Heterocyclic compounds for organic electroluminescent devices

Abstract

The present invention relates to heterocyclic compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these heterocyclic compounds.

Description

[0001] The present invention relates to heterocyclic compounds for use in electronic devices, especially in organic electroluminescent devices, and to electronic devices, especially organic electroluminescent devices, comprising these materials.

[0002] Electronic devices containing organic compounds are well known and commercially available. These devices may, for example, each comprise one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. There is often a need to improve the performance of these devices, and in particular, the compounds used in the layers detailed above have a significant impact on the performance of the devices.

[0003] In addition, the luminescent materials used in organic electroluminescent devices are generally phosphorescent organometallic complexes. For quantum mechanical reasons, the use of organometallic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. In electroluminescent devices, especially those that exhibit triplet luminescence (phosphorescence), there is still a need for improvement. The properties of phosphorescent electroluminescent devices do not depend solely on the triplet emitter used. More particularly, other materials used, such as matrix materials, are also particularly important. Therefore, improvements in these materials can also lead to significant improvements in the performance of electroluminescent devices.

[0004] Analogous statements also apply to organic electroluminescent devices based on fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0005] JP 2021-166280 A and CN 112300144 A disclose heterocyclic compounds that can be used in organic electroluminescent devices. The compounds according to the present invention are not disclosed.

[0006] In general, when these materials are used, for example, as matrix materials and hole-transport materials and / or electron-transport materials, there is still a need for improvement, in particular with regard to the efficiency and operating voltage of the devices, and also with regard to the lifetime.

[0007] It was therefore an object of the present invention to provide a compound which is suitable for use in organic electronic devices, in particular organic electroluminescent devices, and which, when used in such devices, leads to good device properties, and to corresponding electronic devices.

[0008] More particularly, one object addressed by the present invention is to provide compounds which lead to a high lifetime, good efficiency and low operating voltage.In particular, the properties of the matrix material also have a significant influence on the lifetime and efficiency of organic electroluminescent devices.

[0009] Another object of the present invention can be considered to be to provide compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as host materials. A particular object of the present invention is to provide host materials suitable for blue, green, yellow and red phosphorescent electroluminescent devices, in particular for blue phosphorescent electroluminescent devices.

[0010] Furthermore, the compounds, in particular when they are employed as matrix materials, as hole-transport materials or as electron-transport materials in organic electroluminescent devices, should give rise to devices having excellent lifetimes and efficiencies.

[0011] Another object may be considered to be to provide very cheap and stable electronic devices with excellent performance.

[0012] Furthermore, it should be possible to use or modify electronic devices for many purposes. More particularly, the performance of electronic devices should be maintained over a wide temperature range.

[0013] Surprisingly, it has been found that this object is achieved by specific compounds, which will be described in detail later, which are very suitable for use in electroluminescent devices and lead to good properties of organic electroluminescent devices, in particular with regard to lifetime, color purity and efficiency, and operating voltage. The present invention therefore provides these compounds and electronic devices, in particular organic electroluminescent devices, comprising these compounds.

[0014] The present invention provides a compound comprising at least one structure of formula (I), preferably a compound of formula (I),

[0015]

[0016] The symbols are as follows:

[0017] Z is identical or different in each case and is Ar or R, preferably Ar;

[0018] W 1 are the same or different in each case and are -C(R a )2-(Y) n -C(R b )2-group, -C(R c )=C(R c )-group or an ortho-attached aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and substituted by one or more R d group substitution;

[0019] W 2 are the same or different in each case and are -C(R a )2-(Y) n-C(R b )2-group, -C(R c )=C(R c )-group or an ortho-attached aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and substituted by one or more R d group substitution;

[0020] R is identical or different in each case and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R e )2,C(=O)N(Ar)2,C(=O)N(R e )2,C(Ar)3,C(R e )3,Si(Ar)3,Si(R e )3,B(Ar)2,B(R e )2,C(=O)Ar,C(=O)R e , P(=O)(Ar)2, P(=O)(R e )2,P(Ar)2,P(R e )2,S(=O)Ar,S(=O)R e , S(=O)2Ar, S(=O)2R e , OSO2Ar, OSO2R e , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R e group, wherein one or more non-adjacent CH2 groups may be replaced by R e C=CR e 、C≡C、Si(R e )2. C=O, C=S, C=Se, C=NR e 、-C(=O)O-、-C(=O)NR e -、NR e 、P(=O)(R e ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R e An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group and which may be replaced by one or more R e At the same time, the R group can be combined with other groups, preferably with R a Forming a ring system;

[0021] Ar is identical or different in each case and is a cyclic aromatic hydrocarbon having 5 to 60 aromatic ring atoms and may be replaced by one or more R e At the same time, the two Ar groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or selected from B(R e )、C(R e )2、Si(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) and P(=O)R e The bridge is connected to the base bridge;

[0022] R a 、R b are in each case identical or different and are OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、-C(=O)O-、-C(=O)NR 1 -、NR1 、P(=O)(R 1 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R a 、R b The groups may also form a ring system with each other or with other groups, preferably with R;

[0023] n is 0 or 1, wherein when n=0, the Y group is absent, and the two -C(R a )2- and -C(R b )2-groups are directly bonded to each other;

[0024] Y is identical or different in each case and is C(R c )2、C(R c )2-C(R c )2、C(R c )=C(R c );

[0025] R c 、R d 、R e are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,Ge(Ar')3,Ge(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2、Ge(R 1 )2. C=O, C=S, C=Se, C=NR 1 、-C(=O)O-、-C(=O)NR 1 -、NR 1 、P(=O)(R 1 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R c 、R d 、R e The groups may also form a ring system with each other or with other groups, preferably with R a Forming a ring system;

[0026] Ar' is identical or different in each case and is an aromatic ring having 5 to 60 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be separated by a single bond or selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging bases are connected to each other;

[0027] R 1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2,C(=O)Ar”,C(=O)R 2,P(=O)(Ar”)2,P(Ar”)2,B(Ar”)2,B(R 2 )2,C(Ar”)3,C(R 2 )3,Si(Ar”)3,Si(R 2 )3, Ge(Ar”)3, Ge(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2、Ge(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2 and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more, preferably adjacent R 1 The groups may form a ring system with each other; at the same time, one or more R 1 The group may form a ring system with another part of the compound;

[0028] Ar" are identical or different in each case and are aromatic rings having 5 to 30 atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar" groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be separated by a single bond or selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R2 )、P(R 2 ) and P(=O)R 2 The bridging bases are connected to each other;

[0029] R 2 are identical or different in each case and are selected from H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more, preferably adjacent, substituents R 2 Together they can form a ring system;

[0030] It is characterized in that W 1 、W 2 At least one of the groups is -C(R a )2-(Y) n -C(R b )2-group.

