Materials for organic light emitting devices

Abstract

The present invention relates to deuterated OLED materials and to methods to produce such deuterated compounds.

Description

[0001] Materials for organic light emitting devices

[0002] The present application relates to spiroxanthene, spirothiaxanthene and spirobisxanthene, spirobisthiabisxanthenes derivatives substituted by at least one deuterated arylamine group. The compounds are suitable for use in electronic devices.

[0003] Deuterium is one of the two stable isotope of hydrogen and has a natural abundance of approximately 0.0156% (0.312% by mass) of all the naturally occurring hydrogen in the oceans.

[0004] Deuterated compounds or intermediates, in which the level of deuterium is intentionally enriched, are known, and deuterated aromatic compounds have often been used in studies of the course of chemical reactions or conversions in metabolism. Deuterated aromatic compounds are also used as starting materials for pharmaceutical compounds or markers.

[0005] Also well known is the use of deuterated organic or metallorganic compounds in electronic devices. More particularly, the use of deuterated organic or metallorganic compounds in organic electroluminescent device (OLED) can drastically improve the OLEDs performances in terms of efficiency and lifetime as disclosed, for example, in WO 2010 / 099534, WO 2011 / 050888 or J. Phys. Chem. C 2007, 111, 3490-3494. However, the synthesis of deuterated compounds can be quite challenging and also costly. One can obtain a deuterated compound by reacting building blocks together, where at least one of the builing block is partly or completely deuterated (like in WO 2011 / 050888) or by deuterating the compound once it has been synthesized (like in WO 2010 / 099534). In general, the higher the deuteration degree of a compound is, the higher the impact of the deuteration on the properties improvements of the device is. However, the avaibility of Deuterium sources like D2O is limited. Therefore, there is a need for partially deuterated compounds that consume less Deuterium than corresponding fully deuterated compounds but lead to same or even higher OLEDs improvement in terms of efficiency and lifetime.

[0006] Partial deuteration is understood here to mean that at least one hydrogen atom in the compound has been replaced by a deuterium atom, and preferably two or more hydrogen atoms in the compound have been replaced by deuterium atoms, but not all hydrogen atoms, such that there is also at least one hydrogen atom in the compound as well as the one or more deuterium atoms. The term “H atom” or “H” or “hydrogen” or “hydrogen atom” is understood here and in the overall application to mean a protium atom, i.e. the isotope1H. The term “D atom” or “D” or “deuterium” or “deuterium atom” is understood here and in the overall application to mean the isotope2H. The prior art, for example in WO 2014 / 072017 and WO 2018 / 069167, describes spiroxanthene and spirothiaxanthene compounds that bear an arylamino group as OLED functional materials. However, there is still a need for improvement with regard to the performance data of the OLEDs comprising spiroxanthene, spirobisxanthenes, spirobisthiabisxanthenes and spirothiaxanthene compounds, especially operating voltage, lifetime and efficiency.

[0007] In the context of the present invention, it has been found that partially deuterated spiroxanthene, spirothiaxathene or spirothioxanthene diarylamine compounds as described below lead to OLEDs having excellent performance data, while the targeted partial deuteration leads to OLEDs that are as good or even better than OLEDs comprising the corresponding fully deuterated compounds, while being more sustainable due to a lower consumption of D2O resources.

[0008] The present invention therefore relates to a compound A comprising a group of formula (I) and a group of formula (II),

[0009] Formula (I) Formula (II) where the group of formula (I) is bonded to at least one group of formula (II) via the positions denoted by * in formulae (I) and (II);

[0010] X1stands for O or S;

[0011] X2stands for a single bond, O or S;

[0012] Z stands on each occurrence, identically or differently, for OR1or N, or for C if it is bonded to a group of formula (II) via a group — Ar5*;

[0013] X3stands for a single bond, BR2, C(R2)2, C(R2)2-C(R2)2, Si(R2)2, Si(R2)2-Si(R2)2, O, S or Ar1stands for an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R2, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R2radicals;

[0014] Ar2stands for an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R2, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R2radicals;

[0015] Ar5stands for a single bond, an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R1, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R1radicals;

[0016] R1is the same or different at each instance and is selected from H, F, C(=O)R3, CN, Si(R3)3, N(R3)2, P(=O)(R3)2, S(=O)R3, S(=O)2R3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R1radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R3radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R3C=CR3-, -C=C-, Si(R3)2, C=O, C=NR3, -C(=O)O-, C(=O)NR3-, NR3, P(=O)(R3), -O-, -S-, SO or SO2;

[0017] R2is the same or different at each instance and is selected from H, D, F, C(=O)R4, CN, Si(R4)a, N(R4)2, P(=O)(R4)2, S(=O)R4, S(=O)2R4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R2radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R4radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R4C=CR4-, -C=C-, Si(R4)2, C=O, C=NR4, -C(=O)O-, C(=O)NR4-, NR4, P(=O)(R4), -O-, -S-, SO or SO2;

[0018] R3is the same or different at each instance and is selected from H, F, C(=O)R, CN, Si(R)s, N(R)2, P(=O)(R)2, S(=O)R, S(=O)2R, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R3radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R radicals; and where one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -RC=CR-, -C=C-, Si(R)2, C=O, C=NR, -C(=O)O-, C(=O)NR-, NR, P(=O)(R), -O-, -S-, SO or SO2;

[0019] R4is the same or different at each instance and is selected from H, D, F, C(=O)R', CN, Si(R')a, N(R')2, P(=O)(R')2, S(=O)R', S(=O)2R', straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R4radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R' radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R'C=CR'-, -C=C-, Si(R')2, C=O, C=NR', -C(=O)O-, C(=O)NR'-, NR', P(=O)(R'), -O-, -S-, SO or SO2;

[0020] R is the same or different at each instance and is selected from H, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN;

[0021] R' is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R' radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; m is 0 or 1 ; when m is 0 then the group X3is absent n is the same or different at each instance and is 0 or 1 , where the sum of all the indices n is 1, 2, 3 or 4; characterized in that,

[0022] Ar1and Ar2are both deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%; and the group of formula (I) is an undeuterated group.

[0023] When m is 0 then the group X3is absent and the group of formula (II) corresponds to:

[0024] Ar1

[0025] * - N

[0026] Partial deuteration is understood here to mean that at least one hydrogen atom in the compound has been replaced by a deuterium atom, and preferably two or more hydrogen atoms in the compound have been replaced by deuterium atoms, but not all hydrogen atoms, such that there is also at least one hydrogen atom in the compound as well as the one or more deuterium atoms.

