryl group in the context of this invention contains 6 to 40 ring atoms, preferably carbon atoms. A heteroaryl group in the context of this invention contains 5 to 40 ring atoms, where the ring atoms include carbon atoms and at least one heteroatom, with the proviso that the sum total of carbon atoms and heteroatoms adds up to at least 5. The heteroatoms are preferably selected from N, O and/or S. What is meant here by an aryl group or heteroaryl group is 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 having 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, with no restriction in the attachment of the aryl group as substituent. The aryl or heteroaryl group in the context of this invention may bear one or more radicals, where the suitable radical is described below. If no such radical is described, the aryl group or heteroaryl group is unsubstituted.

[0033] An aromatic ring system in the context of this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system also includes aryl groups as described above. An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0034] A heteroaromatic ring system in the context 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.

[0035] What is meant by an aromatic or heteroaromatic ring system in the context of this invention is a system which does not necessarily contain only aryl or heteroaryl groups, but in which it is also possible for a plurality of aryl or heteroaryl groups to be interrupted by a nonaromatic unit (preferably less than 10% of the atoms other than H), for example a carbon or oxygen atom or a carbonyl group. For example, systems such as 9,9-spirobifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ethers, stilbene, etc. shall thus also be regarded as aromatic or heteroaromatic ring systems in the context of this invention, and likewise systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. In addition, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise encompassed by the definition of the aromatic or heteroaromatic ring system.

[0036] An aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be joined to the aromatic or heteroaromatic via any position is understood to mean, for example, groups which are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0037] The abbreviations Ar and Ar are the same or different at each instance and denote an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.2 radicals, where the R.sup.2 radical or the substituents R.sup.2 is/are defined as described above or hereinafter. A preferred definition of Ar and Ar.sub.1 is described hereinafter.

[0038] The abbreviations Ar.sub.2 and Ar.sub.3 are the same or different at each instance and denote 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 R.sup.2 radicals, where the R.sup.2 radical or the substituents R.sup.2 has/have a definition as described above or hereinafter. A preferred definition of Ar.sub.2 and Ar.sub.3 is described hereinafter.

[0039] The abbreviation Ar.sub.5 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.7 radicals, where the R.sup.7 radical or the substituents R.sup.7 is/are defined as described above or hereinafter. A preferred definition of Ar.sub.5 is described hereinafter.

[0040] What is meant by a cyclic alkyl, alkoxy or thioalkyl group in the context of this invention is a monocyclic, a bicyclic or a polycyclic group.

[0041] In the context of the present invention, a straight-chain, branched or cyclic C.sub.1- to C.sub.20-alkyl group is understood to mean, for example, the methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl) octyl, 3-(3,7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)-cyclohex-1-yl, 1-(n-hexyl)-cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl and 1-(n-decyl)-cyclohex-1-yl.

[0042] What is meant by the wording that two or more radicals together may form a ring system is the formation of an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, and, in the context of the present description, it shall mean, inter alia, that the two radicals are joined to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

##STR00007##

[0043] In addition, however, the abovementioned wording shall also be understood to mean that, if one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This will be illustrated by the following scheme:

##STR00008##

[0044] There follows a description of the compounds of the formulae (1a) and (1b) and preferred embodiments thereof. The preferred embodiments are also applicable to the mixture of the invention, formulation of the invention and organic electronic or electroluminescent device of the invention.

[0045] In formulae (1-2) to (1-5), R.sup.1 is preferably H or D.

[0046] In compounds of the formulae (1a) and (1b), Rx preferably represents the formula (1-2).

[0047] In compounds of the formula (1a), Rx is preferably bonded in position 6 or 9, more preferably in position 9, of the diazadibenzofuran or diazadibenzothiophene. Compounds of the formula (1a) are a preferred embodiment of the invention.

[0048] In compounds of the formula (1b), Rx is preferably bonded in position 5, 6 or 7, more preferably in position 5 or 6, most preferably in position 5, of the diazadibenzofuran or diazadibenzothiophene.

[0049] The numbering of the positions is shown by the example of the diazadibenzofuran base skeleton below:

##STR00009##

[0050] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, V is preferably O.

[0051] In one embodiment of the compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the group of linkers L-14 to L-26, which may be partly or fully deuterated.

[0052] In the linkers L-14 to L-26, V.sub.1 is preferably O.

[0053] Particularly preferred linkers from the group of L-1 to L-13 are the linkers L-1 to L-7, which may be partly or fully deuterated. Very particular preference is given to the linker L-2, which may be partly or fully deuterated.

[0054] Particularly preferred linkers from the group of L-14 to L-26 are the linkers L-15, L-16, L-18, L-19, L-23 and L-26, which may be partly or fully deuterated. Very particular preference is given to the linker L-16, which may be partly or fully deuterated.

[0055] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the preferred group of linkers as described above. In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the preferred group of linkers as described above, which are partly or fully deuterated.

[0056] In one embodiment of the compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the combination of linkers L-1 to L-26, where the linkers L-1 to L-26 may be partly or fully deuterated.

[0057] Preferred combinations of linkers L-1 to L-26 are combinations of linkers L-2 and L-3, which may be partly 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 partly or fully deuterated and in which V1 has a definition given above or given with preference. The sequence of the combination is not restricted, and any two of the dashed lines together form the linkage of the linkers to one another, and the two remaining dashed lines denote the attachment to Rx and the rest of the formula (1a) or of the formula (1b).

[0058] Particularly preferred linker combinations for L.sub.1 are:

##STR00010##

which may be partly or fully deuterated.

[0059] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the preferred combination of linkers as described above. In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, L.sub.1 is preferably selected from the preferred combination of linkers as described above, which are partly or fully deuterated.

[0060] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, R #where it occurs is preferably D, F or undeuterated or partly or fully deuterated phenyl, more preferably D or F, most preferably D.

[0061] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, b2 is preferably 3 and R #is D.

[0062] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, b2 is preferably 0 or 1 when R #has a definition given above or given with preference.

[0063] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, the symbol [L] is a linker for 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 partly or fully substituted by D.

[0064] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, the symbol [L] where it occurs is in each case independently preferably a linker selected from the group of L-1 to L-13 and [L-14] to [L-34], which may be unsubstituted or partly or fully substituted by D.

##STR00011## ##STR00012## ##STR00013##

where V.sub.2 is in each case independently O, S or N-aryl, the dashed lines denote the attachment to Ar.sub.2 or Ar.sub.3 and to the rest of the formula (1a) or (1b), and where the abbreviation aryl denotes an aromatic or heteroaromatic ring system which has 5 to 30 ring atoms and may be substituted by one or more R.sup.2 radicals. Aryl is preferably phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl or dibenzothiophenyl, where these radicals may be unsubstituted or partly or fully substituted by D. V.sub.2 is preferably O or N-aryl. V.sub.2 is more preferably O.

[0065] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, the symbol [L] where it occurs is in each case independently more preferably a linker selected from the group of L-2, L-3, L-4, L-5, [L-21] to [L-34], as described above or described with preference, which may be partly or fully substituted by D.

[0066] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, b is preferably 0.

[0067] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, b1 is preferably 0.

[0068] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, Ar and Ar.sub.1 are preferably different.

[0069] Ar and Ar.sub.1 are each independently preferably selected from the following groups Ar-1 to Ar-19:

##STR00014## ##STR00015##

where R is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sub.0).sub.2, NH.sub.2, N(R.sup.2).sub.2, C(O)Ar.sub.0, C(O)H, C(O)R.sup.2, P(O)(Ar.sub.0).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by HCCH, R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NH, NR.sup.2, O, S, CONH or CONR.sup.2, and where one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be substituted by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems, where two or more adjacent substituents R may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.2 radicals; [0070] and [0071] Ar.sub.0 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.2 radicals; [0072] at the same time, one or more R may also be bonded directly to a carbon atom of Ar.sub.0.

[0073] The dashed line indicates the bonding site to the rest of the formulae (1-2), (1-3), (1-4) and (1-5).

[0074] More preferably, Ar or Ar.sub.1 are each independently Ar-1, Ar-2, Ar-6, Ar-11 and Ar-17, where R has a definition given above or specified as preferred hereinafter.

[0075] R in substituents of the formulae Ar-1 to Ar-17 as described above is in each case independently preferably selected from the group of H, D, CN, and an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals.

[0076] R in substituents of the formulae Ar-1 to Ar-17, as described above, is more preferably selected from the group of H and D.

[0077] Ar.sub.0 in substituents of the formulae 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 partly or fully deuterated.

[0078] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) described with preference, Ar.sub.2 and Ar.sub.3 are each independently 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 R.sup.2 radicals.

[0079] In compounds of the formulae (1a) and (1b), or compounds of the formulae (1a) and (1b) mentioned with preference, Ar.sub.2 and Ar.sub.3 are preferably different.

[0080] Ar.sub.2 and Ar.sub.3 are each independently preferably selected from the Ar-1 to Ar-17 groups, as described above or described as preferred, where the dotted line indicates the bonding site to [L] or the rest of the formulae (1a) and (1b).

[0081] In compounds of the formula (1a) and (1b), or compounds of the formulae (1a) and (1b) described as preferred, Ar.sub.2 and Ar.sub.3 are each independently more preferably 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 R.sup.2 radicals, where aryl has a definition given above and R.sup.2 has a definition given above or hereinafter. If the substituent Ar.sub.2 or Ar.sub.3, as described above, is substituted by one or more R.sup.2 radicals, R.sup.2 is preferably in each case independently selected from the group of D, F or CN, more preferably is D.

[0082] In compounds of the formulae (1a) and (1b) or compounds of the formulae (1a) and (1b) described with preference, Ar.sub.2 and Ar.sub.3 are each independently most preferably phenyl, 1,4-biphenyl, carbazol-N-yl or dibenzofuranyl, which may be partly or fully deuterated. The dibenzofuranyl may be attached in any position.

[0083] In a preferred embodiment of the compounds of the formulae (1a) and (1b), these compounds are partly or fully deuterated, more preferably fully deuterated.

[0084] Examples of suitable host materials of the formulae (1a) and (1b) as described above or described as preferred are the structures shown below in table 1.

TABLE-US-00001 TABLE 1 [00016] [00017] [00018] [00019] [00020] [00021] [00022] [00023] [00024] [00025] [00026] [00027] [00028] [00029] [00030] [00031] [00032] [00033] [00034] [00035] [00036] [00037] [00038] [00039] [00040] [00041] [00042] [00043] [00044] [00045] [00046] [00047] [00048] [00049] [00050] [00051] [00052] [00053] [00054] [00055] [00056] [00057] [00058] [00059] [00060] [00061] [00062] [00063] [00064] [00065] [00066] [00067] [00068] [00069] [00070] [00071] [00072] [00073] [00074] [00075] [00076] [00077] [00078] [00079] [00080] [00081] [00082] [00083] [00084] [00085] [00086] [00087] [00088] [00089] [00090] [00091] [00092] [00093] [00094] [00095] [00096] [00097] [00098] [00099] [00100] [00101] [00102] [00103] [00104] [00105] [00106] [00107] [00108] [00109] [00110] [00111] [00112] [00113] [00114] [00115] [00116] [00117] [00118] [00119] [00120] [00121] [00122] [00123] [00124] [00125] [00126] [00127] [00128] [00129] [00130] [00131] [00132] [00133] [00134] [00135] [00136] [00137] [00138] [00139] [00140] [00141] [00142] [00143] [00144] [00145] [00146] [00147] [00148] [00149] [00150] [00151] [00152] [00153] [00154] [00155] [00156] [00157] [00158] [00159] [00160] [00161] [00162] [00163] [00164] [00165] [00166] [00167] [00168] [00169] [00170] [00171] [00172] [00173] [00174] [00175] [00176] [00177] [00178] [00179] [00180] [00181] [00182] [00183] [00184] [00185] [00186] [00187] [00188] [00189]

[0085] Particularly suitable compounds of the formulae (1a) and (1b) as described above or described as preferred are the compounds E1 to E36 in table 2.