[0031] It is preferably possible that the R groups are identical or different in each case and are selected from the group consisting of H, D, C(Ar)3, C(R e )3,Si(Ar)3,Si(R e )3,B(Ar)2,B(R e )2,C(=O)Ar,C(=O)R e , P(=O)(Ar)2, P(=O)(R e )2,P(Ar)2,P(R e )2,S(=O)Ar,S(=O)R e , S(=O)2Ar, S(=O)2R e , OSO2Ar, OSO2R e , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R e group, wherein one or more non-adjacent CH2 groups may be replaced by R e C=CR e 、C≡C、Si(R e )2. C=O, C=S, C=Se, C=NR e 、-C(=O)O-、-C(=O)NR e -、NR e、P(=O)(R e ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R e An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group and which may be replaced by one or more R e At the same time, one R group can be substituted with other groups, preferably with R a Form a ring system. Wherein R is selected from H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R e )2, C(=O)N(Ar)2, C(=O)N(R e )2 are particularly suitable as intermediates for preparing preferred compounds of the present invention.

[0032] Aryl groups in the context of the present invention contain 6 to 40 carbon atoms; heteroaryl groups in the context of the present invention contain 3 to 40 carbon atoms and at least one heteroatom, with the proviso that the total number of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Aryl or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene; or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc.; or fused (annulated) aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

[0033] The electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group with at least one heteroaromatic six-membered ring, and the heteroaromatic six-membered ring has at least one nitrogen-atom. Other aromatic or heteroaromatic five-membered rings or six-membered rings can be fused on this six-membered ring. The example of the electron-deficient heteroaryl group is pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

[0034] In the context of the present invention, an aromatic ring system contains 6 to 60 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system contains 3 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. In the context of the present invention, an aromatic or heteroaromatic ring system is understood to mean a system in which it does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups may also be connected via non-aromatic units, such as carbon, nitrogen or oxygen atoms. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be regarded as aromatic ring systems, as well as systems in which two or more aryl groups are connected, for example, via short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9′-spirobifluorene, 9,9-diarylamine or a group in which two or more aryl and / or heteroaryl groups are linked to each other via a single bond.

[0035] In the context of the present invention, an aliphatic hydrocarbon- or alkyl- radical or an alkenyl- or alkynyl- radical which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be replaced by the abovementioned radicals is preferably understood as meaning a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, 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, heptynyl or octynyl radical. Alkoxy groups having 1 to 40 carbon atoms are preferably understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals having 1 to 40 carbon atoms are to be understood as meaning in particular methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, the alkyl, alkoxy or thioalkyl groups according to the invention may be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; in addition, one or more hydrogen atoms may also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, further preferably by F or CN, particularly preferably by CN.

[0036] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms which in each case may also be substituted by the above-mentioned radicals and which can be linked to the aromatic or heteroaromatic system via any desired position are understood as meaning in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, letrozole, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylidene, terphenyl, terphenylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, 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, phenanthroline, Oxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, Azoles, benzophenones Azoles, naphtho Azoles, anthracenes azole, phenanthroline Azoles, isocyanates azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, 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, phen Oxazine, phenothiazine, fluorescent red ring, 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, or radicals derived from combinations of these systems.

[0037] In the context of this specification, the expression that two or more radicals together can form a ring is understood to mean in particular that the two radicals are linked to one another by a chemical bond under the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0038]

[0039] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0040]

[0041] In a preferred configuration, the compound of the present invention may preferably contain at least one structure of formula (I-1) to (I-18), more preferably a compound selected from formula (I-1) to (I-18),

[0042]

[0043]

[0044]

[0045] The symbols Z and R a 、R b and R c Having the definitions given above, in particular for formula (I), V is B(R d )、C(R d )2、Si(R d )2、N(R d ), O, S, preferably C(R d )2、Si(R d )2、N(R d ), O, and X is N or C (R d ), preferably C(R d ), where R d has the definitions given above, especially for formula (I).

[0046] Preference is given here to structures / compounds of the formulae (I-1) to (I-4) and particular preference to structures / compounds of the formulae (I-1) to (I-3), very particular preference to structures / compounds of the formula (I-1).

[0047] The Z group is preferably Ar, wherein preferred configurations of the Ar group are also presented below in conjunction with the Ar groups that may be part of the Z group.

[0048] Preferably, the Ar or R group is a group having 5 to 18, preferably 5 to 13, more preferably 6 to 13 aromatic ring atoms and can be replaced by one or more R e Aromatic or heteroaromatic ring systems substituted with radicals.

[0049] It is also possible that the Ar radicals are identical or different in each case and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or terphenylidene, each of which may be replaced by one or more R e The substituted group is preferably phenyl, biphenyl, fluorene, dibenzofuran, terphenylidene, carbazole, or indolocarbazole.

[0050] The Ar group may preferably be surrounded by at least one R e A phenyl group substituted with a substituent in which the substituent is in the ortho, meta, or para position based on the site of attachment to the nitrogen atom. For example, if R e If the group is a phenyl group, an ortho-biphenyl, meta-biphenyl or para-biphenyl group can be formed.

[0051] If the Ar group is a triazine group, it is preferably possible that the triazine group has two R groups other than H or D. e Group, where two R e The radical preferably has 5 to 60, preferably 6 to 30, aromatic ring atoms and can be replaced in each case by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0052] Furthermore, the Ar group may preferably be separated by at least one R e The phenyl group substituted by a group, wherein the substituent forms together with the phenyl group represented by the Ar group a fluorene group that may be bonded via the 1-, 2-, 3- or 4-position, a spirobifluorene group that may be bonded via the 1-, 2-, 3- or 4-position, an indole group, a benzofuran group, a benzothiophene group, a carbazole group that may be bonded via the 1-, 2-, 3- or 4-position, a dibenzofuran group that may be bonded via the 1-, 2-, 3- or 4-position, a dibenzothiophene group that may be bonded via the 1-, 2-, 3- or 4-position, an indenocarbazole group or an indolocarbazole group.