[0027] As mentioned above, the group of formula (I) is an undeuterated group. This is understood here to mean that the level of deuterium in this group has not been intentionally increased and deuterium can only be present in this group at his natural abundance level.

[0028] The term “deuterated compound” or “deuterated group” refers here to a compound or group in which deuterium is present in at least 100 times the natural abundance level. A higher deuteration degree than in nature can be achieved by using building blocks which have been prealably enriched with deuterium via a deuteration method or by submitting a compound to a deuteration method.

[0029] In accordance with the present invention, the deuteration degree in % on free aromatic positions (DAP) in a group corresponds to the number of deuterium atoms present on free aromatic positions in the group on the total number of deuterium atoms and protium atoms present on free aromatic positions in the group in %, as follows: DAP = (ND * 100) / (NP+ ND) where:

[0030] ND is the number of deuterium atoms present in free aromatic positions in the group;

[0031] NP is the number of deuterium and protium atoms present in free aromatic positions in the group.

[0032] As mentioned above, the term hydrogen in the present invention design the protium isotope of hydrogen.

[0033] The definitions which follow are applicable to the chemical groups that are used in the present application. They are applicable unless any more specific definitions are given.

[0034] An aryl group in the context of this invention is understood to mean either a single aromatic cycle, i.e. benzene, or a fused aromatic polycycle, for example naphthalene, phenanthrene or anthracene. A fused aromatic polycycle in the context of the present application consists of two or more single aromatic cycles fused to one another. Fusion between cycles is understood here to mean that the cycles share at least one edge with one another. An aryl group in the context of this invention contains 6 to 40 aromatic ring atoms. In addition, an aryl group does not contain any heteroatom as aromatic ring atom, but only carbon atoms.

[0035] A heteroaryl group in the context of this invention is understood to mean either a single heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, for example quinoline or carbazole. A fused heteroaromatic polycycle in the context of the present application consists of two or more single aromatic or heteroaromatic cycles that are fused to one another, where at least one of the aromatic and heteroaromatic cycles is a heteroaromatic cycle. Fusion between cycles is understood here to mean that the cycles share at least one edge with one another. A heteroaryl group in the context of this invention contains 5 to 40 aromatic ring atoms of which at least one is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S.

[0036] An aryl or heteroaryl group, each of which may be substituted by the abovementioned radicals, is especially understood to mean groups derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7- quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo[1,2-a]benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1 ,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, 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] An aromatic ring system in the context of this invention is a system which does not necessarily contain solely aryl groups, but which may additionally contain one or more nonaromatic rings fused to at least one aryl group. These nonaromatic rings contain exclusively carbon atoms as ring atoms. Examples of groups covered by this definition are tetrahydronaphthalene, fluorene and spirobifluorene. In addition, the term "aromatic ring system" includes systems that consist of two or more aromatic ring systems joined to one another via single bonds, for example biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3, 5-diphenyl-1 -phenyl. An aromatic ring system in the context of this invention contains 6 to 40 carbon atoms and no heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0038] A heteroaromatic ring system conforms to the abovementioned definition of an aromatic ring system, except that it must contain at least one heteroatom as ring atom. As is the case for the aromatic ring system, the heteroaromatic ring system need not contain exclusively aryl groups and heteroaryl groups, but may additionally contain one or more nonaromatic rings fused to at least one aryl or heteroaryl group. The nonaromatic rings may contain exclusively carbon atoms as ring atoms, or they may additionally contain one or more heteroatoms, where the heteroatoms are preferably selected from N, O and S. One example of such a heteroaromatic ring system is benzopyranyl. In addition, the term "heteroaromatic ring system" is understood to mean systems that consist of two or more aromatic or heteroaromatic ring systems that are bonded to one another via single bonds, for example 4,6-diphenyl-2-triazi nyl. A heteroaromatic ring system in the context of this invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, where at least one of the ring atoms is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S. The terms "heteroaromatic ring system" and "aromatic ring system" as defined in the present application thus differ from one another in that an aromatic ring system cannot have a heteroatom as ring atom, whereas a heteroaromatic ring system must have at least one heteroatom as ring atom. This heteroatom may be present as a ring atom of a nonaromatic heterocyclic ring or as a ring atom of an aromatic heterocyclic ring.

[0039] In accordance with the above definitions, any aryl group is covered by the term "aromatic ring system", and any heteroaryl group is covered by the term "heteroaromatic ring system".

[0040] An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms is especially understood to mean groups derived from the groups mentioned above under aryl groups and heteroaryl groups, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or from combinations of these groups.

[0041] In the context of the present invention, a straight-chain alkyl group having 1 to 20 carbon atoms and a branched or cyclic alkyl group having 3 to 20 carbon atoms and an alkenyl or alkynyl group having 2 to 40 carbon atoms in which individual hydrogen atoms or CH2 groups may also be substituted by the groups mentioned above in the definition of the radicals are preferably understood to mean the methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl radicals.

[0042] An alkoxy or thioalkyl group having 1 to 20 carbon atoms in which individual hydrogen atoms or CH2 groups may also be substituted by the groups mentioned above in the definition of the radicals is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n- pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n- octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2- trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0043] The wording that two or more radicals together may form a ring, in the context of the present application, shall be understood to mean, inter alia, that the two radicals are joined to one another by a chemical bond. 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.

[0044] Preferably, at least one of groups Ar1and Ar2is selected from a radical comprising at least two rings selected from aromatic and heteroaromatic rings, said radical may optionally be substituted by one or more radicals R2. That is, at least one of groups Ar1and Ar2is an aromatic ring system that comprises two or more simple aromatic rings as aryl groups, or a heteroaromatic ring system that comprises two or more simple aromatic rings, at least one which contains a heteroatom as one of the aromatic ring atoms to form a simple heteroaromatic ring as heteroaryl group. According to the invention, within said at least one radical of group Ar1or Ar2two aromatic or heteroaromatic rings may be condensed or may be connected to each other via a divalent group selected from -C(R4)2-, -N(R4)-, -O-, and -S-, where R4has the same meaning as above.

[0045] More preferably, said at least one radical of group Ar1or Ar2comprises at least two aromatic rings. That is, at least one of groups Ar1and Ar2is an aromatic ring system that comprises two or more simple aromatic rings as aryl groups, which aromatic rings may be condensed or may be connected to each other via a divalent group selected from -C(R4)2-, -N(R4)-, -O-, and -S-.