TABLE-US-00002 TABLE 2 [00190] E1 [00191] E2 [00192] E3 [00193] E4 [00194] E5 [00195] E6 [00196] E7 [00197] E8 [00198] E9 [00199] E10 [00200] E11 [00201] E12 [00202] E13 [00203] E14 [00204] E15 [00205] E16 [00206] E17 [00207] E18 [00208] E19 [00209] E20 [00210] E21 [00211] E22 [00212] E23 [00213] E24 [00214] E25 [00215] E26 [00216] E27 [00217] E28 [00218] E29 [00219] E30 [00220] E31 [00221] E32 [00222] E33 [00223] E34 [00224] E35 [00225] E36

[0086] The compounds of the invention can be prepared by synthesis steps known to those skilled in the art, for example bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0087] Suitable compounds having a diazadibenzofuran or diazadibenzothiophene group are in many cases commercially available, and the starting compounds detailed in the examples are obtainable by known processes, and so reference is made thereto. In the synthesis schemes which follow, the compounds are shown with a small number of substituents to simplify the structures. This does not rule out the presence of any desired further substituents in the processes. The methods shown for synthesis of the compounds of the invention should be regarded as illustrative. The person skilled in the art will be able to develop alternative synthesis routes within the scope of his common knowledge in the art.

##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230##

[0088] Detailed reaction conditions are known from the prior art or are described in the examples section.

[0089] It is possible by these processes, if necessary followed by purification, for example recrystallization or sublimation, to obtain the compounds of the formula (1a) or formula (1b) in high purity, preferably more than 99% (determined by means of 1H NMR and/or HPLC).

[0090] For the processing of the compounds of the invention from liquid phase, for example by spin-coating or by printing methods, formulations of the compounds of the invention or of mixtures of compounds of the invention with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and/or emitters that exhibit TADF, are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, ()-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

[0091] The inventive compounds of the formulae (1a) and (1b) as described above or described as preferred are suitable for use in an organic electroluminescent device, especially as matrix material.

[0092] When the compound of the invention is used as matrix material or, synonymously, host material in an emitting layer, it is preferably used in combination with a further compound.

[0093] The invention therefore further provides a mixture comprising at least one compound of the formula (1a) or (1b) or at least one preferred compound of one of the formulae (1a) and (1b) or a compound from table 1 or one of compounds E1 to E36 and at least one further compound selected from the group of the matrix materials, phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture of the invention are described hereinafter.

[0094] The present invention likewise further provides a formulation comprising at least one compound of the invention, as described above, or a mixture of the invention, as described above, and at least one solvent. The solvent may be an abovementioned solvent or a mixture of these solvents.

[0095] The present invention further provides an organic electronic device comprising an anode, a cathode and at least one organic layer, comprising at least one compound of the formula (1a) or (1b) or at least one preferred compound of one of the formulae (1a) and (1b) or a compound from table 1 or one of compounds E1 to E36.

[0096] The organic electronic device may be selected, for example, from organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, organic photoreceptors.

[0097] The organic electronic device is preferably an organic electroluminescent device.

[0098] The organic electroluminescent device (synonymous with organic electroluminescent device) of the invention 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 of the invention is especially an organic light-emitting diode or an organic light-emitting electrochemical cell. The device of the invention is more preferably an OLED.

[0099] The organic layer of the device of the invention preferably comprises, as well as a light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocker layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocker layer, an electron blocker layer and/or charge generation layers. It is also possible for the device of the invention to include two or more layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL. It is likewise possible for interlayers having an exciton-blocking function, for example, to be introduced between two emitting layers.

[0100] If a plurality of emission layers are present, these preferably have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white emission; in other words, various emitting compounds which may fluoresce or phosphoresce are used in the emitting layers. It is also possible for two or more fluorescent and/or phosphorescent compounds to be present in an emitting layer. Especially preferred are systems having three emitting layers, where the three layers show blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer may also show yellow emission. Combinations of this kind are known to those skilled in the art. The organic electroluminescent device of the invention may also be a tandem electroluminescent device, especially for white-emitting OLEDs.

[0101] The device may also comprise inorganic materials or else layers formed entirely from inorganic materials.

[0102] It presents no difficulties at all to the person skilled in the art to consider a multitude of materials known in the prior art in order to select suitable materials for use in the above-described layers of the organic electroluminescent device. The person skilled in the art here will reflect in a customary manner on the chemical and physical properties of materials, since he knows that the materials interact with one another in an organic electroluminescent device. This relates, for example, to the energy levels of the orbitals (HOMO, LUMO) or else the triplet and singlet energy levels, but also other material properties.

[0103] The inventive compound of the formula (1a) or (1b) as described above or described as preferred can be used in different layers, according to the exact structure. Preference is given to an organic electroluminescent device comprising a compound of formula (1a) or formula (1b) or the above-recited preferred embodiments in an emitting layer as matrix material for fluorescent emitters, phosphorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), especially for phosphorescent emitters. In addition, the compound of the invention can also be used in an electron transport layer and/or in a hole transport layer and/or in an exciton blocker layer and/or in a hole blocker layer. Particular preference is given to using the compound of the invention as matrix material in a light-emitting layer or as electron transport material or hole blocker material in an electron transport layer or hole blocker layer.

[0104] The present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer comprising at least one compound of the formula (1a) or (1b) or the at least one preferred compound of one of the formulae (1a) and (1b) or a compound from table 1 or one of compounds E1 to E36.

[0105] In one embodiment of the invention, for the device of the invention, a further matrix material is selected in the light-emitting layer, and this is used together with compounds of the formula (1a) or (1b) as described above or described as preferred or with the compounds from table 1 or the compounds E1 to E36.

[0106] The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer comprising at least one compound of the formula (1a) or (1b) or the at least one preferred compound of one of the formulae (1a) and (1b) or a compound from table 1 or one of compounds E1 to E36, and a further matrix material.

[0107] Suitable matrix materials that can be used in combination with the compounds of 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. It is likewise possible for a further phosphorescent emitter having shorter-wavelength emission than the actual emitter to be present as co-host in the mixture, or a compound not involved in charge transport to a significant extent, if at all, for example a wide-bandgap compound.

[0108] What is meant herein by a wide-bandgap material is a material within the scope of the disclosure of U.S. Pat. No. 7,294,849 which is characterized by a band gap of at least 3.5 eV, the band gap meaning the gap between the HOMO and LUMO energy of a material. Particularly suitable matrix materials that are advantageously combined in a mixed matrix system with compounds of the formula (1a) or of the formula (1b) as described above or described as preferred may be selected from the compounds of the formulae (6), (7), (8), (9), (10) and (11), as described hereinafter.

[0109] The invention accordingly further provides an organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of the formula (1a) or of the formula (1b) as matrix material 1, as described above or described as preferred, and at least one compound of the formulae (6), (7), (8), (9), (10) and (11) as matrix material 2,

##STR00231## [0110] where the symbols and indices used are as follows: [0111] A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, O or S; [0112] L is a bond, O, S, C(R.sup.7).sub.2 or NR.sup.7; [0113] A at each instance is independently a group of the formula (3) or (4),

##STR00232## [0114] X.sub.2 is the same or different at each instance and is CH, CR.sup.6 or N, where not more than two symbols X.sub.2 can be N; [0115] * indicates the binding site to the formula (9); [0116] U.sup.1, U.sup.2 where they occur are a bond, O, S, C(R.sup.7).sub.2 or NR.sup.7; [0117] R.sup.6 is the same or different at each instance and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.7 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, CO, NR.sup.7, O, S or CONR.sup.7, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be substituted in each case by one or more R.sup.7 radicals; it is also possible here for two R.sup.6 radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; [0118] Ar.sub.5 is the same or different at each instance and is independently an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.7 radicals; [0119] R.sup.7 is the same or different at each instance and is D, F, Cl, Br, I, N(R.sup.8).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(O) R.sup.8, P(O)(R.sup.8).sub.2, S(O) R.sup.8, S(O) 2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.8 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, CO, NR.sup.8, O, S or CONR.sup.8, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted in each case by one or more R.sup.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, the R.sup.7 radicals do not form any such ring system; [0120] R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; [0121] c, c1, c2 at each instance are each independently 0 or 1, where the sum total of the indices at each instance c+c1+c2=1; [0122] d, d1, d2 at each instance are each independently 0 or 1, where the sum total of the indices at each instance d+d1+d2=1; [0123] q, q1, q2 at each instance are each independently 0 or 1; [0124] s is the same or different at each instance and is 0, 1, 2, 3 or 4; [0125] t is the same or different at each instance and is 0, 1, 2 or 3; [0126] u is the same or different at each instance and is 0, 1 or 2; [0127] u1, u2 at each instance are each independently 0 or 1, where the sum total u1+u2=1; and [0128] v is 0 or 1.

[0129] In compounds of the formula (6), (7), (8), (10) or (11), s is preferably 0 or 1 when the R.sup.6 radical is not D, or more preferably 0.

[0130] In compounds of the formula (6), (7) or (8), t is preferably 0 or 1 when the R.sup.6 radical is not D, or more preferably 0.

[0131] In compounds of the formula (6), (7), (8) or (10), u is preferably 0 or 1 when the R.sup.6 radical is not D, or more preferably 0.

[0132] The sum total of the indices s, t and u in compounds of the formulae (6), (7), (8), (10) and (11) is preferably not more than 6, especially preferably not more than 4 and more preferably not more than 2. This is preferably the case when R.sup.6 is not D.

[0133] In compounds of the formula (9), c, c1, c2 at each instance are each independently 0 or 1, where the sum total of the indices at each instance c+c1+c2 is 1. c2 is preferably defined as 1.

[0134] In compounds of the formula (9), L is preferably a single bond or C(R.sup.7).sub.2 where R.sup.7 has a definition given above; more preferably, L is a single bond.

[0135] In formula (4), U.sup.1 or U.sup.2 where they occur are preferably a single bond or C(R.sup.7).sub.2 where R.sup.7 has a definition given above; more preferably, U.sup.1 or U.sup.2 where they occur are a single bond.

[0136] In a preferred embodiment of the compounds of the formulae (6), (7), (8), (9), (10) and (11) that can be combined in accordance with the invention with compounds of the formula (1a) or of the formula (1b), as described above, R.sup.6 is the same or different at each instance and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group may in each case be substituted by one or more R.sup.7 radicals, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms, preferably 5 to 40 ring atoms, and may be substituted in each case by one or more R.sup.7 radicals.