[0053] In another embodiment, it is possible that the structure / compound according to the invention comprises at least one electron transporting group and / or electron withdrawing group, preferably a triazine group and / or a phosphine oxide group. Electron transporting groups are well known in the art and promote the ability of the compound to transport and / or conduct electrons. Examples of electron transporting groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole groups, with triazine groups being particularly preferred. Electron withdrawing groups include in particular S(=O)2Ar', S(=O)2R e , B(R e )、B(Ar')、P(R e)O, P(Ar')O, said groups may exist, for example, as substituents of Ar or R groups. In addition, these electron-withdrawing groups may also exist as substituents R a 、R b 、R c 、R d 、R e present in the structures / compounds of formula (I) and / or formula (I-1) to (I-18), for example, as substituents B(Ar')2, B(R 1 )2, P(=O)(Ar')2, P(=O)(R 1 )2、S(=O)2Ar'、S(=O)2R 1 Present in the structure / compound of formula (I) and / or formula (I-1) to (I-18). In addition, the electron-withdrawing group also includes, for example, a C=O group or a CN group, which may be present in the structure as a substituent, for example, as a substituent C(=O)Ar, C(=O)Ar', C(=O)R e 、C(=O)R e or C(=O)R 1 Exists in the structure.

[0054] In another embodiment, it is possible that the structure / compound according to the invention comprises at least one hole-transporting group. Hole-transporting groups are likewise known in the art and preferably comprise triarylamine or carbazole groups.

[0055] The compounds of the present invention are particularly suitable as host materials for luminophores, preferably as host materials for singlet, triplet and TADF luminophores, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials, and hole blocking materials in electronic devices. The specific properties of the compound depend on the type and number of the corresponding functional groups. Compounds containing one, two or more electron transport groups and / or electron withdrawing groups but not containing hole transport groups are particularly suitable as host materials, electron transport materials, electron injection materials and / or hole blocking materials. Compounds containing one, two or more hole transport groups but not containing electron transport groups and / or electron withdrawing groups are particularly suitable as host materials, hole conducting materials, hole injection materials and / or electron blocking materials. Compounds containing one, two or more hole transport groups and one, two or more electron transport groups and / or electron withdrawing groups are particularly suitable as host materials.

[0056] Other feasible situations are, R, R c 、R d 、R eAt least one of the groups is not H, preferably not H, D, OH, NO2, F, Cl, Br, I. Other possible situations are that R, R a 、R b 、R c 、R d 、R e The groups are not OH, NO2, F, Cl, Br, or I.

[0057] In another preferred embodiment, it is possible that the compound of the present invention comprises a structure of formula (II-1) to (II-8), wherein the compound of the present invention can more preferably be selected from the compounds of formula (II-1) to (II-8),

[0058]

[0059]

[0060] The symbol R a 、R b 、R c and R d has the definitions given above, especially for formula (I), and the other symbols are as follows:

[0061] Y e are identical or different in each case and are B(R e )、C(R e )2、Si(R e )2、Ge(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) or P(=O)R e , preferably N(R e )、O、S、B(R e )、C(R e )2 or Si(R a )2, more preferably N(R e ), O or S, where R e has the definitions given above, in particular for formula (I), or if there are groups bonded to the structure, then Y e For B, C (R e )-、Si(R e )-;

[0062] X e are identical or different in each case and are N, CR e , or if there is a group bonded to the structure, then Xe C, X e Preferably CR e or C, provided that there are no more than three X in the ring e The group is N, where R e has the definitions given above, in particular for formula (I);

[0063] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0064] Preference is given here to structures / compounds of the formulae (II-1), (II-2), (II-3), (II-5), (II-6) and (II-7), particular preference to structures / compounds of the formulae (II-1) and (II-5).

[0065] In formulae (II-1) to (II-8), it is possible that if there is a group bonded to a specific structure, then X e is C. The group is particularly e The ring structure of the group is shown in formulas (II-5) to (II-8). The ring structure can be connected via X e Group or through Y e bonding, in which case Y e For B, C (R e )-、Si(R e )-.

[0066] In one embodiment, it is possible that in the structures / compounds of formula (II-1) to (II-8), no more than three, preferably two, X e The group is N, preferably all X e CR e Preferably at least one, more preferably at least two X per ring e The group is selected from CH and CD.

[0067] It is further possible that at least one, preferably at least two, more preferably three X e The groups are N, wherein these groups are preferably not adjacent. These structures / compounds preferably contain electron-transporting groups and are therefore particularly suitable as electron-transporting materials and / or matrix materials.

[0068] In another preferred embodiment, it is possible that the compound of the present invention comprises a structure of formula (III-1) to (III-32), wherein the compound of the present invention can more preferably be selected from the compounds of formula (III-1) to (III-32),

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] The symbol R a 、R b 、R c 、R d and R e has the definitions given above, especially for formula (I), and the other symbols are as follows:

[0075] Y e are identical or different in each case and are B(R e )、C(R e )2、Si(R e )2、Ge(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) or P(=O)R e , preferably N(R e )、O、S、B(R e )、C(R e )2 or Si(R e )2, more preferably N(R e ), O or S;

[0076] j is 0, 1, or 2;

[0077] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0078] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0079] l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0080] Preferred here are structures / compounds of formula (III-1), (III-2), (III-5), (III-7), (III-9), (III-10), (III-13), (III-15), (III-21), (III-23), and (III-25), particularly preferred are structures / compounds of formula (III-1), (III-2), (III-5), (III-9), and (III-10), and very particularly preferred are structures / compounds of formula (III-1), (III-2), and (III-9).

[0081] The sum of the indices j, m, n and l in the structures / compounds of the formulae (III-1) to (III-32) is preferably not greater than 6, particularly preferably not greater than 4, and more preferably not greater than 2.

[0082] When in particular one can be selected from R, R a 、R b 、R c 、R d 、R e 、R 1 and / or R 2 When two groups of the ring system form a ring system with each other, the ring system may be a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system. In this case, the groups that together form the ring system may be adjacent, which means that these groups are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they may be further apart from each other.