[0046] Even more preferably, groups Ar1and Ar2are, identically or differently, selected from radicals comprising at least two rings selected from aromatic and heteroaromatic rings, which radicals may each optionally be substituted by one or more radicals R2. That is, each of groups Ar1and Ar2is either an aromatic ring system that comprises two or more simple aromatic rings as aryl groups, or a heteroaromatic ring system that comprises two or more simple aromatic rings, at least one which contains a heteroatom as one of the aromatic ring atoms to form a simple heteroaromatic ring as heteroaryl group. According to the invention, within at least one of said radicals or within both of said radicals of groups Ar1and Ar2two aromatic or heteroaromatic rings may be condensed or may be connected to each other via a divalent group selected from -C(R4)2-, -N(R4)-, -O-, and -S-. It is particularly preferred that said radicals of groups Ar1and Ar2each comprises at least two aromatic rings. That is, groups Ar1and Ar2are, identically or differently, selected from aromatic ring systems that comprise two or more simple aromatic rings as aryl groups, wherein within one or within both of said groups Ar1and Ar2the aromatic rings may be condensed or may be connected to each other via a divalent group selected from -C(R4)2-, -N(R4)-, -O-, and -S-.

[0047] According to another embodiment, it is preferred that said aromatic or heteroaromatic rings are neither condensed nor connected.

[0048] Preferably, groups Ar1and Ar2are, identically or differently, selected from radicals derived from the following groups or from combinations of 2 or 3 of the following groups: phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, phenanthrenyl, fluorenyl, especially 9,9'- dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl and oxazole, where each of these groups is optionally substituted by one or more radicals R2.

[0049] Particularly preferred groups Ar1and Ar2are, identically or differently, selected from phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, phenanthrenyl, fluorenyl, especially 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, oxazole, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl- substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, each of which may optionally be substituted by one or more radicals R2.

[0050] Preferred groups Ar1and Ar2are, identically or differently, selected from groups of the formulae (A-1) to (A-51):

[0051] (A-1) (A-2) (A-3) where the dashed bonds indicate the bonds to the nitrogen atom, where the groups (A-1) to (A-51) are deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%, and the groups (A-1) to (A-51) may further be substituted by one, two or three radicals R2other than H or D.

[0052] Among the groups of formulae (A-1) to (A-51), following groups are preferred: (A-1), (A-2), (A-3), (A-4), (A-11), (A-12), (A-15), (A-16), (A-17), (A-19), (A-25), (A-26), (A-31), (A-32), (A-33), (A-35), (A-36), (A-37), (A-43).

[0053] Very preferred groups Ar1and Ar2are, identically or differently, selected from groups of the formulae (Ar-1) to (Ar-278): where the dashed bonds indicate the bonds to the nitrogen atom, where the groups of formulae (Ar-1) to (Ar-278) may further be substituted by one, two or three radicals R2other than H or D but are preferably not further substituted by a group R2other than D, and where the groups (Ar-1) to (Ar-278) are deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%.

[0054] Preferably, Ar1and Ar2are both deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 60%, more preferably equal to or higher than 70%, even more preferably equal to or higher than 80%, particularly preferably equal to or higher than 90%. Preferably, Ar1and Ar2comprise at least 3, more preferably at least 4, even more preferably at least 5, particularly preferably at least 6 free aromatic positions, which are deuterated.

[0055] Examples of preferred groups Ar1and Ar2are the following groups: where (D)3-s means that the corresponding ring can bear 3 to 5 Deuterium atoms.

[0056] Preferably, the groups of formulae (A-1) to (A-51) are deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 60%, more preferably equal to or higher than 70%, even more preferably equal to or higher than 80%, particularly preferably equal to or higher than 90%.

[0057] Preferably, in formulae (A-1) to (A-51), the 6-membered ring which is directly bonded to the nitrogen atom is deuterated and has a deuteration degree on free aromatic positions equal to or higher than 50%, preferably equal to or higher than 60%, more preferably equal to or higher than 70%, even more preferably equal to or higher than 80%, particularly preferably equal to or higher than 90%.

[0058] Preferably, the groups of formulae (Ar-1) to (Ar-278) are deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 60%, more preferably equal to or higher than 70%, even more preferably equal to or higher than 80%, particularly preferably equal to or higher than 90%. Preferably, in the groups of formulae (Ar-1) to (Ar-278), the 6-membered ring which is directly bonded to the nitrogen atom is deuterated and has a deuteration degree on free aromatic positions equal to or higher than 50%, preferably equal to or higher than 60%, more preferably equal to or higher than 70%, even more preferably equal to or higher than 80%, particularly preferably equal to or higher than 90%.

[0059] Examples of deuteration degree on free aromatic positions DAP on groups Ar1and Ar2according to the invention (the dashed bonds indicate the bonds to the nitrogen atom):

[0060] In accordance with a preferred embodiment, the compound A is a monoamine, meaning that the compound contains only a single triarylamino group, preferably only a single amino group. Groups such as carbazole, indole and pyrrole and the derivatives thereof are preferably not regarded as groups containing a triarylamino group or as groups containing an amino group. A triarylamino group is understood here to mean all groups in which a nitrogen atom binds to three groups, where the groups are selected from optionally substituted aromatic and heteroaromatic ring systems, especially from optionally substituted aryl and heteroaryl groups.

[0061] Furthermore, it is preferred that X1stands for O or S and X2stands for a single bond or O, very preferred X1stands for O and X2stands for a single bond.

[0062] Preferably, Z stands on each occurrence, identically or differently, for OR1, or for C if it is bonded to a group of formula (II) via a group — Ar5*.

[0063] Preferably, Ar5stands for a single bond, a phenyl or biphenyl group, which might be substituted by one or more R1radicals. More preferbaly, Ar5stands for a single bond.

[0064] Preferably, the group of formula (I) is selected from the groups of formulae (1-1), (I-2), (I- 3), (I-4) and (I-5),

[0065] Among the groups of formulae (1-1) to (I-5), (1-1) and (I-2) are preferred.

[0066] More preferably, the groups of formulae (1-1) and (I-2) are selected from the groups of

[0067] (I-2C) (I-2D) where the symbols have the same meaning as above and formula (1-1 A), (1-1 C), (I-2A) ans (I-2C) is preferred.