[0137] In a preferred embodiment of the compounds of the formulae (6), (7), (8), (9), (10) and (11) that can be combined in accordance with the invention with compounds of the formula (1a) or of the formula (1b), R.sup.6 is the same or different at each instance and is selected from the group consisting of D and an aromatic or heteroaromatic ring system which has 6 to 30 ring atoms and may be substituted by one or more R.sup.7 radicals.

[0138] Preferably, Ar.sub.5 in compounds of the formulae (6), (7), (8), (10) and (11) is selected from phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorenyl which may be joined via the 1, 2, 3 or 4 position, spirobifluorenyl which may be joined via the 1, 2, 3 or 4 position, naphthyl, especially 1- or 2-bonded naphthyl, or radicals derived from indole, benzofuran, benzothiophene, carbazole which may be joined via the 1, 2, 3 or 4 position, dibenzofuran which may be joined via the 1, 2, 3 or 4 position, dibenzothiophene which may be joined via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more R.sup.7 radicals. Ar.sub.5 is preferably unsubstituted.

[0139] When A.sup.1 in formula (7) or (8) or (11) is NR.sup.7, the substituent R.sup.7 bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may also be substituted by one or more R.sup.8 radicals. In a particularly preferred embodiment, this substituent R.sup.7 is the same or different at each instance and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, especially having 6 to 18 aromatic ring atoms. Preferred embodiments of R.sup.7 are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, and radicals derived from triazine, pyrimidine and quinazoline, which may be substituted by one or more R.sup.8 radicals.

[0140] When A.sup.1 in formula (7) or (8) or (11) is C(R.sup.7).sub.2, the substituents R.sup.7 bonded to this carbon atom are preferably the same or different at each instance and are a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more R.sup.8 radicals. Most preferably, R.sup.7 is a methyl group or a phenyl group. In this case, the R.sup.7 radicals together may also form a ring system, which leads to a spiro system.

[0141] In a preferred embodiment of the compounds of the formulae (6), (7), (8), (9), (10) and (11), these compounds are partly or fully deuterated, more preferably fully deuterated.

[0142] The preparation of the compounds of the formulae (6), (7), (8), (9), (10) and (11) is generally known, and some of the compounds are commercially available.

[0143] Compounds of the formula (9) are disclosed, for example, in WO2021/180614, pages 110 to 119, especially as examples on pages 120 to 127. The preparation thereof is disclosed in WO2021/180614 on page 128, and in the synthesis examples on pages 214 to 218.

[0144] The preparation of the triarylamines of the formula (11) is known to the person skilled in the art, and some of the compounds are commercially available.

[0145] If the further matrix material is a deuterated compound, it is possible that the further matrix material is a mixture of deuterated compounds of the same chemical base structure that differ merely by the level of deuteration.

[0146] In a preferred embodiment of the further matrix material, this is a mixture of deuterated compounds of the formulae (6), (7), (8), (9), (10) and (11), as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%. The figures 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.

[0147] A suitable method of deuterating a compound by exchange of one or more hydrogen atoms for deuterium atoms is a treatment of the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source. The term deuterium source means any compound that contains one or more deuterium atoms and is able to release them under suitable conditions.

[0148] The platinum catalyst is preferably dry platinum on charcoal, preferably 5% dry platinum on charcoal. The palladium catalyst is preferably dry palladium on charcoal, preferably 5% dry palladium on charcoal. A suitable deuterium source is D.sub.2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4 or toluene-d8. A preferred deuterium source is D.sub.2O or a combination of D.sub.2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D.sub.2O with a fully deuterated organic solvent, where the fully deuterated solvent here is not restricted. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D.sub.2O and toluene-d8. The reaction is preferably conducted with heating, more preferably with heating to temperatures between 100 C. and 200 C. In addition, the reaction is preferably conducted under pressure.

[0149] Examples of suitable further matrix materials for a combination with compounds of the formula (1a) or of the formula (1b), as described above or described as preferred, are the compounds described in WO2019/229011, table 3, pages 137 to 203, which may also be partly or fully deuterated.

[0150] Examples of suitable further matrix materials for a combination with compounds of the formula (1a) or of the formula (1b), as described above or described as preferred, are the compounds described in WO2011/088877, table on page 30, compounds 1 to 166, which may also be partly or fully deuterated.

[0151] Examples of suitable further matrix materials for a combination with compounds of the formula (1a) or of the formula (1b), as described above or described as preferred, are the compounds described in WO2011/128017, table on page 23, compounds 1 to 151, which may also be partly or fully deuterated.

[0152] Compounds of the formula (6) that are especially suitable for a combination with a compound of the formula (1a) or of the formula (1b), as described above or described with preference, are those in which at least one Ar.sub.5 group is a heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.7 radicals or compounds of the formula (9) or (10).

[0153] Compounds of the formula (9) or (10) are suitable with very particular preference for a combination with a compound of the formula (1a) or of the formula (1b).

[0154] Compounds of the formula (10) are suitable with very particular preference for a combination with a compound of the formula (1a) or of the formula (1b).

[0155] Further examples of suitable host materials of the formulae (6), (7), (8), (9), (10) and (11) for a combination with compounds of the formula (1a) or (1b), as described above or described as preferred, are the structures in table 3 and table 4 that are given below.

TABLE-US-00003 TABLE 3 [00233] [00234] [00235] [00236] [00237] [00238] [00239] [00240] [00241] [00242] [00243] [00244] [00245] [00246] [00247] [00248] [00249] [00250] [00251] [00252] [00253] [00254] [00255] [00256] [00257] [00258] [00259] [00260] [00261] [00262] [00263] [00264] [00265] [00266] [00267] [00268] [00269] [00270] [00271] [00272] [00273] [00274] [00275] [00276] [00277] [00278] [00279] [00280] [00281] [00282] [00283] [00284] [00285] [00286] [00287] [00288] [00289] [00290] [00291] [00292] [00293] [00294] [00295] [00296] [00297] [00298]

[0156] Particularly suitable compounds of the formulae (6), (7), (8), (9), (10) and (11) that are selected in accordance with the invention and are preferably used in combination with at least one compound of the formula (1a) or of the formula (1b) in the electroluminescent device of the invention are the compounds in table 4.

TABLE-US-00004 TABLE 4 [00299] H1 [00300] H2 [00301] H3 [00302] H4 [00303] H5 [00304] H6 [00305] H7 [00306] H8 [00307] H9 [00308] H10 [00309] H11 [00310] H12 [00311] H13 [00312] H14 [00313] H15 [00314] H16 [00315] H17 [00316] H18 [00317] H19 [00318] H20 [00319] H21 [00320] H22 [00321] H23 [00322] H24 [00323] H25 [00324] H26 [00325] H27

[0157] The aforementioned host materials of the formulae (1a) and (1b) and the embodiments thereof that are described as preferred or the compounds from table 1 and compounds E1 to E36 can be combined as desired in the device of the invention with the aforementioned matrix materials/host materials, the matrix materials/host materials of the formulae (6), (7), (8), (9), (10) and (11) and their embodiments in table 3 that are described as preferred, or compounds H1 to H27.

[0158] The invention further provides a mixture comprising at least one compound of formula (1a) or formula (1b),

##STR00326## [0159] where the symbols and indices used are as follows: [0160] V at each instance is independently O or S; [0161] L.sub.1 is a linker selected from L-1 to L26 that may be partly or fully deuterated, or a combination of the linkers L-1 to L-26, where the linkers L-1 to L-26 may be partly or fully deuterated,

##STR00327## ##STR00328## ##STR00329## ##STR00330## [0162] V.sub.1 is O or S; [0163] the dashed lines denote the attachment to Rx and the remainder of the formula (1a) or formula (1b); [0164] Rx conforms to one of the formulae (1-2), (1-3), (1-4) and (1-5)

##STR00331## [0165] * denotes the attachment to L.sub.1, [0166] R.sup.1 at each instance is independently H, D, or undeuterated or partly or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; [0167] Ar, Ar.sub.1 are the same or different at each instance and are an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R.sup.2 radicals; [0168] Ar.sub.2, Ar.sub.3 are the same or different at each instance and are an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 9 to 40 ring atoms, each of which may be substituted by one or more R.sup.2 radicals; [0169] R.sup.2 is the same or different at each instance and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where one or more nonadjacent CH.sub.2 groups may be replaced by O or S and where one or more hydrogen atoms may be replaced by D, F, or CN; [0170] R #where it occurs is D or undeuterated or partly or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; [0171] [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 partly or fully substituted by D; [0172] b, b1 are each independently 0 or 1; [0173] b2 are each independently 0, 1, 2 or 3; [0174] with the condition for compounds of the formula (1a) that, when L.sub.1 is an undeuterated linker L-3 or L-8, L.sub.1-Rx is bound to the remainder of the formula (1a) only in position 6, 7 or 9, [0175] and at least one further compound selected from the group of the matrix materials, phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence).

[0176] Very particularly preferred mixtures of the compounds of the formulae (1a) and (1b) with the host materials of the formulae (6), (7), (8), (9), (10) and (11) for the device of the invention are obtained by combination of compounds E1 to E36 with compounds H1 to H27 as shown hereinafter in table 5. The first mixture M1, for example, is a combination of compound E1 with H1.