[0083] In a preferred embodiment of the present invention, it is possible that at least two preferably adjacent R a 、R b 、R c 、R d 、R e Group with the two R a 、R b 、R c 、R d 、R eThe other groups to which the group is bonded together form a condensed ring. In a preferred configuration, it is feasible that a ring structure described in the following document is formed: document WO 2022 / 079068 A1, application number PCT / EP2021 / 078240 filed with the European Patent Office on October 13, 2021; For the purpose of disclosure, the condensed ring structures shown in these documents and the descriptions of the ring elements of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or (RB) on pages 37 to 40 of document WO 2022 / 079068A1 are incorporated herein by reference. The ring structures detailed above of the ring elements shown in detail in document WO 2022 / 079068 A1 and preferably comprising formulas (RA-1) to (RA-12) and (RA-1a) to (RA-4f) particularly cause the structure / compound of the present invention to have a surprisingly low refractive index.

[0084] Another feasible situation is that the substituents R, R a 、R b 、R c 、R d 、R e 、R 1 and R 2 Not with the substituent R, R a 、R b 、R c 、R d 、R e 、R 1 and R 2 The ring atoms of the ring system to which they are bonded form a fused aromatic or heteroaromatic ring system, more preferably not fused with the substituents R, R a 、R b 、R c 、R d 、R e 、R 1 and R 2 The ring atoms of the ring system to which the substituent R is bonded form any ring system. This includes the ring atoms of the ring system to which the substituent R is bonded. a 、R b 、R c 、R d 、R e and R 1 Possible substituents R 2 A fused aromatic or heteroaromatic ring system is formed.

[0085] It is also possible that at least one R c 、R d 、R eThe radicals are identical or different in each case and are selected from H, D, branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 20 carbon atoms or aromatic or heteroaromatic ring systems selected from the radicals of the following formulae Ar-1 to Ar-76, or R c 、R d 、R e The groups are identical or different in each case and are selected from H, D or an aromatic or heteroaromatic ring system selected from the group consisting of the following formulae Ar-1 to Ar-76, and / or the Ar' groups are identical or different in each case and are selected from the group consisting of the following formulae Ar-1 to Ar-76,

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] where R 1 Having the definitions given above, a dotted bond represents a bond to the corresponding group, and in addition:

[0094] Ar 1 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a group;

[0095] A is identical or different in each case and is C(R 1 )2、NR 1 , O or S;

[0096] p is 0 or 1, wherein p=0 means Ar 1 The group is not present and the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding group;

[0097] q is 0 or 1, wherein q=0 means that no A group is bonded to this position, and R 1 The groups are bonded to the corresponding carbon atoms.

[0098] Here, preferred formulas are (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar -45), (Ar-46), (Ar-69), (Ar-70), and (Ar-76) structures, particularly preferably the structures of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16).

[0099] When the above groups for the structures of formula (Ar-1) to (Ar-76) have two or more A groups, all possible options include all combinations from the definition of A. In this case, a preferred embodiment is that one of the A groups is NR 1 and the other A group is C(R 1 )2 or wherein both A groups are NR 1 or those cases where both A groups are O.

[0100] When A is NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may also be replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which does not have any fused aryl groups and any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are directly fused to one another, and which may in each case also be replaced by one or more R 2 Phenyl, biphenyl, terphenyl and quaterphenyl are preferred. Also preferred are triazines, pyrimidines and quinazolines as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, wherein these structures may be replaced by one or more R 2 Groups substituted instead of R 1 replace.

[0101] When A is C(R 1 )2, the substituent R bonded to the carbon atom 1 are preferably identical or different in each case and are a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more R 2Most preferably, R 1 is a methyl group or a phenyl group. In this case, R 1 The groups together can also form ring systems, giving rise to spirocyclic systems.

[0102] Next, the preferred R c 、R d and R e group.

[0103] In a preferred embodiment of the present invention, R c 、R d and R e are in each case identical or different and are selected from the group consisting of H, D, F, CN, NO2, Si(R 1 )3,B(OR 1 )2, a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case being substituted by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0104] In another preferred embodiment of the present invention, the group R c 、R d and R e are identical or different in each case and are selected from H, D, F, straight-chain alkyl radicals having 1 to 20 carbon atoms or branched or cyclic alkyl radicals having 3 to 20 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case being substituted by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0105] It is also possible that at least one R c 、R d and R e group, preferably a substituent R c 、R d and R e , are identical or different in each case and are selected from H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, or N(Ar')2 group; more preferably, at least one substituent R c 、R d and R eare identical or different in each case and are selected from the group consisting of aromatic rings having 6 to 30 atoms and which may be replaced by one or more R 1 In another preferred embodiment of the present invention, the substituent R c 、R d and R e Form a fused ring, or R c 、R d and R e The radicals are identical or different in each case and are selected from H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 More preferably, R c 、R d and R e Group, preferably substituent R c 、R d and R e , which are identical or different in each case and are selected from H, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms, and which may in each case be replaced by one or more R 1 Group substitution.

[0106] It is also possible that R c 、R d and R e At least one of the groups is selected from the structure of the following formula (Het-I):

[0107]

[0108] The dotted bond represents the bond connected to the corresponding group, and the other symbols are as follows:

[0109] W 3 、W 4 are the same or different in each case and are -C(R 3 )2-(Y 1 ) n -C(R 3 )2-group, -C(R 1 )=C(R 1 )-group or an ortho-attached aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and substituted by one or more R 1 Group substitution; R 1 has the definitions given above, in particular for formula (I);

[0110] Y 1are identical or different in each case and are selected from C(R 1 )2、C(R 1 )2-C(R 1 )2、C(R 1 )=C(R 1 ), where R 1 has the definitions given above, in particular for formula (I); and

[0111] R 3 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2,C(=O)Ar”,C(=O)R 2 ,P(=O)(Ar”)2,P(Ar”)2,B(Ar”)2,B(R 2 )2,C(Ar”)3,C(R 2 )3,Si(Ar”)3,Si(R 2 )3, Ge(Ar”)3, Ge(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2、Ge(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more, preferably adjacent R 3 The groups together can form a ring system; at the same time, one or more R3 The group may form a ring system with another part of the compound, wherein R 2 has the definitions given above, especially for formula (I).

[0112] The preferred feasible situation is that W 3 、W 4 At least one of the groups is -C(R 3 )2-(Y 1 ) n -C(R 3 )2-group.