[0068] Preferably, the radical R1is selected from H, F, CN, Si(R3)3, N(R3)2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R1radicals may be joined to one another and may form a ring; where the alkyl and alkoxy groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R3radicals. More preferably, the radical R1is selected from H, F, straight-chain alkyl groups having 1 to 10, preferably 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 10, preferably 3 to 6 carbon atoms, aromatic ring systems having 6 to 30, preferably 6 to 24, more preferably 6 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 30, preferably 5 to 24, more preferably 5 to 18 aromatic ring atoms; where two or more R1radicals may be joined to one another and may form a ring; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R3radicals. Even more preferably, the radical R1is selected from H, straightchain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, phenyl and biphenyl. Preferably, the radical R2is selected from H, D, F, CN, Si(R4)s, N(R4)2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R2radicals may be joined to one another and may form a ring; where the alkyl and alkoxy groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R4radicals. More preferably, the radical R2is selected from H, D, F, straight-chain alkyl groups having 1 to 10, preferably 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 10, preferably 3 to 6 carbon atoms, aromatic ring systems having 6 to 30, preferably 6 to 24, more preferably 6 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 30, preferably 5 to 24, more preferably 5 to 18 aromatic ring atoms; where two or more R2radicals may be joined to one another and may form a ring; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R4radicals. Even more preferably, the radical R2is selected from H, D, straightchain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, phenyl and biphenyl.

[0069] Preferably, R3is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl or alkoxy groups having 1 to 10 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms, and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where two or more R3radicals may be joined to one another and may form a ring; where the alkyl and alkoxy groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R radicals. More preferably, R3is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, aromatic ring systems having 6 to 12 aromatic ring atoms, and heteroaromatic ring systems having 5 to 12 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R radicals. Even more preferably, R3is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl groups mentioned may each be substituted by one or more R radicals.

[0070] Preferably, R4is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl or alkoxy groups having 1 to 10 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms, and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where two or more R4radicals may be joined to one another and may form a ring; where the alkyl and alkoxy groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R' radicals. More preferably, R4is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, aromatic ring systems having 6 to 12 aromatic ring atoms, and heteroaromatic ring systems having 5 to 12 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R' radicals. Even more preferably, R4is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl groups mentioned may each be substituted by one or more R' radicals.

[0071] Preferably, R is the same or different at each instance and is selected from H, F, CN, alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 18, preferably 6 to 12 aromatic ring atoms and heteroaromatic ring systems having 5 to 18, preferably 5 to 12 aromatic ring atoms. More preferably, R is the same or different at each instance and is selected from H, F, CN, alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms.

[0072] Preferably, R' is the same or different at each instance and is selected from H, D, F, CN, alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 18, preferably 6 to 12 aromatic ring atoms and heteroaromatic ring systems having 5 to 18, preferably 5 to 12 aromatic ring atoms. More preferably, R' is the same or different at each instance and is selected from H, D, F, CN, alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms.

[0073] Preferred embodiments of compounds A are shown in the following table:

[0074] Compounds A are preferably obtained by reacting building blocks together, wherein one building block is the intermediate compound for a group of formula (I) and is not deuterated, whereas the other building block is the intermediate compound for a group of formula (II) and is at least partly deuterated.

[0075] The application thus provides a process for preparing a compound A, said process comprising the step of performing a chemical reaction between an intermediate compound of formula (lnt-1) with an intermediate compound of formula (lnt-2-Deut) to obtain a compound A: where

[0076] Y1corresponds to a leaving group selected, identically or differently on each occurrence, from the group consisting of halogens, trifluoromethanesulfonate (CF3SO3-), tosylate (CH3C6H4SO3-) or mesylate (CH3SO3-);

[0077] Y2stands for H or D; the other symbols and indices have the same meaning as above, and where

[0078] Ar1and Ar2in formula (lnt-2-Deut) are as described above and are both deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%; and the intermediate compound of formula (lnt-1) is an undeuterated intermediate compound. Preferably, the chemical reaction between an intermediate compound of formula (lnt-1) with an intermediate compound of formula (lnt-2-Deut) to obtain a compound A is selected from amination reactions, more preferably from Buchwald-Hartwig or Ullmann aminations reactions as well as nucleophilic aromatic substitution reactions.

[0079] Preferably, the deuterated intermediate compound (lnt-2-Deut) is obtained via an H-D exchange method, more preferably an H-D exchange method by metal catalysis, an H-D exchange method by acid catalysis or mixture thereof.

[0080] The compounds and mixtures according to the application are suitable for use in an electronic device, especially an organic electroluminescent device (OLED). Depending on the substitution, they can be used in different functions and layers. Preference is given to use as a hole-transporting material in a hole-transporting layer, especially an electron blocker layer, and / or as matrix material in an emitting layer, more preferably in combination with a phosphorescent emitter.

[0081] The invention therefore further provides for the use of a compound or mixture according to the application in an electronic device. This electronic device is preferably selected from the group consisting of organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and more preferably organic electroluminescent devices (OLEDs).

[0082] The invention further provides an electronic device comprising at least one compound or mixture according to the application. This electronic device is preferably selected from the abovementioned devices.

[0083] Particular preference is given to an organic electroluminescent device comprising an anode, cathode and at least one emitting layer, characterized in that at least one organic layer comprising at least one compound or mixture according to the application is present in the device. Preference is given to an organic electroluminescent device comprising an anode, cathode and at least one emitting layer, characterized in that at least one organic layer in the device, selected from hole-transporting and emitting layers, comprises at least one compound or mixture according to the application.

[0084] A hole-transporting layer is understood here to mean all layers disposed between anode and emitting layer, preferably hole injection layer, hole transport layer and electron blocker layer. A hole injection layer is understood here to mean a layer that directly adjoins the anode. A hole transport layer is understood here to mean a layer which is between the anode and emitting layer but does not directly adjoin the anode, and preferably does not directly adjoin the emitting layer either. An electron blocker layer is understood here to mean a layer which is between the anode and emitting layer and directly adjoins the emitting layer. An electron blocker layer preferably has a high-energy LU MO and hence prevents electrons from exiting from the emitting layer.

[0085] Apart from the cathode, anode and emitting layer, the electronic device may comprise further layers. These are selected, for example, from in each case one or more hole injection layers, hole transport layers, hole blocker layers, electron transport layers, electron injection layers, electron blocker layers, exciton blocker layers, interlayers, charge generation layers and / or organic or inorganic p / n junctions. However, it should be pointed out that not every one of these layers need necessarily be present and the choice of layers always depends on the compounds used and especially also on whether the device is a fluorescent or phosphorescent electroluminescent device.

[0086] The sequence of layers in the electronic device is preferably as follows: -anode-

[0087] -hole injection layer-

[0088] -hole transport layer-

[0089] -optionally further hole transport layers-

[0090] -electron blocker layer-

[0091] -emitting layer-

[0092] -optionally hole blocker layer-

[0093] -electron transport layer- -electron injection layer- -cathode-.

[0094] It is not obligatory for all the layers mentioned to be present, and / or further layers may additionally be present.