TABLE-US-00005 TABLE 5 M1 E1 H1 M2 E2 H1 M3 E3 H1 M4 E4 H1 M5 E5 H1 M6 E6 H1 M7 E7 H1 M8 E8 H1 M9 E9 H1 M10 E10 H1 M11 E11 H1 M12 E12 H1 M13 E13 H1 M14 E14 H1 M15 E15 H1 M16 E16 H1 M17 E17 H1 M18 E18 H1 M19 E19 H1 M20 E20 H1 M21 E21 H1 M22 E22 H1 M23 E23 H1 M24 E24 H1 M25 E25 H1 M26 E26 H1 M27 E27 H1 M28 E1 H2 M29 E2 H2 M30 E3 H2 M31 E4 H2 M32 E5 H2 M33 E6 H2 M34 E7 H2 M35 E8 H2 M36 E9 H2 M37 E10 H2 M38 E11 H2 M39 E12 H2 M40 E13 H2 M41 E14 H2 M42 E15 H2 M43 E16 H2 M44 E17 H2 M45 E18 H2 M46 E19 H2 M47 E20 H2 M48 E21 H2 M49 E22 H2 M50 E23 H2 M51 E24 H2 M52 E25 H2 M53 E26 H2 M54 E27 H2 M55 E1 H3 M56 E2 H3 M57 E3 H3 M58 E4 H3 M59 E5 H3 M60 E6 H3 M61 E7 H3 M62 E8 H3 M63 E9 H3 M64 E10 H3 M65 E11 H3 M66 E12 H3 M67 E13 H3 M68 E14 H3 M69 E15 H3 M70 E16 H3 M71 E17 H3 M72 E18 H3 M73 E19 H3 M74 E20 H3 M75 E21 H3 M76 E22 H3 M77 E23 H3 M78 E24 H3 M79 E25 H3 M80 E26 H3 M81 E27 H3 M82 E1 H4 M83 E2 H4 M84 E3 H4 M85 E4 H4 M86 E5 H4 M87 E6 H4 M88 E7 H4 M89 E8 H4 M90 E9 H4 M91 E10 H4 M92 E11 H4 M93 E12 H4 M94 E13 H4 M95 E14 H4 M96 E15 H4 M97 E16 H4 M98 E17 H4 M99 E18 H4 M100 E19 H4 M101 E20 H4 M102 E21 H4 M103 E22 H4 M104 E23 H4 M105 E24 H4 M106 E25 H4 M107 E26 H4 M108 E27 H4 M109 E1 H5 M110 E2 H5 M111 E3 H5 M112 E4 H5 M113 E5 H5 M114 E6 H5 M115 E7 H5 M116 E8 H5 M117 E9 H5 M118 E10 H5 M119 E11 H5 M120 E12 H5 M121 E13 H5 M122 E14 H5 M123 E15 H5 M124 E16 H5 M125 E17 H5 M126 E18 H5 M127 E19 H5 M128 E20 H5 M129 E21 H5 M130 E22 H5 M131 E23 H5 M132 E24 H5 M133 E25 H5 M134 E26 H5 M135 E27 H5 M136 E1 H6 M137 E2 H6 M138 E3 H6 M139 E4 H6 M140 E5 H6 M141 E6 H6 M142 E7 H6 M143 E8 H6 M144 E9 H6 M145 E10 H6 M146 E11 H6 M147 E12 H6 M148 E13 H6 M149 E14 H6 M150 E15 H6 M151 E16 H6 M152 E17 H6 M153 E18 H6 M154 E19 H6 M155 E20 H6 M156 E21 H6 M157 E22 H6 M158 E23 H6 M159 E24 H6 M160 E25 H6 M161 E26 H6 M162 E27 H6 M163 E1 H7 M164 E2 H7 M165 E3 H7 M166 E4 H7 M167 E5 H7 M168 E6 H7 M169 E7 H7 M170 E8 H7 M171 E9 H7 M172 E10 H7 M173 E11 H7 M174 E12 H7 M175 E13 H7 M176 E14 H7 M177 E15 H7 M178 E16 H7 M179 E17 H7 M180 E18 H7 M181 E19 H7 M182 E20 H7 M183 E21 H7 M184 E22 H7 M185 E23 H7 M186 E24 H7 M187 E25 H7 M188 E26 H7 M189 E27 H7 M190 E1 H8 M191 E2 H8 M192 E3 H8 M193 E4 H8 M194 E5 H8 M195 E6 H8 M196 E7 H8 M197 E8 H8 M198 E9 H8 M199 E10 H8 M200 E11 H8 M201 E12 H8 M202 E13 H8 M203 E14 H8 M204 E15 H8 M205 E16 H8 M206 E17 H8 M207 E18 H8 M208 E19 H8 M209 E20 H8 M210 E21 H8 M211 E22 H8 M212 E23 H8 M213 E24 H8 M214 E25 H8 M215 E26 H8 M216 E27 H8 M217 E1 H9 M218 E2 H9 M219 E3 H9 M220 E4 H9 M221 E5 H9 M222 E6 H9 M223 E7 H9 M224 E8 H9 M225 E9 H9 M226 E10 H9 M227 E11 H9 M228 E12 H9 M229 E13 H9 M230 E14 H9 M231 E15 H9 M232 E16 H9 M233 E17 H9 M234 E18 H9 M235 E19 H9 M236 E20 H9 M237 E21 H9 M238 E22 H9 M239 E23 H9 M240 E24 H9 M241 E25 H9 M242 E26 H9 M243 E27 H9 M244 E1 H10 M245 E2 H10 M246 E3 H10 M247 E4 H10 M248 E5 H10 M249 E6 H10 M250 E7 H10 M251 E8 H10 M252 E9 H10 M253 E10 H10 M254 E11 H10 M255 E12 H10 M256 E13 H10 M257 E14 H10 M258 E15 H10 M259 E16 H10 M260 E17 H10 M261 E18 H10 M262 E19 H10 M263 E20 H10 M264 E21 H10 M265 E22 H10 M266 E23 H10 M267 E24 H10 M268 E25 H10 M269 E26 H10 M270 E27 H10 M271 E1 H11 M272 E2 H11 M273 E3 H11 M274 E4 H11 M275 E5 H11 M276 E6 H11 M277 E7 H11 M278 E8 H11 M279 E9 H11 M280 E10 H11 M281 E11 H11 M282 E12 H11 M283 E13 H11 M284 E14 H11 M285 E15 H11 M286 E16 H11 M287 E17 H11 M288 E18 H11 M289 E19 H11 M290 E20 H11 M291 E21 H11 M292 E22 H11 M293 E23 H11 M294 E24 H11 M295 E25 H11 M296 E26 H11 M297 E27 H11 M298 E1 H12 M299 E2 H12 M300 E3 H12 M301 E4 H12 M302 E5 H12 M303 E6 H12 M304 E7 H12 M305 E8 H12 M306 E9 H12 M307 E10 H12 M308 E11 H12 M309 E12 H12 M310 E13 H12 M311 E14 H12 M312 E15 H12 M313 E16 H12 M314 E17 H12 M315 E18 H12 M316 E19 H12 M317 E20 H12 M318 E21 H12 M319 E22 H12 M320 E23 H12 M321 E24 H12 M322 E25 H12 M323 E26 H12 M324 E27 H12 M325 E1 H13 M326 E2 H13 M327 E3 H13 M328 E4 H13 M329 E5 H13 M330 E6 H13 M331 E7 H13 M332 E8 H13 M333 E9 H13 M334 E10 H13 M335 E11 H13 M336 E12 H13 M337 E13 H13 M338 E14 H13 M339 E15 H13 M340 E16 H13 M341 E17 H13 M342 E18 H13 M343 E19 H13 M344 E20 H13 M345 E21 H13 M346 E22 H13 M347 E23 H13 M348 E24 H13 M349 E25 H13 M350 E26 H13 M351 E27 H13 M352 E1 H14 M353 E2 H14 M354 E3 H14 M355 E4 H14 M356 E5 H14 M357 E6 H14 M358 E7 H14 M359 E8 H14 M360 E9 H14 M361 E10 H14 M362 E11 H14 M363 E12 H14 M364 E13 H14 M365 E14 H14 M366 E15 H14 M367 E16 H14 M368 E17 H14 M369 E18 H14 M370 E19 H14 M371 E20 H14 M372 E21 H14 M373 E22 H14 M374 E23 H14 M375 E24 H14 M376 E25 H14 M377 E26 H14 M378 E27 H14 M379 E1 H15 M380 E2 H15 M381 E3 H15 M382 E4 H15 M383 E5 H15 M384 E6 H15 M385 E7 H15 M386 E8 H15 M387 E9 H15 M388 E10 H15 M389 E11 H15 M390 E12 H15 M391 E13 H15 M392 E14 H15 M393 E15 H15 M394 E16 H15 M395 E17 H15 M396 E18 H15 M397 E19 H15 M398 E20 H15 M399 E21 H15 M400 E22 H15 M401 E23 H15 M402 E24 H15 M403 E25 H15 M404 E26 H15 M405 E27 H15 M406 E1 H16 M407 E2 H16 M408 E3 H16 M409 E4 H16 M410 E5 H16 M411 E6 H16 M412 E7 H16 M413 E8 H16 M414 E9 H16 M415 E10 H16 M416 E11 H16 M417 E12 H16 M418 E13 H16 M419 E14 H16 M420 E15 H16 M421 E16 H16 M422 E17 H16 M423 E18 H16 M424 E19 H16 M425 E20 H16 M426 E21 H16 M427 E22 H16 M428 E23 H16 M429 E24 H16 M430 E25 H16 M431 E26 H16 M432 E27 H16 M433 E1 H17 M434 E2 H17 M435 E3 H17 M436 E4 H17 M437 E5 H17 M438 E6 H17 M439 E7 H17 M440 E8 H17 M441 E9 H17 M442 E10 H17 M443 E11 H17 M444 E12 H17 M445 E13 H17 M446 E14 H17 M447 E15 H17 M448 E16 H17 M449 E17 H17 M450 E18 H17 M451 E19 H17 M452 E20 H17 M453 E21 H17 M454 E22 H17 M455 E23 H17 M456 E24 H17 M457 E25 H17 M458 E26 H17 M459 E27 H17 M460 E1 H18 M461 E2 H18 M462 E3 H18 M463 E4 H18 M464 E5 H18 M465 E6 H18 M466 E7 H18 M467 E8 H18 M468 E9 H18 M469 E10 H18 M470 E11 H18 M471 E12 H18 M472 E13 H18 M473 E14 H18 M474 E15 H18 M475 E16 H18 M476 E17 H18 M477 E18 H18 M478 E19 H18 M479 E20 H18 M480 E21 H18 M481 E22 H18 M482 E23 H18 M483 E24 H18 M484 E25 H18 M485 E26 H18 M486 E27 H18 M487 E1 H19 M488 E2 H19 M489 E3 H19 M490 E4 H19 M491 E5 H19 M492 E6 H19 M493 E7 H19 M494 E8 H19 M495 E9 H19 M496 E10 H19 M497 E11 H19 M498 E12 H19 M499 E13 H19 M500 E14 H19 M501 E15 H19 M502 E16 H19 M503 E17 H19 M504 E18 H19 M505 E19 H19 M506 E20 H19 M507 E21 H19 M508 E22 H19 M509 E23 H19 M510 E24 H19 M511 E25 H19 M512 E26 H19 M513 E27 H19 M514 E1 H20 M515 E2 H20 M516 E3 H20 M517 E4 H20 M518 E5 H20 M519 E6 H20 M520 E7 H20 M521 E8 H20 M522 E9 H20 M523 E10 H20 M524 E11 H20 M525 E12 H20 M526 E13 H20 M527 E14 H20 M528 E15 H20 M529 E16 H20 M530 E17 H20 M531 E18 H20 M532 E19 H20 M533 E20 H20 M534 E21 H20 M535 E22 H20 M536 E23 H20 M537 E24 H20 M538 E25 H20 M539 E26 H20 M540 E27 H20 M541 E1 H21 M542 E2 H21 M543 E3 H21 M544 E4 H21 M545 E5 H21 M546 E6 H21 M547 E7 H21 M548 E8 H21 M549 E9 H21 M550 E10 H21 M551 E11 H21 M552 E12 H21 M553 E13 H21 M554 E14 H21 M555 E15 H21 M556 E16 H21 M557 E17 H21 M558 E18 H21 M559 E19 H21 M560 E20 H21 M561 E21 H21 M562 E22 H21 M563 E23 H21 M564 E24 H21 M565 E25 H21 M566 E26 H21 M567 E27 H21 M568 E1 H22 M569 E2 H22 M570 E3 H22 M571 E4 H22 M572 E5 H22 M573 E6 H22 M574 E7 H22 M575 E8 H22 M576 E9 H22 M577 E10 H22 M578 E11 H22 M579 E12 H22 M580 E13 H22 M581 E14 H22 M582 E15 H22 M583 E16 H22 M584 E17 H22 M585 E18 H22 M586 E19 H22 M587 E20 H22 M588 E21 H22 M589 E22 H22 M590 E23 H22 M591 E24 H22 M592 E25 H22 M593 E26 H22 M594 E27 H22 M595 E1 H23 M596 E2 H23 M597 E3 H23 M598 E4 H23 M599 E5 H23 M600 E6 H23 M601 E7 H23 M602 E8 H23 M603 E9 H23 M604 E10 H23 M605 E11 H23 M606 E12 H23 M607 E13 H23 M608 E14 H23 M609 E15 H23 M610 E16 H23 M611 E17 H23 M612 E18 H23 M613 E19 H23 M614 E20 H23 M615 E21 H23 M616 E22 H23 M617 E23 H23 M618 E24 H23 M619 E25 H23 M620 E26 H23 M621 E27 H23 M622 E1 H24 M623 E2 H24 M624 E3 H24 M625 E4 H24 M626 E5 H24 M627 E6 H24 M628 E7 H24 M629 E8 H24 M630 E9 H24 M631 E10 H24 M632 E11 H24 M633 E12 H24 M634 E13 H24 M635 E14 H24 M636 E15 H24 M637 E16 H24 M638 E17 H24 M639 E18 H24 M640 E19 H24 M641 E20 H24 M642 E21 H24 M643 E22 H24 M644 E23 H24 M645 E24 H24 M646 E25 H24 M647 E26 H24 M648 E27 H24 M649 E1 H25 M650 E2 H25 M651 E3 H25 M652 E4 H25 M653 E5 H25 M654 E6 H25 M655 E7 H25 M656 E8 H25 M657 E9 H25 M658 E10 H25 M659 E11 H25 M660 E12 H25 M661 E13 H25 M662 E14 H25 M663 E15 H25 M664 E16 H25 M665 E17 H25 M666 E18 H25 M667 E19 H25 M668 E20 H25 M669 E21 H25 M670 E22 H25 M671 E23 H25 M672 E24 H25 M673 E25 H25 M674 E26 H25 M675 E27 H25 M676 E1 H26 M677 E2 H26 M678 E3 H26 M679 E4 H26 M680 E5 H26 M681 E6 H26 M682 E7 H26 M683 E8 H26 M684 E9 H26 M685 E10 H26 M686 E11 H26 M687 E12 H26 M688 E13 H26 M689 E14 H26 M690 E15 H26 M691 E16 H26 M692 E17 H26 M693 E18 H26 M694 E19 H26 M695 E20 H26 M696 E21 H26 M697 E22 H26 M698 E23 H26 M699 E24 H26 M700 E25 H26 M701 E26 H26 M702 E27 H26 M703 E1 H27 M704 E2 H27 M705 E3 H27 M706 E4 H27 M707 E5 H27 M708 E6 H27 M709 E7 H27 M710 E8 H27 M711 E9 H27 M712 E10 H27 M713 E11 H27 M714 E12 H27 M715 E13 H27 M716 E14 H27 M717 E15 H27 M718 E16 H27 M719 E17 H27 M720 E18 H27 M721 E19 H27 M722 E20 H27 M723 E21 H27 M724 E22 H27 M725 E23 H27 M726 E24 H27 M727 E25 H27 M728 E26 H27 M729 E27 H27 M730 H1 E28 M731 H2 E28 M732 H3 E28 M733 H4 E28 M734 H5 E28 M735 H6 E28 M736 H7 E28 M737 H8 E28 M738 H9 E28 M739 H10 E28 M740 H11 E28 M741 H12 E28 M742 H13 E28 M743 H14 E28 M744 H15 E28 M745 H16 E28 M746 H17 E28 M747 H18 E28 M748 H19 E28 M749 H20 E28 M750 H21 E28 M751 H22 E28 M752 H23 E28 M753 H24 E28 M754 H25 E28 M755 H26 E28 M756 H27 E28 M757 H1 E29 M758 H2 E29 M759 H3 E29 M760 H4 E29 M761 H5 E29 M762 H6 E29 M763 H7 E29 M764 H8 E29 M765 H9 E29 M766 H10 E29 M767 H11 E29 M768 H12 E29 M769 H13 E29 M770 H14 E29 M771 H15 E29 M772 H16 E29 M773 H17 E29 M774 H18 E29 M775 H19 E29 M776 H20 E29 M777 H21 E29 M778 H22 E29 M779 H23 E29 M780 H24 E29 M781 H25 E29 M782 H26 E29 M783 H27 E29 M784 H1 E30 M785 H2 E30 M786 H3 E30 M787 H4 E30 M788 H5 E30 M789 H6 E30 M790 H7 E30 M791 H8 E30 M792 H9 E30 M793 H10 E30 M794 H11 E30 M795 H12 E30 M796 H13 E30 M797 H14 E30 M798 H15 E30 M799 H16 E30 M800 H17 E30 M801 H18 E30 M802 H19 E30 M803 H20 E30 M804 H21 E30 M805 H22 E30 M806 H23 E30 M807 H24 E30 M808 H25 E30 M809 H26 E30 M810 H27 E30 M811 H1 E31 M812 H2 E31 M813 H3 E31 M814 H4 E31 M815 H5 E31 M816 H6 E31 M817 H7 E31 M818 H8 E31 M819 H9 E31 M820 H10 E31 M821 H11 E31 M822 H12 E31 M823 H13 E31 M824 H14 E31 M825 H15 E31 M826 H16 E31 M827 H17 E31 M828 H18 E31 M829 H19 E31 M830 H20 E31 M831 H21 E31 M832 H22 E31 M833 H23 E31 M834 H24 E31 M835 H25 E31 M836 H26 E31 M837 H27 E31 M838 H1 E32 M839 H2 E32 M840 H3 E32 M841 H4 E32 M842 H5 E32 M843 H6 E32 M844 H7 E32 M845 H8 E32 M846 H9 E32 M847 H10 E32 M848 H11 E32 M849 H12 E32 M850 H13 E32 M851 H14 E32 M852 H15 E32 M853 H16 E32 M854 H17 E32 M855 H18 E32 M856 H19 E32 M857 H20 E32 M858 H21 E32 M859 H22 E32 M860 H23 E32 M861 H24 E32 M862 H25 E32 M863 H26 E32 M864 H27 E32 M865 H1 E33 M866 H2 E33 M867 H3 E33 M868 H4 E33 M869 H5 E33 M870 H6 E33 M871 H7 E33 M872 H8 E33 M873 H9 E33 M874 H10 E33 M875 H11 E33 M876 H12 E33 M877 H13 E33 M878 H14 E33 M879 H15 E33 M880 H16 E33 M881 H17 E33 M882 H18 E33 M883 H19 E33 M884 H20 E33 M885 H21 E33 M886 H22 E33 M887 H23 E33 M888 H24 E33 M889 H25 E33 M890 H26 E33 M891 H27 E33 M892 H1 E34 M893 H2 E34 M894 H3 E34 M895 H4 E34 M896 H5 E34 M897 H6 E34 M898 H7 E34 M899 H8 E34 M900 H9 E34 M901 H10 E34 M902 H11 E34 M903 H12 E34 M904 H13 E34 M905 H14 E34 M906 H15 E34 M907 H16 E34 M908 H17 E34 M909 H18 E34 M910 H19 E34 M911 H20 E34 M912 H21 E34 M913 H22 E34 M914 H23 E34 M915 H24 E34 M916 H25 E34 M917 H26 E34 M918 H27 E34 M919 H1 E35 M920 H2 E35 M921 H3 E35 M922 H4 E35 M923 H5 E35 M924 H6 E35 M925 H7 E35 M926 H8 E35 M927 H9 E35 M928 H10 E35 M929 H11 E35 M930 H12 E35 M931 H13 E35 M932 H14 E35 M933 H15 E35 M934 H16 E35 M935 H17 E35 M936 H18 E35 M937 H19 E35 M938 H20 E35 M939 H21 E35 M940 H22 E35 M941 H23 E35 M942 H24 E35 M943 H25 E35 M944 H26 E35 M945 H27 E35 M946 H1 E36 M947 H2 E36 M948 H3 E36 M949 H4 E36 M950 H5 E36 M951 H6 E36 M952 H7 E36 M953 H8 E36 M954 H9 E36 M955 H10 E36 M956 H11 E36 M957 H12 E36 M958 H13 E36 M959 H14 E36 M960 H15 E36 M961 H16 E36 M962 H17 E36 M963 H18 E36 M964 H19 E36 M965 H20 E36 M966 H21 E36 M967 H22 E36 M968 H23 E36 M969 H24 E36 M970 H25 E36 M971 H26 E36 M972 H27 E36