[0113] In a preferred configuration, it is possible that R c 、R d and R e At least one of the groups, preferably R d and R e At least one of the groups, more preferably R e At least one of the groups is selected from the structures of the following formulae (Het-II) to (Het-XIX),

[0114]

[0115]

[0116]

[0117] The symbol R 1 and R 3 has the definitions given above, in particular for formula (I) or (Het-I), V 1 B(R 1 )、C(R 1 )2、Si(R 1 )2、N(R 1 ), O, S, preferably C(R 1 )2、Si(R 1 )2、N(R 1 ), O, and X 1 N or C(R 1 ), preferably C(R 1 ).

[0118] Preference is given here to the structures of the formulae (Het-II) to (Het-V), particular preference is given to the structure of the formula (Het-XIX), very particular preference is given to the structure of the formula (Het-II).

[0119] The preferred feasible case is that R 3 The groups are identical or different in each case and are selected from B(Ar")2, B(R 2)2,C(Ar”)3,C(R 2 )3,Si(Ar”)3,Si(R 2 )3, Ge(Ar”)3, Ge(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2、Ge(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more, preferably adjacent R 3 The groups together can form a ring system; at the same time, one or more R 3 The group may form a ring system with another part of the compound, wherein R 2 has the definitions given above, especially for formula (I).

[0120] Further preferences for the groups shown in the structures of formulae (Het-I) to (Het-XIX) will be apparent from the description of the compounds of the invention, wherein W shown in formulae (I) and (I-1) to (I-18) 1 、W 2 , X, V, R a 、R b 、R c 、R d and R e The group should be accordingly W 3 、W 4 、X1 、V 1 、R 1 and R 3 Particularly preferred groups are correspondingly derived from structures / compounds of formulae (II-1) to (II-8) or (III-1) to (III-32), wherein X e and Y e The groups should be adjusted accordingly so that R e The group should be R 1 Particularly preferred R 3 Group from R a and R b It will be apparent from the description of the groups that R 1 The group should be R 2 Group replacement.

[0121] It is also possible that at least one R c 、R d and R e A radical is a radical having 5 to 13 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0122] It is preferred that at least one group, preferably one substituent R c 、R d and R e , selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or terphenylene, each of which may be replaced by one or more R 1 The expression "substituent" here more particularly refers to R c 、R d and R e is not H, preferably is not H and is not D. Furthermore, if two or more substituents are present from the aromatic or heteroaromatic groups mentioned, the substituents R c 、R d and R e Can be the same or different.

[0123] Preferably, R, R a 、R b 、R c 、R d and R eAlternatively, the aromatic or heteroaromatic ring system represented by the Ar or Ar' group is selected from phenyl; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-terphenyl or a branched quaterphenyl; fluorene, which may be attached via the 1-, 2-, 3- or 4-position; spirobifluorene, which may be attached via the 1-, 2-, 3- or 4-position; naphthalene, in particular 1- bonded or 2-bonded naphthalene; indole; benzofuran; benzothiophene; carbazole which may be attached via the 1-, 2-, 3- or 4-position; dibenzofuran which may be attached via the 1-, 2-, 3- or 4-position; dibenzothiophene which may be attached via the 1-, 2-, 3- or 4-position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; isoquinoline; quinazoline; quinoxaline; phenanthrene or terphenylene, each of which may be substituted by one or more R e 、R 1 or R 2 Particularly preferably, R, R a 、R b 、R c 、R d and R e Alternatively, the aromatic or heteroaromatic ring system represented by the Ar or Ar' group is the structures (Ar-1) to (Ar-76) described in detail above, preferably the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-76), and particularly preferably the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16). With respect to structures (Ar-1) to (Ar-76), it should be noted that these structures are replaced by the possible substituents R 1 In the case of the ring system Ar, these possible substituents R 1 Should be replaced by R e .

[0124] Other suitable R c 、R d and R e The group is of formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 、Ar 3 and Ar 4 are identical or different in each case and have 5 to 24 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group.2 、Ar 3 and Ar 4 The total number of aromatic ring atoms in is not more than 60, preferably not more than 40.

[0125] Here, Ar 4 and Ar 2 It can also be selected from C(R 1 )2、NR 1 , O or S groups are bonded to each other, and / or Ar 2 and Ar 3 It can also be selected from C(R 1 )2、NR 1 , O or S groups are bonded to each other. Preferably, Ar 4 and Ar 2 are connected to each other at the corresponding ortho positions bonded to the nitrogen atom and Ar 2 and Ar 3 In another embodiment of the present invention, Ar 2 、Ar 3 and Ar 4 The groups are not bonded to each other.

[0126] Preferably, Ar 4 is a ring having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms and in each case may be replaced by one or more R 1 More preferably, Ar 4 Selected from o-phenylene, m-phenylene or p-phenylene or o-biphenyl, m-biphenyl or p-biphenyl, each of which may be replaced by one or more R 1 Most preferably, Ar 4 is an unsubstituted phenylene group.

[0127] Preferably, Ar 2 and Ar 3 are identical or different in each case and are aromatic rings having 6 to 24 atoms and may be replaced by one or more R 1 Ar is particularly preferably an aromatic or heteroaromatic ring system substituted with a group. 2 and Ar 3The radicals are identical or different in each case and are selected from: benzene; o-, m- or p-biphenyl; o-, m- or p-terphenyl or branched terphenyl; o-, m- or p-terphenyl or branched terphenyl; o-, m- or p-terphenyl or branched terphenyl; 1-, 2-, 3- or 4-fluorenyl; 1-, 2-, 3- or 4-spirobifluorenyl; 1- or 2-naphthyl; indole; benzofuran; benzothiophene; 1-carbamide oxazole, 2-carbazole, 3-carbazole or 4-carbazole; 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran or 4-dibenzofuran; 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene or 4-dibenzothiophene; indenocarbazole; indolocarbazole; 2-pyridine, 3-pyridine or 4-pyridine; 2-pyrimidine, 4-pyrimidine or 5-pyrimidine; pyrazine; pyridazine; triazine; phenanthrene or terphenylene, each of which may be replaced by one or more R 1 Most preferably, Ar 2 and Ar 3 are in each case identical or different and are selected from: benzene; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-terphenyl or a branched quaterphenyl; fluorene, in particular 1-, 2-, 3- or 4-fluorene; or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0128] Due to the limitation specified in claim 1, for R c 、R d and R e The preferences described for the group also apply to R a and R b group.

[0129] It is further possible that R bonded to a carbon atom a The groups are the same.

[0130] It is also possible that R bonded to different carbon atoms a The groups are the same.