[0095] The sequence of layers in the electronic device is more preferably as follows: -anode-

[0096] -hole injection layer-

[0097] -hole transport layer-

[0098] -electron blocker layer-

[0099] -emitting layer-

[0100] -hole blocker layer- -electron transport layer-

[0101] -electron injection layer- -cathode-.

[0102] The compound or mixture according to the application is preferably present here in the hole transport layer or electron blocker layer of the electronic device with the abovementioned layer sequence, preferably in the electron blocker layer.

[0103] A hole transport layer is also called a hole-transporting layer (HTL). An electron blocker layer is also called a electron-blocking layer (EBL). An electron transport layer is also called a electron-transporting layer (ETL). A hole blocker layer is also called a hole-blocking layer (HBL).

[0104] In a preferred embodiment, the electronic device containing the compound or mixture according to the application contains multiple emitting layers arranged in succession, each having different emission maxima between 380 nm and 750 nm. In other words, different emitting compounds used in each of the multiple emitting layers fluoresce or phosphoresce and emit blue, green, yellow, orange or red light. In a preferred embodiment, the electronic device contains three emitting layers in succession in a stack, of which one in each case exhibits blue emission, one green emission, and one orange or red, preferably red, emission. Preferably, in this case, the blue-emitting layer is a fluorescent layer, and the green-emitting layer is a phosphorescent layer, and the red- or orange-emitting layer is a phosphorescent layer. The compound or mixture according to the application is preferably present in a hole-transporting layer or in the emitting layer. It should be noted that, for the production of white light, rather than a plurality of coloremitting emitter compounds, an emitter compound used individually which emits over a broad wavelength range may also be suitable.

[0105] It is preferable that the compound or mixture according to the application is used as hole transport material, especially in an electron blocker layer. The emitting layer here may be a fluorescent emitting layer, or it may be a phosphorescent emitting layer. The emitting layer is preferably a blue-fluorescing layer or a green-phosphorescing layer.

[0106] When the device containing the compound or mixture according to the application contains a phosphorescent emitting layer, it is preferable that this layer contains two or more, preferably exactly two, different matrix materials (mixed matrix system). Preferred embodiments of mixed matrix systems are described in detail further down.

[0107] If the compound or mixture according to the application is used as hole transport material in a hole transport layer, a hole injection layer or an electron blocker layer, the compound or mixture according to the application can be used on its own, i.e. in a proportion of 100%, in the hole transport layer, or it can be used in combination with one or more further compounds.

[0108] In a preferred embodiment, a hole-transporting layer comprising the compound or mixture according to the application additionally comprises one or more further hole-transporting compounds. These further hole-transporting compounds are preferably selected from triarylamine compounds, more preferably from monotriarylamine compounds. They are most preferably selected from the preferred embodiments of hole transport materials that are specified further down. In the preferred embodiment described, the compound or mixture according to the application and the one or more further hole-transporting compounds are preferably each present in a proportion of at least 10%, more preferably each in a proportion of at least 20%.

[0109] In a preferred embodiment, a hole-transporting layer comprising the compound or mixture according to the application additionally contains one or more p-dopants. p-Dopants used according to the present invention are preferably those organic electron acceptor compounds capable of oxidizing one or more of the other compounds in the mixture.

[0110] Particularly preferred as p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides comprising at least one transition metal or a metal from main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as binding site. Preference is further given to transition metal oxides as dopants, preferably oxides of rhenium, molybdenum and tungsten, more preferably Re2O?, MoOa, WO3 and ReCh. Still further preference is given to complexes of bismuth in the (III) oxidation state, more particularly bismuth(lll) complexes with electron-deficient ligands, more particularly carboxylate ligands.

[0111] The p-dopants are preferably in substantially homogeneous distribution in the p-doped layers. This can be achieved, for example, by co-evaporation of the p-dopant and the hole transport material matrix. The p-dopant is preferably present in a proportion of 1% to 10% in the p-doped layer.

[0112] Especially preferred p-dopants are the compounds shown in the table on page 99 to page 100 of WO2021 / 104749 A1. In a preferred embodiment, a hole injection layer that conforms to one of the following embodiments is present in the device: a) it contains a triarylamine and a p-dopant; b) it contains a single electron-deficient material (electron acceptor) or c) it contains a hole transport material, a compound with a low HOMO level, and a p-dopant.. In a preferred embodiment of embodiment a), the triarylamine is a monotriarylamine, especially one of the preferred triarylamine derivatives mentioned further down. In a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755. In a preferred embodiment of embodiment c) the hole transport material, the compound with a low HOMO level and the p-dopant are the ones as disclosed in WO 2024 / 133366 A1. Further mixtures of a hole transport material and a compound with a low HOMO level are the followings mixtures 1 to 5:

[0113] In mixtures 1-5, following compounds 1 and 2 can be mixed accordingly as follows: proportion compound 1 : compound 2 can be between 10:90 to 90:10. More preferred it is between 80:20 and 30:70, like 75:25, 70:30, 50:50, 40:60 or 30:70.

[0114] The compounds of the mixtures 1 to 5 can be synthesized according to the methods as disclosed in the patent applications which are put in brackets below the corresponding compounds. The use of these mixtures in the hole-injection layer of devices is not limited to the devices as disclosed herein.

[0115] The compound or mixture according to the application may be present in a hole injection layer, in a hole transport layer and / or in an electron blocker layer of the device. When the compound is present in a hole injection layer or in a hole transport layer, it has preferably been p-doped, meaning that it is in mixed form with a p-dopant, as described above, in the layer.

[0116] Further hole transport materials that can be used in any of the layers that require materials with hole transporting capabilities, e.g. hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL) or the emissive layer (EML) are listed in the following table. The compounds can be prepared easily according to the disclosure cited for each of the compounds. The compounds HT-1 to HT-20 exhibit excellent stability and electronic devices comprising the compounds show high efficiencies, low voltages and improved lifetimes.

[0117] The teachings on the use of the compounds and the methods of making the compounds contained in the above patent applications are hereby expressly incorporated by reference into the present disclosure. The compounds HT-1 to HT-20 exhibit excellent properties when used in OLEDs, in particular excellent lifetime and efficiency. This is particularly the case when they are used in a hole transport layer of the OLED.

[0118] More preferably, the compound or mixture according to the application is present in an electron blocker layer. In this case, it is preferably not p-doped. Further preferably, in this case, it is preferably present alone in the layer without addition of a further compound. In an alternative preferred embodiment, the compound or mixture according to the application is used in an emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds. The phosphorescent emitting compounds here are preferably selected from red- phosphorescing and green-phosphorescing compounds.