[0177] The concentration of the host material of the formula (1a) or of the formula (1b) as described above or described as preferred in the mixture of the invention or in the light-emitting layer of the device of the invention is typically in the range from 5% by weight to 90% by weight, preferably in the range from 10% by weight to 85% by weight, more preferably in the range from 20% by weight to 85% by weight, even more preferably in the range from 30% by weight to 80% by weight, very especially preferably in the range from 20% by weight to 60% by weight and most preferably in the range from 30% by weight to 50% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0178] The concentration of the host material of one of the formulae (6), (7), (8), (9), (10) and (11) as described above or described as preferred in the mixture of the invention or in the light-emitting layer of the device of the invention is typically in the range from 10% by weight to 95% by weight, preferably in the range from 15% by weight to 90% by weight, more preferably in the range from 15% by weight to 80% by weight, even more preferably in the range from 20% by weight to 70% by weight, very especially preferably in the range from 40% by weight to 80% by weight and most preferably in the range from 50% by weight to 70% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

[0179] The present invention also relates to a mixture which, as well as the aforementioned host materials of the formula (1a) or of the formula (1b), called host material 1 hereinafter, and the host material of one of the formulae (6), (7), (8), (9), (10) and (11), called host material 2 hereinafter, as described above or described as preferred, especially mixtures M1 to M972, also comprises at least one phosphorescent emitter.

[0180] The present invention also relates to an organic electroluminescent device as described above or described as preferred, wherein the light-emitting layer, as well as the aforementioned host materials of the formulae (1a) and (1b) and one of the formulae (6), (7), (8), (9), (10) and (11), as described above or described as preferred, especially the material combinations M1 to M972, also comprises at least one phosphorescent emitter. The term phosphorescent emitters typically encompasses compounds where the light is emitted through a spin-forbidden transition from an excited state having higher spin multiplicity, i.e. a spin state >1, for example through a transition from a triplet state or a state having an even higher spin quantum number, for example a quintet state. This preferably means a transition from a triplet state.

[0181] Suitable phosphorescent emitters (=triplet emitters) are especially compounds which, when suitably excited, emit light, preferably in the visible region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the abovementioned metals are regarded as phosphorescent emitters.

[0182] In general, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to those skilled in the art in the field of organic electroluminescent devices are suitable.

[0183] Preferred phosphorescent emitters according to the present invention conform to the formula (IIIa)

##STR00332## [0184] where the symbols and indices for this formula (IIIa) are defined as follows: [0185] n+m is 3, n is 1 or 2, m is 2 or 1, [0186] X is the same or different at each instance and is N or CR, [0187] R is the same or different at each instance and is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated, branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be partly or fully substituted by deuterium, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be partly or fully substituted by deuterium.

[0188] The invention accordingly further provides an organic electroluminescent device as described above or described as preferred, characterized in that the light-emitting layer, as well as the host materials 1 and 2, comprises at least one phosphorescent emitter conforming to the formula (IIIa) as described above.

[0189] In emitters of the formula (IIIa), n is preferably 1 and m is preferably 2.

[0190] In emitters of the formula (IIIa), preferably, one X is selected from N and the other X are CR, or all X are the same or different at each instance and are CR.

[0191] In emitters of the formula (IIIa), at least one R is preferably different than H. In emitters of the formula (IIIa), preferably two R are different than H and have one of the other definitions given above for the emitters of the formula (IIIa).