[0131] Another possible situation is that R bonded to different carbon atoms a The groups are different.

[0132] In a preferred configuration, it is possible that R bonded to the carbon atom a The group is selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 1 The substituents R aTogether they can form a ring system.

[0133] Alternatively, R bonded to a carbon atom a The radical is selected from the group consisting of aromatic rings having 5 to 20 atoms and each of which may be replaced by one or more R 1 An aromatic or heteroaromatic ring system which is substituted by a radical and which is preferably in each case substituted by one or more R 1 A phenyl group substituted with a radical, preferably deuterated, wherein two or more, preferably adjacent, substituents R a Together they can form a ring system.

[0134] It is also possible that R bonded to a carbon atom b The groups are the same.

[0135] Another possible situation is that R bonded to different carbon atoms b The groups are the same.

[0136] It is further possible that R bonded to different carbon atoms b The groups are different.

[0137] In a preferred configuration, it is possible that R bonded to the carbon atom b The group is selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 1 substituted by a group, preferably deuterated, wherein two or more, preferably adjacent, substituents R a Together they can form a ring system.

[0138] Alternatively, R bonded to a carbon atom b The radical is selected from the group consisting of aromatic rings having 5 to 20 atoms and each of which may be replaced by one or more R 1 An aromatic or heteroaromatic ring system which is substituted by a radical and which is preferably in each case substituted by one or more R 1 A phenyl group substituted with a radical, preferably deuterated, wherein two or more, preferably adjacent, substituents R b Together they can form a ring system.

[0139] It is also possible that R a The group is preferably adjacent to R b The groups together form a 1 A radically substituted aliphatic or heteroaliphatic ring system, wherein the ring system preferably contains 3 to 10 carbon atoms.

[0140] In another preferred embodiment of the present invention, R 1are identical or different in each case and are selected from H, D, F, CN, straight-chain alkyl radicals having 1 to 10 carbon atoms or branched or cyclic alkyl radicals having 3 to 10 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 2 or having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 2 In a particularly preferred embodiment of the present invention, R 1 are in each case identical or different and are selected from H, a linear alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 substituted, but preferably unsubstituted, or having 6 to 13 aromatic ring atoms and in each case substituted by one or more R 2 The aromatic or heteroaromatic ring system may be substituted by substituted groups, but is preferably unsubstituted.

[0141] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are: H, an alkyl radical having 1 to 4 carbon atoms or an aryl radical having 6 to 10 carbon atoms, which may be substituted by an alkyl radical having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0142] At the same time, in the compounds of the invention processed by vacuum evaporation, the alkyl group preferably has no more than 5 carbon atoms, more preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. For compounds processed from solution, suitable compounds are also those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or with oligoarylene groups such as o-, m- or p-terphenyl or branched terphenyl or quaterphenyl groups.

[0143] In a preferred configuration, the structures / compounds of the present invention preferably have a high degree of deuteration. Preferably, the degree of deuteration is at least 50%, preferably at least 80%, particularly preferably at least 90%, and most preferably at least 95%. 1 The numerical ratio of the sum of the H hydrogens (D / (D+H)×100) is determined. The compounds are particularly preferably fully deuterated.

[0144] The compounds of the present invention are particularly suitable for use in blue luminescent electroluminescent devices. Depending on the layer, these require materials with high triplet energy levels. However, many substituents with fused aromatic or heteroaromatic groups can cause a decrease in the triplet energy level.

[0145] Therefore, a naphthyl structure is preferred to anthracene structure. Furthermore, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothiophenyl structure is preferred to a naphthyl structure.

[0146] Particular preference is given to unfused structures such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0147] It is further more preferable that Ar or R groups do not contain anthracene groups; preferably, Ar, R, R a 、R b 、R c 、R d 、R e The groups do not contain anthracene groups.

[0148] It is also very particularly preferred that the Ar or R radical does not contain an aromatic or heteroaromatic ring system having three linearly fused aromatic 6-membered rings, wherein preferably Ar, R, R a 、R b 、R c 、R d 、R e None of the groups contain an aromatic or heteroaromatic ring system having three linearly fused aromatic 6-membered rings.

[0149] When the compound of the present invention is replaced by an aromatic or heteroaromatic R a 、R b 、R c 、R d 、R e 、R 1 or R 2 When the substituents are substituted, it is preferred that these do not have any following aryl or heteroaryl groups, the aryl or heteroaryl groups having more than two aromatic six-membered rings directly fused to each other. More preferably, the substituents do not have any following aryl or heteroaryl groups, the aryl or heteroaryl groups having six-membered rings directly fused to each other. The reason for this preference is the low triplet energy of such structures. According to the present invention, fused aryl groups having more than two aromatic six-membered rings directly fused to each other but still having good applicability are phenanthrene and terphenylene, because they also have high triplet energy levels.

[0150] Another feasible situation is that Ar, R, R a 、R b 、R c 、R d and R e The groups do not contain or form fluorenone groups, preferably Ar, R, R a 、R b 、R c 、R d 、Re 、R 1 and R 2 The groups do not contain or form fluorenone groups. This includes Ar, R, R a 、R b 、R c 、R d 、R e Fluorenone comprises a five-membered ring having a CO group fused to two aromatic six-membered rings.

[0151] When the compounds of the formula (I) or the preferred embodiments are used as matrix materials for phosphorescent emitters or in a layer directly adjacent to the phosphorescent layer, it is also preferred that the compounds do not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to one another. Phenanthrene and terphenylidene are exceptions, and they may be preferred despite the presence of fused aromatic six-membered rings due to their high triplet energy.

[0152] In a preferred embodiment of the present invention, it is possible that the compound

[0153]

[0154] are excluded from the scope of protection.

[0155] It is also possible that the compound contains exactly two, exactly three or exactly four structures of the formulae (I), (I-1) to (I-18), (II-1) to (II-8) and / or (III-1) to (III-32).

[0156] In a preferred configuration, the compound is selected from compounds of formula (D-1),

[0157]

[0158] Among them L 1 The group is a linking group, preferably a bond or a cyclic aromatic group having 5 to 40, preferably 5 to 30, aromatic ring atoms and can be supported by one or more R e an aromatic or heteroaromatic ring system substituted with a radical, and the other symbols used have the meanings given above, in particular for formula (I), in which L 1 The group replaces the hydrogen atom or substituent to form a bond to the basic structure; preferably, L 1 Group and Z, W 1 、W 2 Group bonded, preferably with Z group. A further feasible situation is that it can be bonded with L 1 The Z group to which the group is bonded is also shared by the two base structures, so that the compound of formula (D1) has only one Z group and L 1 is given by the Z group.