[0119] The proportion of the matrix material in the emitting layer in this case is between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5% by volume, and more preferably between 85.0% and 97.0% by volume.

[0120] Correspondingly, the proportion of the emitting compound is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, and more preferably between 3.0% and 15.0% by volume.

[0121] An emitting layer of an organic electroluminescent device may also contain systems comprising a plurality of matrix materials (mixed matrix systems) and / or a plurality of emitting compounds. In this case too, the emitting compounds are generally those compounds having the smaller proportion in the system and the matrix materials are those compounds having the greater proportion in the system. In individual cases, however, the proportion of a single matrix material in the system may be less than the proportion of a single emitting compound.

[0122] It is preferable that the compound or mixture according to the application is used as a component of mixed matrix systems, preferably for phosphorescent emitters. The mixed matrix systems preferably comprise two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material having hole-transporting properties and the other material is a material having electron-transporting properties. It is further preferable when one of the materials is selected from compounds having a large energy differential between HOMO and LIIMO (wide-bandgap materials). The compound or mixture according to the application in a mixed matrix system is preferably the matrix material having hole-transporting properties. Correspondingly, when the compound or mixture according to the application is used as matrix material for a phosphorescent emitter in the emitting layer of an OLED, a second matrix compound having electron-transporting properties is present in the emitting layer. The two different matrix materials may be present here in a ratio of 1 :50 to 1:1 , preferably 1 :20 to 1 : 1 , more preferably 1 : 10 to 1 : 1 and most preferably 1 :4 to 1:1.

[0123] The desired electron-transporting and hole-transporting properties of the mixed matrix components may, however, also be combined mainly or entirely in a single mixed matrix component, in which case the further mixed matrix component(s) fulfil(s) other functions.

[0124] Preference is given to using the following material classes in the abovementioned layers of the device:

[0125] Phosphorescent emitters:

[0126] The term "phosphorescent emitters" typically encompasses compounds where the emission of light is effected through a spin-forbidden transition, for example a transition from an excited triplet state or a state having a higher spin quantum number, for example a quintet state.

[0127] Suitable phosphorescent 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. Preference is given to using, as phosphorescent emitters, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0128] 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 for use in the devices according to the application.

[0129] Fluorescent emitters:

[0130] Preferred fluorescent emitting compounds are selected from the class of the arylamines. An arylamine or an aromatic amine in the context of this invention is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9 position. An aromatic anthracenediamine is understood to mean 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.

[0131] Matrix materials for fluorescent emitters:

[0132] Preferred matrix materials for fluorescent emitters are selected from the classes of the oligoarylenes (e.g. 2,2’,7,7’-tetraphenylspirobifluorene), especially the oligoarylenes containing fused aromatic groups, the oligoarylenevinylenes, the polypodal metal complexes, the hole-conducting compounds, the electron-conducting compounds, especially ketones, phosphine oxides and sulfoxides; the atropisomers, the boronic acid derivatives or the benzanthracenes. Particularly preferred matrix materials are selected from the classes of the oligoarylenes comprising naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of the oligoarylenes comprising anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. An oligoarylene in the context of this invention shall be understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

[0133] Matrix materials for phosphorescent emitters:

[0134] Preferred matrix materials for phosphorescent emitters, as well as the compounds or mixtures according to the application, are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g. CBP (N,N- biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0135] Electron-transporting materials:

[0136] Suitable electron-transporting materials are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0137] Materials used for the electron transport layer may be any materials that are used as electron transport materials in the electron transport layer according to the prior art. Especially suitable are aluminum complexes, for example Alqa, zirconium complexes, for example Zrq4, lithium complexes, for example Liq, 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.

[0138] Preferred electron transport and electron injection materials are the compounds shown in the table on page 122 to page 123 of WO2020 / 127176.

[0139] In a preferred embodiment, the electron transport layer(s) and the hole blocker layer of the electronic device containing at least one compound or mixture according to the application contain a compound containing a triazine group.

[0140] In a further preferred embodiment of the invention, the electron transport layer(s), preferably the electron transport layer(s) and the electron injection layer, of the electronic device contain a mixture containing lithium quinolinate and at least one further compound.

[0141] Hole-transporting materials:

[0142] Further compounds which, in addition to the compounds or mixtures according to the application, are used with preference in hole-transporting layers of the OLEDs according to the application are indenofluoreneamine derivatives, amine derivatives, hexaazatri phenylene derivatives, amine derivatives with fused aromatic systems, monobenzoindenofluoreneamines, dibenzoindenofluoreneamines, spirobifluoreneamines, fluoreneamines, spirodibenzopyranamines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrenediarylamines, spirotribenzotropolones, spirobifluorenes having meta-phenyldiamine groups, spirobisacridines, xanthenediarylamines, and 9,10-dihydroanthracene spiro compounds having diarylamino groups. Preferred hole-transporting compounds are especially the compounds disclosed in the table from the bottom of page 116 to the bottom of page 120 in WO 2021 / 104749.

[0143] Besides the compounds of the invention, further deuterated compounds that are suitable for use in layers having a hole-transporting function in any OLEDs are depicted below:

[0144] Deuterated compounds can be obtained by different processes, for example by reacting building blocks together, where at least one of the builing block is partly or completely deuterated (like in WO 2011 / 050888) or by deuterating the compound once it has been synthesized (like in WO 2010 / 099534). For example, undeuterated compounds can be treated with deuterated acids such as D2SO4 or D3PO4 for several hours to obtain deuterated compounds. It is also possible to react undeuterated compound in a deuterated solvent in the presence of a Lewis acid such as aluminum trichloride to obtain deuterated compounds. There are also some deuteration methods using high temperatures and electrical voltage or radiation. Other deuteration methods use D2 gas, D2O, or a deuterated solvent such as CeDe as a deuterium source to perform a H-D exchange by metal catalysis like in WO 2016 / 073425 or KR101978651. Other methods for deuteration of aromatic compounds use an acid catalyst and a deuterated aromatic solvent as deuterium source like in WO 2011 / 053334.

[0145] Preferred cathodes of the electronic device 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, Mg, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is 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, U2O, BaF2, MgO, NaF, CsF, CS2CO3, 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.

[0146] Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. AI / Ni / NiOx, AI / PtOx) may also be preferred. For some applications, at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the emission 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.

[0147] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by a sublimation process. In this case, the materials are applied by vapor deposition in vacuum sublimation systems at an initial pressure of less than 10’5mbar, preferably less than 10'6mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10'7mbar.

[0148] Preference is likewise given to an electronic device, 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 10’5mbar 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).

[0149] Preference is additionally given to an electronic device, characterized in that one or more layers are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds are needed. High solubility can be achieved by suitable substitution of the compounds.