[0192] Preferred phosphorescent emitters according to the present invention conform to the formulae (I), (II), (III), (IV) or (V)

##STR00333## [0193] where the symbols and indices for these formulae (I), (II), (III), (IV) and (V) are defined as follows: [0194] R.sup.1 is H or D, R.sup.2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group which has 4 to 10 carbon atoms and may be partly or fully substituted by deuterium.

[0195] Preferred phosphorescent emitters according to the present invention conform to the formulae (VI), (VII) or (VIII)

##STR00334## [0196] where the symbols and indices for these formulae (VI), (VII) and (VIII) are defined as follows: [0197] R.sub.1 is H or D, R.sub.2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group which has 4 to 10 carbon atoms and may be partly or fully substituted by deuterium.

[0198] 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 description by this reference.

[0199] Particularly preferred examples of phosphorescent emitters are listed in table 6 below.

TABLE-US-00006 TABLE 6 [00335] [00336] [00337] [00338] [00339] [00340] [00341] [00342] [00343] [00344] [00345] [00346] [00347] [00348] [00349] [00350] [00351] [00352] [00353] [00354] [00355] [00356] [00357] [00358] [00359] [00360] [00361] [00362] [00363] [00364] [00365] [00366] [00367] [00368] [00369] [00370] [00371] [00372] [00373] [00374] [00375] [00376] [00377] [00378] [00379] [00380] [00381] [00382] [00383] [00384] [00385] [00386] [00387] [00388] [00389] [00390] [00391] [00392] [00393] [00394] [00395] [00396] [00397] [00398] [00399] [00400] [00401] [00402] [00403]

[0200] In the mixtures of the invention or in the light-emitting layer of the device of the invention, any 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 formulae (I) to (VIII) or a compound from table 6.

[0201] The light-emitting layer in the organic electroluminescent device of the invention, comprising at least one phosphorescent emitter, is preferably an infrared-emitting or yellow-, orange-, red-, green-, blue- or ultraviolet-emitting layer, more preferably a yellow- or green-emitting layer and most preferably a green-emitting layer.

[0202] What is meant here by a yellow-emitting layer is a layer having a photoluminescence maximum within the range from 540 to 570 nm. What is meant by an orange-emitting layer is a layer having a photoluminescence maximum within the range from 570 to 600 nm. What is meant by a red-emitting layer is a layer having a photoluminescence maximum within the range from 600 to 750 nm. What is meant by a green-emitting layer is a layer having a photoluminescence maximum within the range from 490 to 540 nm. What is meant by a blue-emitting layer is a layer having a photoluminescence maximum within the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined here by measuring the photoluminescence spectrum of the layer having a layer thickness of 50 nm at room temperature, the layer having the inventive combination of the host materials of the formulae (1a) and (1b) and one of the formulae (6), (7), (8), (9), (10) and (11) and the appropriate emitter.

[0203] The photoluminescence spectrum of the layer is recorded, for example, with a commercial photoluminescence spectrometer.

[0204] The photoluminescence spectrum of the emitter chosen is generally measured in oxygen-free solution, 10.sup.5 molar, at room temperature, a suitable solvent being any in which the chosen emitter dissolves in the concentration mentioned. Particularly suitable solvents are typically toluene or 2-methyl-THF, but also dichloromethane. Measurement is effected with a commercial 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 by: E(T1 in eV)=1240/E(T1 in nm)=1240/PLmax. (in nm).

[0205] Preferred phosphorescent emitters are accordingly yellow emitters, preferably of the formula (IIIa), of the formulae (I) to (VIII) or from table 6, the triplet energy T1 of which is preferably 2.3 eV to 2.1 eV.

[0206] Preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (IIIa), of the formulae (I) to (VIII) or from table 6, the triplet energy T1 of which is preferably 2.5 eV to 2.3 eV.

[0207] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (IIIa), of the formulae (I) to (VIII) or from table 6 as described above, the triplet energy T1 of which is preferably 2.5 eV to 2.3 eV.

[0208] Most preferably, green emitters, preferably of the formula (IIIa), of the formulae (I) to (VIII) or from table 6, as described above, are selected for the mixture of the invention or emitting layer of the invention.

[0209] It is also possible for fluorescent emitters to be present in the light-emitting layer of the device of the invention or in the mixture of the invention.

[0210] Preferred fluorescent emitting compounds are selected from the class of the arylamines, where preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines or aromatic chrysenediamines. What is meant by an aromatic anthraceneamine is a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9 position. What is meant by an aromatic anthracenediamine is a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 positions. Aromatic pyreneamines, pyrenediamines, chryseneamines and chrysenediamines are defined analogously, where the diarylamino groups are bonded to the pyrene preferably in the 1 position or 1,6 positions. Further preferred emitting compounds are indenofluoreneamines or -diamines, benzoindenofluoreneamines or -diamines, and dibenzoindenofluoreneamines or -diamines, and indenofluorene derivatives having fused aryl groups. Likewise preferred are pyrenearylamines. Likewise preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives joined to furan units or to thiophene units. The light-emitting device or the mixture of the invention may additionally also comprise materials that exhibit TADF (thermally activated delayed fluorescence).

[0211] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device, as well as the host materials 1 and 2 as described above or described as preferred, may comprise further host materials or matrix materials, called mixed matrix systems. The mixed matrix systems preferably comprise three or four different matrix materials, more preferably three different matrix materials (in other words, one further matrix component in addition to the host materials 1 and 2 as described above). Particularly suitable matrix materials which can be used in combination as matrix component in a mixed matrix system are selected from wide-band gap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM). Preferably, the mixed matrix system is optimized for an emitter of the formula (IIIa), the formulae (I) to (VIII), or from table 6.

[0212] In one embodiment of the present invention, the mixture, as well as the constituents of the host material of the formula (1a) or of the formula (1b) and the host material 2 as described above, does not comprise any further constituents, i.e. functional materials. These are material mixtures that are used as such for production of the light-emitting layer. These mixtures are also referred to as premix systems that are used as the sole material source in the vapor deposition of the host materials for the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, it is possible in a simple and rapid manner to achieve the vapor deposition of a layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

[0213] In an alternative embodiment of the present invention, the mixture, as well as the constituents of the host material of the formula (1a) or of the formula (1b) and the host material 2 as described above, also comprises a phosphorescent emitter, as described above. In the case of a suitable mixing ratio in the vapor deposition, this mixture may also be used as the sole material source as described above.

[0214] The components or constituents of the light-emitting layer of the device of the invention may thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2 as described above or described as preferred, optionally with the phosphorescent emitter as described above or described as preferred, are provided for that purpose in a formulation containing at least one solvent. Suitable formulations have been described above.

[0215] The light-emitting layer in the device of the invention, according to the preferred embodiments and the emitting compound, contains preferably between 99.9% and 1% by volume, further preferably between 99% and 10% by volume, especially preferably between 98% and 60% by volume, very especially preferably between 97% and 80% by volume, of matrix material composed of at least one compound of the formula (1a) or of the formula (1b) and at least one compound of the one of the formulae (6), (7), (8), (9), (10) and (11) according to the preferred embodiments, based on the overall composition of emitter and matrix material. Correspondingly, the light-emitting layer in the device of the invention preferably contains between 0.1% and 99% by volume, further preferably between 1% and 90% by volume, more preferably between 2% and 40% by volume, most preferably between 3% and 20% by volume, of the emitter based on the overall composition of the light-emitting layer composed of emitter and matrix material. If the compounds are processed from solution, preference is given to using the corresponding amounts in % by weight rather than the above-specified amounts in % by volume.

[0216] The present invention also relates to an organic electroluminescent device as described above or described as preferred, wherein the organic layer comprises a hole injection layer (HIL) and/or a hole transport layer (HTL), the hole-injecting material and hole-transporting material of which belongs to the class of the arylamines.

[0217] The sequence of layers in the organic electroluminescent device of the invention is preferably as follows: [0218] anode/hole injection layer/hole transport layer/emitting layer/hole blocker layer/electron transport layer/electron injection layer/cathode.

[0219] This sequence of the layers is a preferred sequence.

[0220] At the same time, it should be pointed out again that not all the layers mentioned need be present and/or that further layers may additionally be present.

[0221] Materials used for the electron transport layer may be any materials as used according to the prior art as electron transport materials in the electron transport layer. Especially suitable are aluminum complexes, for example Alq.sub.3, zirconium complexes, for example Zrq.sub.4, 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.

[0222] Suitable cathodes of the device of the invention are metals having a low work function, metal alloys or multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals having a relatively high work function, for example Ag or Al, in which case combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag, for example, are generally used. It may also be preferable to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, Li.sub.2O, BaF.sub.2, MgO, NaF, CsF, Cs.sub.2CO.sub.3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

[0223] Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal/metal oxide electrodes (e.g. Al/Ni/NiO.sub.x, Al/PtO.sub.x) may also be preferred. For some applications, at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the outcoupling 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). Preference is further given to conductive doped organic materials, especially conductive doped polymers. In addition, the anode may also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0224] The organic electroluminescent device of the invention, in the course of production, is appropriately (according to the application) structured, contact-connected and finally sealed, since the lifetime of the devices of the invention is shortened in the presence of water and/or air.

[0225] The production of the device of the invention is not restricted here. It is possible that one or more organic layers, including the light-emitting layer, are coated by a sublimation method. In this case, the materials are applied by vapor deposition in vacuum sublimation systems at an initial pressure of less than 10.sup.5 mbar, preferably less than 10.sup.6 mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10.sup.7 mbar.

[0226] The organic electroluminescent device of the invention is preferably characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of a carrier gas sublimation. In this case, the materials are applied at a pressure between 10.sup.5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the materials are applied directly by a nozzle and thus structured (for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0227] The organic electroluminescent device of the invention is further preferably characterized in that one or more organic layers comprising the composition of the invention are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble host materials 1 and 2 and phosphorescent emitters are needed. Processing from solution has the advantage that, for example, the light-emitting layer can be applied in a very simple and inexpensive manner. This technique is especially suitable for the mass production of organic electroluminescent devices.

[0228] In addition, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0229] These methods are known in general terms to those skilled in the art and can be applied to organic electroluminescent devices.

[0230] The invention therefore further provides a process for producing the organic electroluminescent device of the invention as described above or described as preferred, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and/or hole transport layer, is applied by gas phase deposition, especially by a sublimation method and/or by an OVPD (organic vapor phase deposition) method and/or with the aid of a carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.

[0231] In the case of production by means of gas phase deposition, there are in principle two ways in which the organic layer, preferably the light-emitting layer, of the invention can be applied or vapor-deposited onto any substrate or the prior layer. Firstly, the materials used can each be initially charged in a material source and ultimately evaporated from the different material sources (co-evaporation). Secondly, the various materials can be premixed (premix systems) and the mixture can be initially charged in a single material source from which it is ultimately evaporated (premix evaporation). In this way, it is possible in a simple and rapid manner to achieve the vapor deposition of the light-emitting layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

[0232] The invention accordingly further provides a process for producing the device of 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 the formula (1a) or of the formula (1b) is deposited from the gas phase together with the further materials that form the light-emitting layer, successively or simultaneously from at least two material sources.

[0233] In a preferred embodiment of the present invention, the light-emitting layer is applied by means of gas phase deposition, wherein the constituents of the composition are premixed and evaporated from a single material source.