[0159] In another preferred embodiment of the present invention, L 1 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which ring system may be replaced by one or more R e Groups are substituted, but preferably are unsubstituted, wherein R e may have the definitions given above, in particular the definitions given for formula (I). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be replaced by one or more R 1 Groups are substituted, but preferably are unsubstituted, wherein R 1 may have the definitions given above, in particular for formula (I).

[0160] In addition, preferably, the symbol L shown in formula (D1) 1 In particular, these are in each case identical or different and are a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the corresponding atom of the other group.

[0161] Another possible situation is that L shown in formula (D1) 1 The radical comprises an aromatic ring system having not more than four, preferably not more than three, more preferably not more than two fused aromatic and / or heteroaromatic 6-membered rings, and preferably does not comprise any fused aromatic or heteroaromatic ring systems.

[0162] Suitable aromatic or heteroaromatic ring systems L 1 Examples of are selected from: o-phenylene, m-phenylene or p-phenylene; o-biphenylene, m-biphenylene or p-biphenylene; terphenylene, especially branched terphenylene; quaterphenylene, especially branched quaterphenylene; fluorene; spirobifluorene; dibenzofuranene; dibenzothiophene; and carbazole, each of which may be replaced by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0163] In a preferred embodiment, the compound of the present invention may be represented by at least one structure of formula (I), (I-1) to (I-18), (II-1) to (II-8) and / or (III-1) to (III-32). Preferably, the molecular weight of the compound of the present invention preferably comprising the structure of formula (I), (I-1) to (I-18), (II-1) to (II-8) and / or (III-1) to (III-32) is not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, especially preferably not more than 2000 g / mol, more especially preferably not more than 1200 g / mol, and most preferably not more than 900 g / mol.

[0164] Furthermore, a feature of the preferred compounds of the present invention is that they are sublimable. The molar mass of these compounds is generally less than about 1200 g / mol.

[0165] It is also possible that the compound comprising the structure of formula (I), preferably the compound of formula (I) or preferred embodiments of this structure / compound is not in direct contact with a metal atom and is preferably not a ligand of a metal complex.

[0166] The preferred embodiments mentioned above can be combined with one another as desired within the limits defined in claim 1. In a particularly preferred embodiment of the invention, the preferred embodiments mentioned above occur simultaneously.

[0167] Examples of preferred compounds according to the above detailed embodiments are the compounds detailed in the following table:

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] The basic structure of the compound of the present invention can be prepared by the path outlined in the following scheme. Each synthesis step herein, for example, the coupling reaction causing C-C bond formation and / or C-N bond formation is in principle well known to those skilled in the art. These include Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira, and Hiyama reactions.

[0183] Additional information concerning the synthesis of compounds of the present invention can be found in the synthetic examples.

[0184] The following schemes describe, by way of example, the preparation of compounds of formula (I-1), (I-2) and (I-3) according to the present invention, so that other compounds of the present invention, in particular compounds of formula (I-4) to (I-18) can be obtained by analogous synthetic routes starting from different parent structures. A person skilled in the art will use the corresponding amine compounds for the preparation of compounds of formula (I-4) to (I-18).

[0185] For example, the compounds of the present invention can be prepared in four steps from synthetic units known from the literature, tetrasubstituted 1,2-diaminoethane (1) and 2-fluoronitrobenzene or 2-chloronitrobenzene (2) (wherein X: CR) or N-heterocyclic analogs (X: CR and at least one X = N) (see Scheme 1).

[0186] First, according to this protocol, a tetrasubstituted 1,2-diaminoethane is reacted with 2-fluoronitrobenzene or 2-chloronitrobenzene in a bipolar aprotic medium such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), or acetonitrile, optionally with the addition of a sterically demanding base such as a Hünig base in a nucleophilic aromatic substitution to form a C-N bond, thereby affording an o-nitroarylamine (3) (step 1); see, for example, P. Zhang et al., J. Med. Chem., 2009, 52(18), 5703. Subsequently, the nitro group is reduced to an amino group with the aid of hydrogen / platinum(IV) oxide or Pd / C to afford a triamine (4) (step 2); see, for example, JA Pollock et al., Tetrahedron Letters, 2015, 56, 6097. The triamine (4) is preferably reacted with phosgene in dichloromethane (DCM) to give the amide (see MT Blázquez et al., Heterocycles, 2006, 69, 73 - or alternatively triphosgene or trialkyl chloroformate or alkyl carbonate is used), which is then dehydrated in situ with polyphosphoric acid to give the guanidine (5) (see WO 2012 / 130709). Finally, the guanidine (5) is preferably reacted with an aryl or heteroaryl halide or triflate Ar / HetArX (X = F, Cl, Br, I, OTf) by Buchwald-Hartwig, Ullmann coupling or nucleophilic aromatic substitution (see, for example, WO 2012 / 130709) to give the compounds (6a) and (6b) according to the invention. The isomeric compounds (6a) and (6b) can be separated by standard methods (chromatography, fractional crystallization).

[0187] Option 1:

[0188]

[0189] Similarly, compounds of the present invention (10) can be prepared by first reacting a tetrasubstituted 1,2-diaminoethane (1) with a 2,2,3,3-tetraalkylaziridine (7) known from the literature to prepare a triamine (8); see Scheme 2. Other compounds of the present invention are obtained via the corresponding amine compounds.

[0190] The triamine (8) is preferably reacted with phosgene in dichloromethane (DCM) to give the amide (see MT Blázquez et al., Heterocycles, 2006, 69, 73 - alternatively triphosgene or trialkyl chloroformate or alkyl carbonate can be used), which is then dehydrated in situ with polyphosphoric acid to give the guanidine (9) (see WO 2012 / 130709). Finally, the guanidine (9) is preferably reacted with an aryl or heteroaryl halide or triflate Ar / HetArX (X = F, Cl, Br, I, OTf) by Buchwald-Hartwig, Ullmann coupling or nucleophilic aromatic substitution (see, for example, WO 2012 / 130709) to give the compound of the invention (10). If all R groups are identical, the product is compound (10) in isomerically pure form; if the R groups in reactants (1) and (7) are chosen differently, two isomeric compounds (10a and 10b) are obtained analogously to Scheme 1, which in turn can be separated by standard methods (chromatography, fractional crystallization).