[0150] It is further preferable that an electronic device according to the application is produced by applying one or more layers from solution and one or more layers by a sublimation method.

[0151] After application of the layers, according to the use, the device is structured, contact- connected and finally sealed, in order to rule out damaging effects of water and air. According to the invention, the electronic devices comprising a compound or mixture according to the application can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications.

[0152] Examples

[0153] The deuteration degree and deuterium positions in the following compounds are determined by quantitative1H-NMR and by 2D-NMR-spectroscopie.

[0154] A) Synthesis examples

[0155] 1) Synthesis of Starting Material SM26

[0156] 178 g of dry Pt-C-5% (45.7 moles; 0.06 eq.), 2.7 L of deuterium oxide (148.6 moles; 188 eq.) and 1.9 L of decaline [CAS: 91-17-8] are stired for 10 min under inert atmosphere. Then 10.8 g (0.3 mol, 0.36 eq.) of sodium borhydride [CAS: 16940-66-2] is added in portions. 299 g (0.8 mol, 1.0 eq.) of N-(9,9-Dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-1- amine [CAS: 2225845-23-6] is added and heated to reflux for 22 h. The cold mixture is filtered and the solvent is removed under reduced pressure. Final purification is done via recrystallization from toluene, methanol. Yield: 248 g (0.6 mol; 79% of theoretical yield) of SM 26.

[0157] The compounds from the following table are synthesized in similar manner:

[0158] 2) Synthesis of compound 26

[0159] Under inert atmosphere, 559 mg (1.36 mmol; 1 mol%) of Dicyclohexyl-(2',6'-dimethoxy- biphenyl-2-yl)-phosphane (SPhos) [CAS 657408-07-6], and 632 mg (0.68 mmol; 0.5 mol%) of Tris(dibenzylidenacetone)dipalladium [CAS 51364-51-3] are added to a mixture of 50.0 g (136 mmol; 1.00 eq.) of 7'-Chlorospiro[fluorene-9,9'-xanthene] [CAS 2361169- 35-7], 56.9 g (143 mmol; 1.05 eq.) of SM 26, and 45.0 g (408 mmol; 3.00 eq.) of Sodium- tert-pentoxide [CAS 14593-46-5] in 1 L of toluene [CAS 108-88-3], The reaction mixture is heated to 100°C for 18 hours. Then, 500 ml of water is added to the cold reaction mixture. The aqueous phase is separed from the organic layer and extracted twice with 100 ml of toluene. The combined organic layers are washed with water and brine, dried with sodium sulfate and the solvent is removed under reduced pressure. By addition of heptane, a precipitate is formed. Final purification is done via recrystallization from heptane:toluene mixtures and sublimation. Yield: 43.3 g (60.1 mmol, 44% of theoretical yield) of a colorless solid.

[0160] The compounds from the following table are synthesized in similar manner:

[0161] 3) Synthesis of comparative compounds CC1, CC2, CC3, CC4, CC5 und CC6

[0162] The comparative compounds CC1 , CC3 and CC5 are synthesized in similar manner as compound 26.

[0163] Synthesis of CC2, CC4 and CC6:

[0164] 50 g of CC1 (0.07 moles; 1.0 equivalent), 30 g of dry Pt-C-5% (0.15 moles; 2.2 equivalents), 0.27 L of deuterium oxide (15 moles; 212 equivalents) and 2.4 L of cyclohexane is stirred for 10 minutes under nitrogen atmosphere. The reaction mixture is heated to 140°C for 40 hours. The cold mixture is filtered off and the residue is washed several times with hot toluene. The solvent is removed under reduced pressure to obtain the product. Purification via recrystallization from toluene, methylcyclohexane, or xylol and sublimation yields in 5 g (6.8 millimoles; 10% of theoretical yield, d-degree via1H-NMR 49%) of CC2 as a colorless solid. CC4 (Starting Material CC3, Yield 15%, d-degree via1H-NMR 55%) and CC6 (starting material CC5, Yield 8%, d-degree via1H-NMR 52%) are synthesized in similar manner as CC2.

[0165] B) Device examples

[0166] 1) General production process for the OLEDs and characterization of the OLEDs

[0167] Glass plaques which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm are the substrates to which the OLEDs are applied.

[0168] The OLEDs basically have the following layer structure: substrate I hole injection layer (HIL) I hole transport layer (HTL) I electron blocker layer (EBL) I emission layer (EML) I electron transport layer, optionally with second layer (ETL) I electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in the tables which follow. The materials used for production of the OLEDs are shown in a table below.

[0169] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer consists of at least one matrix material (host material) and an emitting dopant which is added to the matrix material(s) in a particular proportion by volume by coevaporation. Details given in such a form as H:SEB (3%) mean here that the material H is present in the layer in a proportion by volume of 97% and SEB in a proportion of 3%.

[0170] In an analogous manner, the electron transport layer and the hole injection layer also consist of a mixture of two materials. The structures of the materials that are used in the OLEDs are shown in Table 3.

[0171] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming Lambertian radiation characteristics, and the lifetime are determined. The parameter EQE @ 10 mA / cm2refers to the external quantum efficiency which is attained at 10 mA / cm2. The parameter U @ 10 mA / cm2refers to the operating voltage at 10 mA / cm2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion in the course of operation with constant current density. An LT80 figure means here that the lifetime reported corresponds to the time after which the luminance has dropped to 80% of its starting value. The figure @60 mA / cm2means here that the lifetime in question is measured at 60 mA / cm2. The figure Rel LT80 @ 60 mA / cm2 (%) means the LT80@60 mA / cm2in relation to the given comparative example in percentage.

[0172] 2) Inventive OLEDs containing a compound of the formula (I) in the EBL of bluefluorescing OLEDs

[0173] Devices as shown in the following table are produced:

[0174] Following results were achieved:

[0175] For better comparison, the value for “Rel. LT80” is always set to 100% for the undeuterated compound.

[0176] The working example shows that similar driving voltage and efficienciy is achieved via deuteration, while the life time was increased. Only amine deuteration had the same impact on lifetime increase as deuteration of the entire molecule.