[0234] The invention accordingly further provides a process for producing the device of 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 the formula (1a) or of the formula (1b) is deposited from the gas phase together with at least one further matrix material as premix, successively or simultaneously with the light-emitting materials selected from the group of the phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence).

[0235] The electronic devices of the invention, especially organic electroluminescent devices, are notable for one or more of the following surprising advantages over the prior art: [0236] 1. Electronic devices, especially organic electroluminescent devices, comprising compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter, especially as matrix material, have a very good lifetime. In this context, these compounds especially bring about low roll-off, i.e. a small drop in power efficiency of the device at high luminances. [0237] 2. Electronic devices, especially organic electroluminescent devices, comprising compounds of formula (1a) or formula (1b) or the preferred embodiments as matrix materials recited above and hereinafter, have excellent efficiency. In this context, inventive compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter bring about a low operating voltage when used in electronic devices. [0238] 3. The inventive compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter exhibit very high stability and lifetime. [0239] 4. With compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter, it is possible to avoid the formation of optical loss channels in electronic devices, especially organic electroluminescent devices. As a result, these devices feature a high PL efficiency and hence high EL efficiency of emitters, and excellent energy transmission of the matrices to dopants. [0240] 5. The use of compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter in layers of electronic devices, especially organic electroluminescent devices, leads to high mobility of the electron conductor structures. [0241] 6. Compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter have excellent glass film formation. [0242] 7. Compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter form very good films from solutions. [0243] 8. The compounds of formula (1a) or formula (1b) or the preferred embodiments recited above and hereinafter have a triplet level T1 which may, for example, be in the range of 2.50 eV-2.90 eV.

[0244] These abovementioned advantages are not accompanied by an inordinately high deterioration in the further electronic properties.

[0245] It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Any feature disclosed in the present invention, unless stated otherwise, should therefore be considered as an example from a generic series or as an equivalent or similar feature.

[0246] All features of the present invention may be combined with one another in any manner, unless particular features and/or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

[0247] The technical teaching disclosed with the present invention may be abstracted and combined with other examples.

[0248] The invention is illustrated in detail by the examples which follow, without any intention of restricting it thereby.

EXAMPLES

General Methods

[0249] In all quantum-chemical calculations, the Gaussian 16 (Rev. B.01) software package is used. 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 B3LYP/6-31G(d)-optimized ground state energy. Then TD-DFT singlet and triplet excitations (vertical excitations) are calculated by the same method (B3LYP/6-31G(d)) and with the optimized ground state geometry. The standard settings for SCF and gradient convergence are used.

[0250] From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (alpha occ. eigenvalues) and LUMO as the first unoccupied orbital (alpha virt. eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units respectively. This is used to determine the HOMO and LUMO value in electron volts, calibrated by cyclic voltammetry measurements, as follows:

[00001]$\mathrm{HOMO}\mathrm{corr}=0.90603*\mathrm{HOMO}-0.84836$$\mathrm{LUMO}\mathrm{corr}=0.99687*\mathrm{LUMO}-0.72445$

[0251] The triplet level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state having the lowest energy which is found by the quantum-chemical energy calculation.

[0252] The singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state having the second-lowest energy which is found by the quantum-chemical energy calculation.

[0253] The energetically lowest singlet state is referred to as S0.

[0254] The method described herein is independent of the software package used and always gives the same results. Examples of frequently utilized programs for this purpose are Gaussian09 (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In the present case, the energies are calculated using the software package Gaussian16 (Rev. B.01).

SYNTHESIS EXAMPLES

[0255] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared by means of synthesis methods known to those skilled in the art.

a) (3-Amino-4-chloro-2-benzofuranyl)phenylmethanone

##STR00404##

[0256] To a solution of 99 g (489 mmol) of 2-bromo-6-hydroxybenzonitrile and 99.5 g (489 mmol) of bromoacetophenone in 790 ml of acetone are added in portions, at room temperature under argon, 319 g (979 mmol) of cesium carbonate.

[0257] The reaction mixture is heated to 60 for 2 hours. Subsequently, the mixture is cooled to room temperature, then filtered and then concentrated to dryness under reduced pressure, and recrystallized from heptane.

[0258] The yield is 107 g (316 mmol), corresponding to 69% of theory.

[0259] In an analogous manner, the following brominated compounds are prepared:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield 1a [00405] [00406] [00407] 66% 2a [00408] [00409] [00410] 54% 3a [00411] [00412] [00413] 57% 4a [00414] [00415] [00416] 52% 5a [00417] [00418] [00419] 57%

b) 6-Bromo-2-cyanophenyl Benzoate

##STR00420##

[0260] An initially charged 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 CH.sub.2Cl.sub.2 is 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 Et.sub.2O. The combined organic phase is dried over MgSO.sub.4. 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).

[0261] Yield: 10.4 g (33 mmol), 70% of theory.

c) S-(2-Cyano-3-bromophenyl)benzenecarbothionate

##STR00421##

[0262] 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 CuI, 0.9 (20 mol %, 5 mmol) of 1,10-phenanthroline and 5.1 g (37.5 mmol) of thiobenzoic acid are added under nitrogen to 20 ml of degassed toluene, and the mixture is stirred at 100 C. for 24 h. The reaction mixture is cooled to room temperature. Diethyl ether (1000 ml) and saturated sodium chloride solution (1000 ml) are added, and the mixture is stirred. The organic phase is separated, and the aqueous phase is extracted with diethyl ether (21000 ml). The combined organic phases are dried over Na.sub.2SO.sub.4, and the product is isolated by column chromatography.

[0263] Yield: 5.3 g (16.2 mmol), 65% of theory

d) (2-Amino-4-Bromo-3-benzofuranyl)phenylmethanone

##STR00422##

[0264] A baked-out flask under argon is initially charged with 0.67 g (30 mmol) of Pd (OAc) 2, 1.69 g (6 mmol) of PCy.sub.3 (tricyclohexylphosphine), 1.96 g (30 mmol) of zinc powder and 3 g of 4 molecular sieve (MS4A) 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 then stirred at 100 C. overnight. The mixture is then admixed with saturated NaCl solution and the aqueous phase is extracted with Et.sub.2O (100 ml3). The combined organic phases are dried over MgSO.sub.4 and filtered. The organic solvent is removed under reduced pressure, and the residue is purified by flash column chromatography on silica gel (hexane/AcOEt=7/1-2/1).

[0265] Yield: 6.2 g (20 mmol), 67% of theory.

[0266] In an analogous manner, the following brominated compounds are prepared:

TABLE-US-00008 Reactant 1 Product Yield 1d [00423] [00424] 41% 2d [00425] [00426] 52%

e) 9-Bromo-2,4-diphenylbenzofuro[3,2-d]pyrimidine

##STR00427##

[0267] To an initial charge under argon of 107 g (316 mmol) of (3-amino-4-chloro-2-benzofuranyl)phenylmethanone and 104 g (1015 mmol) of benzonitrile in 1000 ml of o-xylene are added 56 g (677 mmol) of sodium 2-methylprop-2-olate. The mixture is stirred at 140 C. for 5 hours. 30 ml of water are discharged from the water separator, and then a little acetone is added and the mixture is stirred for a further hour. After cooling, the mixture is quenched with one liter of water. The organic phase is separated off, washed three times with 300 ml of water, dried over MgSO.sub.4 and filtered, and the solvent is removed under reduced pressure. The residue is purified by column chromatography. The yield is 64 g (160 mmol), corresponding to 48% of theory.

[0268] The following compounds are prepared in an analogous manner:

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield 1e [00428] [00429] [00430] 41% [52673-90-2] 2e [00431] [00432] [00433] 49% [141104-58-7] 3e [00434] [00435] [00436] 42% [2920-38-9] 4e [00437] [00438] [00439] 41% [142475-01-2] 5e [00440] [00441] [00442] 45% [29021-90-7] 6e [00443] [00444] [00445] 52% 7e [00446] [00447] [00448] 46% [141104-58-7] 8e [00449] [00450] [00451] 40% [2920-38-9] 9e [00452] [00453] [00454] 46% 10e [00455] [00456] [00457] 47% [2920-38-9] 11e [00458] [00459] [00460] 42% 12e [00461] [00462] [00463] 47% [141104-58-7] 13e [00464] [00465] [00466] 43% 14e [00467] [00468] [00469] 49% 15e [00470] [00471] [00472] 43% [52673-90-2] [2920-38-9] 16e [00473] [00474] [00475] 42% [1777814-10-4] 17e [00476] [00477] [00478] 46% [1251582-17-8] 18e [00479] [00480] [00481] 41% [2007154-59-6] 19e [00482] [00483] [00484] 45% 20e [00485] [00486] [00487] 47%

f) 2,9-Dichloro-4-phenylbenzofuro[3,2-d]pyrimidine

##STR00488##

[0269] 13 g (110.0 mmol) of phenylboronic acid, 15.1 g (56 mmol) of 2,4,9-trichlorobenzofuro[3,2-d]pyrimidine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. To this suspension are added 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium (II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/heptane. Yield: 13.1 g (42 mmol), 75% of theory.

[0270] The following compounds are prepared in an analogous manner:

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield 1f [00489] [00490] [00491] 57% [2268673-77-2] 2f [00492] [00493] [00494] 78% [2486241-23-8] E2 3f [00495] [00496] [00497] 55% [2268673-77-2] 4f [00498] [00499] [00500] 69% [2173554-87-3] 6f [00501] [00502] [00503] 65% [2305626-41-7] E8 7f [00504] [00505] [00506] 62% [2036359-98-3] E1 8f [00507] [00508] [00509] 71% [1612243-82-9] 9f [00510] [00511] [00512] 65% [1313018-07-3] E9 10f [00513] [00514] [00515] 74% [2173554-91-9] 11f [00516] [00517] [00518] 70% [1821235-72-6] 12f [00519] [00520] [00521] 66% [2173554-91-9] 13f [00522] [00523] [00524] 54% [2036359-98-3] E11 14f [00525] [00526] [00527] 52% [2305626-41-7] E27 15f [00528] [00529] [00530] 63% [2036359-98-3] E12 16f [00531] [00532] [00533] 60% [1678536-28-1] [2173554-87-3] 17f [00534] [00535] [00536] 58% [2173554-87-3] 18f [00537] [00538] [00539] 61% [2173554-87-3] E26 19f [00540] [00541] [00542] 73% [1199616-48-2] E24 20f [00543] [00544] [00545] 54% [ 2376887-12-4] [2173554-87-3] 21f [00546] [00547] [00548] 58% [2173554-87-3] E23 22f [00549] [00550] [00551] 50% [2036359-98-3] 23f [00552] [00553] [00554] 54% [2173554-87-3] E22 24f [00555] [00556] [00557] 54% [2036359-98-3] E21 25f [00558] [00559] [00560] 63% [2036359-98-3] E19 26f [00561] [00562] [00563] 60% [1848256-39-2] 27f [00564] [00565] [00566] 57% [2173554-87-3] E18 28f [00567] [00568] [00569] 56% [2226916-85-2] 29f [00570] [00571] [00572] 55% [2268673-77-2] 30f [00573] [00574] [00575] 75% E7 31f [00576] [00577] [00578] 70% [2226916-85-2] 32f [00579] [00580] [00581] 73% 33f [00582] [00583] [00584] 65% [2036359-98-3] E25 34f [00585] [00586] [00587] 69% [2036359-98-3] 35f [00588] [00589] [00590] 60% [2765540-65-4] [2036359-98-3] E17 36f [00591] [00592] [00593] 67% [2036359-98-3] E16 37f [00594] [00595] [00596] 62% [2226916-85-2] 38f [00597] [00598] [00599] 65% [2376837-33-9] [2226916-85-2] E15 39f [00600] [00601] [00602] 57% [2268673-77-2] E14 40f [00603] [00604] [00605] 56% [2173554-87-3] 41f [00606] [00607] [00608] 61% [2173554-87-3] E13 42f [00609] [00610] [00611] 67% [2144459-61-8] [2036359-98-3] 43f [00612] [00613] [00614] 59% [2765540-35-8] [2173554-87-3] E3 44f [00615] [00616] [00617] 54% [2173554-87-3] E10 45f [00618] [00619] [00620] 62% [2765540-35-8] [2173554-87-3] 46f [00621] [00622] [00623] 57% [2765540-35-8] [1612243-82-9] E6 47f [00624] [00625] [00626] 56% [2268673-77-2] E5 48f [00627] [00628] [00629] 61% [ 2376887-12-4] [1612243-82-9] E4 49f [00630] [00631] [00632] 65% [1678536-28-1] [2268673-77-2] E20 50f [00633] [00634] [00635] 60% [2173554-87-3] 51f [00636] [00637] [00638] 72% [162607-19-4] 52f [00639] [00640] [00641] 77% [162607-19-4]

Production of the OLEDs

[0271] In examples V1 to V11 and B1 to B40 which follow (see tables 7 and 8), the data of various OLEDs are presented.