Claims

Claims1 . Compound A comprising a group of formula (I) and a group of formula (II),Formula (I) Formula (II) where the group of formula (I) is bonded to at least one group of formula (II) via the positions denoted by * in formulae (I) and (II); andX1stands for O or S;X2stands for a single bond, O or S;Z stands on each occurrence, identically or differently, for CR1or N, or for C if it is bonded to a group of formula (II) via a group — Ar5*;X3stands for a single bond, BR2, C(R2)2, C(R2)2-C(R2)2, Si(R2)2, Si(R2)2-Si(R2)2, O, S or NR2;Ar1stands for an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R2, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R2radicals;Ar2stands for an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R2, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R2radicals;Ar5stands for a single bond, an aromatic ring system having 6 to 30 aromatic ring atoms, which might be substituted by one or more radicals R1, or for an heteroaromatic ring system having 5 to 30 aromatic ring atoms, which might be substituted by one or more R1radicals;R1is the same or different at each instance and is selected from H, F, C(=O)R3, CN, Si(R3)3, N(R3)2, P(=O)(R3)2, S(=O)R3, S(=O)2R3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R1radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R3radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R3C=CR3-, -C=C-, Si(R3)2, C=O, C=NR3, -C(=O)O-, C(=O)NR3-, NR3, P(=O)(R3), -O-, -S-, SO or SO2;R2is the same or different at each instance and is selected from H, D, F, C(=O)R4, CN, Si(R4)3, N(R4)2, P(=O)(R4)2, S(=O)R4, S(=O)2R4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R2radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R4radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R4C=CR4-, -C=C-, Si(R4)2, C=O, C=NR4, -C(=O)O-, C(=O)NR4-, NR4, P(=O)(R4), -O-, -S-, SO or SO2;R3is the same or different at each instance and is selected from H, F, C(=O)R, CN, Si(R)3, N(R)2, P(=O)(R)2, S(=O)R, S(=O)2R, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R3radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -RC=CR-, -C=C-, Si(R)2, C=O, C=NR, -C(=O)O-, C(=O)NR-, NR, P(=O)(R), -O-, -S-, SO or SO2;R4is the same or different at each instance and is selected from H, D, F, C(=O)R', CN, Si(R')3, N(R')2, P(=O)(R')2IS(=O)R', S(=O)2R', straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R4radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R' radicals; and where one or more CH2groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R'C=CR'-, - C=C-, Si(R')2, C=O, C=NR', -C(=O)O-, C(=O)NR'-, NR', P(=O)(R'), -O-, -S-, SO or SO2;R is the same or different at each instance and is selected from H, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN;R' is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R' radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; m is 0 or 1 ; when m is 0 then the group X3is absent n is the same or different at each instance and is 0 or 1 , where the sum of all the indices n is 1 , 2, 3 or 4; characterized in that,Ar1and Ar2are both deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%, and the group of formula (I) is an undeuterated group.

2. Compound A according to claim 1, characterized in that X1stands for O and X2stands for a single bond.

3. Compound A according to claim 1 or 2, characterized in that Ar1and Ar2are, identically or differently, selected from groups of the formulae (A-1) to (A-51):where the dashed bonds indicate the bonds to the nitrogen atom, where the groups (A-1) to (A-51) are deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%, and the groups (A-1) to (A-51) may further be substituted by one, two or three radicals R2other than H or D.

4. Compound A according to claim 3, characterized in that, in formulae (A-1) to (A-51), the 6-membered ring which is directly bonded to the nitrogen atom has a deuteration degree on free aromatic positions equal to or higher than 50%.

5. Compound A according to one or more of the preceding claims, characterized in that: R1is selected from H, F, straight-chain alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 18 aromatic ring atoms; where two or more R1radicals may be joined to one another and may form a ring; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R3radicals;R2is selected from H, D, F, straight-chain alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 18 aromatic ring atoms; where two or more R2radicals may be joined to one another and may form a ring; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R4radicals;R3is the same or different at each instance and is selected from H, F, CN, straightchain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, aromatic ring systems having 6 to 12 aromatic ring atoms, and heteroaromatic ring systems having 5 to 12 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R radicals;R4is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms, aromatic ring systems having 6 to 12 aromatic ring atoms, and heteroaromatic ring systems having 5 to 12 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R' radicals;R is the same or different at each instance and is selected from H, F, CN, alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms; andR' is the same or different at each instance and is selected from H, D, F, CN, alkyl groups having 1 to 6 carbon atoms, branched or cyclic alkyl groups having 3 to 6 carbon atoms.

6. Compound A according to one or more of the preceding claims, characterized in that the group of formula (I) is selected from the groups of formulae (1-1), (I-2), (I-3), (I-4) and (I-5),where the symbols have the same meaning as in claim 1.

7. Compound A according to one or more of the preceding claims, characterized in that the group of formula (I) is selected from the groups of formulae (1-1 A) to (1-1 D) and (I- 2A) to (I-2D)where the symbols have the same meaning as in claim 1.

8. Process for preparing a compound A as defined in one or more of claims 1 to 7, said process comprising the step of performing a chemical reaction between an intermediate compound of formula (lnt-1) with an intermediate compound of formula (lnt-2-Deut) to obtain a compound A:(lnt-1) whereY1corresponds to a leaving group selected, identically or differently on each occurrence, from the group consisting of halogens, trifluoromethanesulfonate (CF3SO3-), tosylate (CH3C6H4SO3-) or mesylate (CH3SO3-);Y2stands for H or D; and the other symbols and indices have the same meaning as in claim 1 , and whereAr1and Ar2in formula (lnt-2-Deut) are have the same definition as in claim 1 and are both deuterated groups having a deuteration degree on free aromatic positions equal to or higher than 50%; the intermediate compound of formula (lnt-1) is an undeuterated intermediate compound.

9. Process according to claim 8, characterized in that the chemical reaction between an intermediate compound of formula (lnt-1) with an intermediate compound of formula (lnt-2-Deut) is selected from amination reactions, more preferably from Buchwald- hartwig or Ullmann aminations reactions as well as nucleophilic aromatic substitution reactions.

10. Process according to claim 8 or claim 9, characterized in that the intermediate compound (lnt-2-Deut) is obtained via an H-D exchange method.

11. Process according to claim 10, characterized in that the H-D exchange method is selected from H-D exchange by metal catalysis and H-D exchange by acid catalysis or mixture thereof.

12. Electronic device comprising at least one compound A according to one or more of claims 1 to 8.

13. Electronic device according to claim 12, characterized in that it is an organic electroluminescent device and that it comprises an anode, a cathode and at least oneemitting layer, and in that the compound according to one or more of claims 1 to 8 is contained in a hole transporting layer or in an emitting layer of the device.

14. Electronic device according to claim 12 or 13 comprising in the following order:-anode--hole injection layer--hole transport layer--electron blocker layer--emitting layer--hole blocker layer--electron transport layer--electron injection layer--cathode- where the compound A according to claim 1 to 8 is present in the electron blocker layer of the electronic device.

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