[0272] Examples B1 to B40 show data for OLEDs of the invention. Substrates used for the OLEDs in table 7 are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm.

[0273] The exact structure of the OLEDs can be found in table 7. The materials required for production of the OLEDs are shown in table 9 if not described above.

[0274] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (also host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details reported in the form SdT1:H2:TEG1 (33%:60%:7%) 30 nm indicate the presence of material SdT1 in a proportion by volume of 33% as host material 1, the compound H2 as host material 2 in a proportion of 60% and TEG1 in a proportion of 7% in a 30 nm thick layer. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0275] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured; these are used to calculate the EQE. The calculation is effected assuming Lambertian emission characteristics. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to calculate the CIE 1931 x and y color coordinates. The parameter U1000 in table 8 refers here to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0276] The lifetime LT is defined as the time after which the luminance drops from a starting luminance L0 (in cd/m.sup.2) to a certain proportion L1 (in cd/m.sup.2) in the course of operation with constant current density j.sub.0 in mA/cm.sup.2. A figure of L1/L0=80% in table 8 means that the lifetime reported in the LT column corresponds to the time (in h) after which the luminance falls to 80% of its starting value (L0).

Use of Mixtures of the Invention in OLEDs

[0277] The compounds or material combinations of the invention can be used in the emission layer in phosphorescent green OLEDs.

[0278] The data for the various OLEDs are collated in table 8. Examples V1 to V11 are comparative examples according to the prior art; examples B1 to B40 show data of OLEDs of the invention. The inventive examples show a clear benefit in the lifetime of the device.

TABLE-US-00011 TABLE 7 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness V1 SpMA1:PD1 SpMA1 SpMA2 SdT1:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B1 SpMA1:PD1 SpMA1 SpMA2 E1:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V2 SpMA1:PD1 SpMA1 SpMA2 SdT2:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B2 SpMA1:PD1 SpMA1 SpMA2 E2:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V3 SpMA1:PD1 SpMA1 SpMA2 SdT3:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B3 SpMA1:PD1 SpMA1 SpMA2 E20:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V4 SpMA1:PD1 SpMA1 SpMA2 SdT4:H5:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B4 SpMA1:PD1 SpMA1 SpMA2 E4:H5:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V5 SpMA1:PD1 SpMA1 SpMA2 SdT5:H4:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B5 SpMA1:PD1 SpMA1 SpMA2 E5:H4:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V6 SpMA1:PD1 SpMA1 SpMA2 SdT6:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B6 SpMA1:PD1 SpMA1 SpMA2 E6:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V7 SpMA1:PD1 SpMA1 SpMA2 SdT7:H14:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V8 SpMA1:PD1 SpMA1 SpMA2 SdT7:H1:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V9 SpMA1:PD1 SpMA1 SpMA2 SdT7:H5:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (23%:70%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V10 SpMA1:PD1 SpMA1 SpMA2 SdT7:H22:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm V11 SpMA1:PD1 SpMA1 SpMA2 SdT7:SpMA3:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B7 SpMA1:PD1 SpMA1 SpMA2 E27:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B8 SpMA1:PD1 SpMA1 SpMA2 E26:H1:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B9 SpMA1:PD1 SpMA1 SpMA2 E7:H1:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B10 SpMA1:PD1 SpMA1 SpMA2 E8:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B11 SpMA1:PD1 SpMA1 SpMA2 E9:H2:TEG1 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B12 SpMA1:PD1 SpMA1 SpMA2 11f:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B13 SpMA1:PD1 SpMA1 SpMA2 E11:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B14 SpMA1:PD1 SpMA1 SpMA2 E12:H5:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B15 SpMA1:PD1 SpMA1 SpMA2 16f:H5:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B16 SpMA1:PD1 SpMA1 SpMA2 E23:H5:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B17 SpMA1:PD1 SpMA1 SpMA2 E3:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B18 SpMA1:PD1 SpMA1 SpMA2 E14:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B19 SpMA1:PD1 SpMA1 SpMA2 E22:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B20 SpMA1:PD1 SpMA1 SpMA2 E24:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B21 SpMA1:PD1 SpMA1 SpMA2 E17:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B22 SpMA1:PD1 SpMA1 SpMA2 17f:H2:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B23 SpMA1:PD1 SpMA1 SpMA2 E1:H22:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B24 SpMA1:PD1 SpMA1 SpMA2 E1:H4:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B25 SpMA1:PD1 SpMA1 SpMA2 E1 H16:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B26 SpMA1:PD1 SpMA1 SpMA2 E1:H9:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B27 SpMA1:PD1 SpMA1 SpMA2 E1:H22:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B28 SpMA1:PD1 SpMA1 SpMA2 34f:H8:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B29 SpMA1:PD1 SpMA1 SpMA2 34f:H3:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B30 SpMA1:PD1 SpMA1 SpMA2 3f:H22:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B31 SpMA1:PD1 SpMA1 SpMA2 34f:H22:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B32 SpMA1:PD1 SpMA1 SpMA2 E18:H3:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B33 SpMA1:PD1 SpMA1 SpMA2 E18:H14:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B34 SpMA1:PD1 SpMA1 SpMA2 E18:H22:TEG2 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B35 SpMA1:PD1 SpMA1 SpMA2 E10:H8:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B36 SpMA1:PD1 SpMA1 SpMA2 E10:H1:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B37 SpMA1:PD1 SpMA1 SpMA2 E10:H5:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (23%:70%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B38 SpMA1:PD1 SpMA1 SpMA2 E10:H22:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B39 SpMA1:PD1 SpMA1 SpMA2 E10:SpMA3:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm B40 SpMA1:PD1 SpMA1 SpMA2 E1:H14:TEG3 ST2 ST2:LiQ LiQ (95%:5%) 215 nm 20 nm (33%:60%:7%) 10 nm (50%:50%) 1 nm 20 nm 30 nm 30 nm

TABLE-US-00012 TABLE 8 U1000 EQE1000 CIE x/y at j0 L1/L0 LT Ex. (V) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) V1 3.6 16.1 0.33/0.61 20 80 330 B1 3.3 17.5 0.34/0.61 20 80 650 V2 3.7 16.2 0.34/0.62 20 80 310 B2 3.3 17.8 0.34/0.62 20 80 625 V3 3.6 16.4 0.35/0.621 20 80 305 B3 3.4 18.1 0.34/0.62 20 80 600 V4 3.8 16.5 0.33/0.63 20 80 320 B4 3.3 18.5 0.34/0.62 20 80 560 V5 4.3 18.1 0.34/0.61 20 80 350 B5 3.2 19 0.35/0.63 20 80 890 V6 3.8 16.8 0.35/0.61 20 80 330 B6 3.1 18.8 0.34/0.63 20 80 820 V7 3.6 25.6 0.35/0.61 20 80 460 V8 3.3 26.8 0.35/0.63 20 80 345 V9 3.4 26.4 0.34/0.63 20 80 430 V10 3.3 26.0 0.34/0.62 20 80 360 V11 3.2 25.9 0.34/0.61 20 80 220 B7 3.2 19.1 0.34/0.62 20 80 830 B8 3.3 18.9 0.35/0.62 20 80 795 B9 3.3 19.4 0.35/0.63 20 80 815 B10 3.3 19.5 0.34/0.61 20 80 840 B11 3.2 18.0 0.35/0.61 20 80 790 B12 3.1 19.3 0.34/0.61 20 80 830 B13 3.3 19.0 0.34/0.62 20 80 855 B14 3.4 25.9 0.33/0.63 20 80 1080 B15 3.3 25.1 0.35/0.61 20 80 1190 B16 3.2 24.3 0.35/0.63 20 80 1200 B17 3.1 19.0 0.34/0.62 20 80 840 B18 3.3 17.5 0.35/0.62 20 80 770 B19 3.2 19.2 0.35/0.61 20 80 880 B20 3.4 18.7 0.33/0.64 20 80 860 B21 3.2 19.1 0.33/0.63 20 80 820 B22 3.4 17.5 0.35/0.62 20 80 780 B23 3.2 18.3 0.33/0.61 20 80 790 B24 3.4 26.3 0.33/0.63 20 80 1130 B25 3.2 19.3 0.35/0.62 20 80 870 B26 3.5 17.3 0.34/0.61 20 80 785 B27 3.2 18.7 0.34/0.62 20 80 860 B28 3.5 18.8 0.34/0.61 20 80 810 B29 3.2 19.1 0.33/0.63 20 80 880 B30 3.5 18.3 0.34/0.62 20 80 530 B31 3.3 18.5 0.33/0.63 20 80 830 B32 3.4 18.7 0.34/0.61 20 80 835 B33 3.2 26.2 0.35/0.62 20 80 1100 B34 3.2 19.1 0.35/0.62 20 80 860 B35 3.1 26.5 0.34/0.61 20 80 1990 B36 2.9 27.3 0.33/0.62 20 80 1390 B37 3.0 27.0 0.35/0.62 20 80 1730 B38 2.8 26.4 0.35/0.61 20 80 1450 B39 2.8 26.8 0.33/0.63 20 80 885 B40 3.4 24.9 0.35/0.61 20 80 1400

TABLE-US-00013 TABLE 9 Materials used, if not described above [00642] PD1 (CAS Reg. No. 1224447-88-4) [00643] SpMA1 [00644] SpMA2 [00645] SpMA3 [00646] ST2 [00647] LiQ [00648] TEG1 [00649] TEG2 [00650] TEG3 [00651] SdT1 US20150207082 [00652] SdT2 US20150207082 [00653] SdT3 WO15169412 [00654] SdT4 KR20170005637 [00655] SdT5 WO2019017731 [00656] SdT6 WO2019098765 [00657] SdT7 CN114560864