[0191] Option 2:

[0192]

[0193] Compounds according to the invention (6) can be further functionalized, for example by regioselective bromination (see WO 2014 / 009317) followed by conversion of the bromide thus obtained in a CC or CN coupling reaction such as Suzuki, Negishi, Grignard-Cross, Sonogashira, Buchwald-Hartwig, Ullmann coupling; see Scheme 3.

[0194] Option 3:

[0195]

[0196] The definitions of the symbols used in the schemes presented above essentially correspond to those for formula (I), the numbering and complete representation of all symbols being omitted for the sake of clarity.

[0197] Therefore, the present invention also provides a method for preparing the compounds of the present invention, wherein a basic skeleton having an amino group is synthesized and at least one aromatic or heteroaromatic group is introduced, preferably by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0198] For the sake of completeness, it is pointed out that, for example, the structures of formula (I-2) and (I-3) can in many cases be converted into each other by rearrangement at high temperatures. These mixtures can be separated or used as such. This also applies to the other isomers. The mixtures obtained or formed here by rearrangement can be used to produce electronic devices as described above and will be described in more detail later.

[0199] By these methods, if necessary followed by purification, for example by recrystallization or sublimation, it is possible to obtain high purities, preferably greater than 99% (by means of 1 H-NMR and / or HPLC determination) of the compounds of the present invention.

[0200] The compounds of the present invention can also be mixed with polymers. Similarly, these compounds can be covalently incorporated into polymers. This can especially be used for compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters or by reactive polymerizable groups such as olefins or oxetanes. It has been found that these can be used as monomers for making corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably achieved via a halogen functional group or a boronic acid functional group or via a polymerizable group. In addition, polymers can be cross-linked via this group. The compounds of the present invention and polymers can be used in the form of a crosslinked or uncrosslinked layer.

[0201] The present invention also provides an oligomer, polymer or dendrimer comprising one or more of the structures of formula (I) and preferred embodiments thereof, or compounds of the invention, as described above, wherein one or more bonds of the compounds of the invention or of the structures of formula (I) and preferred embodiments thereof are present to the polymer, oligomer or dendrimer. Depending on the structure of formula (I) and preferred embodiments thereof or the linkage of the compound, these may form side chains of the oligomer or polymer or may be bonded within the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. The same preferences as above apply to the repeating units of the compounds of the invention in the oligomers, dendrimers and polymers.

[0202] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of formula (I) or the preferred embodiments described above and below are present in a range of 0.01 mol % to 99.9 mol %, preferably 5 mol % to 90 mol %, more preferably 20 mol % to 80 mol %. Suitable and preferred comonomers forming the basic backbone of the polymer are selected from the group consisting of: fluorene (e.g. according to EP 842208 or WO 2000 / 022026), spirobifluorene (e.g. according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (e.g. according to WO 92 / 18552), carbazole (e.g. according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (e.g. according to EP 1028136), dihydrophenanthrene (e.g. according to WO 2005 / 014689), cis- and trans-indenofluorene (e.g. according to WO 2004 / 041901 or WO 2004 / 113412), ketone (e.g. according to WO 2005 / 040302), phenanthrene (e.g. according to WO 2004 / 070772 or WO 2004 / 113468), 2005 / 104264 or WO 2007 / 017066) or other multiples of these units. The polymers, oligomers and dendrimers may also contain other units, such as: hole transport units, especially those based on triarylamines; and / or electron transport units.

[0203] In addition, compounds of the present invention that are characterized by a high glass transition temperature are of particular interest. In this regard, compounds of the present invention comprising the structure of formula (I) or the preferred embodiments described above and below are particularly preferred, having a glass transition temperature of at least 70° C., more preferably at least 110° C., even more preferably at least 125° C., and particularly preferably at least 150° C., as measured according to DIN 51005 (2005-08 edition).

[0204] In order to process the compounds of the present invention from the liquid phase, for example by spin coating or by printing, a formulation of the compounds of the present invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, Alkanes, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchonone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, NMP, p-cymene , phenethyl ether, 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 a mixture of these solvents.

[0205] Therefore, the present invention also provides a kind of preparation or composition, described preparation or composition comprises at least one compound of the present invention and at least one other compound.Other compound can be, for example, solvent, especially one of the above-mentioned solvents or mixture of these solvents.If other compound comprises solvent, then this mixture is referred to as preparation in this article.Other compound or can be at least one other organic or inorganic compound similarly used in electronic device, such as luminescent compound and / or other matrix material.Preferably feasible situation is, at least one other compound is selected from fluorescent light emitter, phosphorescent light emitter, luminophore that shows TADF, host material, electron transport material, electron injection material, hole conducting material, hole injection material, electron blocking material and hole blocking material, preferably host material.

[0206] The present invention also provides the use of the compounds of the present invention in electronic devices, particularly in organic electroluminescent devices. Preferably, the compounds of the present invention are used as host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials, or hole blocking materials in electronic devices.

[0207] It is further feasible that the compound of the present invention is used as a host material, an electron transport material, an electron injection material or a hole blocking material, and the compound of the present invention contains at least one electron transport group and / or an electron withdrawing group, wherein preferred electron transport groups and / or electron withdrawing groups have been defined above.

[0208] It is further possible that the compound according to the invention is used as host material, hole-conducting material, hole-injecting material or electron-blocking material and comprises at least one hole-transporting group, wherein preferred hole-transporting groups have been defined above.

[0209] It is also possible that the compound of the present invention is used as a host material, and the compound of the present invention contains at least one hole transport group and at least one electron transport group and / or electron withdrawing group, wherein preferred hole transport groups, electron transport groups and / or electron withdrawing groups have been defined above.

[0210] The present invention further provides an electronic device comprising at least one compound according to the invention. An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also comprise other layers formed entirely of inorganic materials or inorganic materials.

[0211] The electronic device is more preferably selected from: organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), light-emitting electrochemical cells (LEC), organic laser diodes (O-lasers), organic plasma light-emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quenching devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), more preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), especially phosphorescent OLEDs.

[0212] The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, the organic electroluminescent device may also comprise other layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers in each case. An intermediate layer having, for example, an exciton blocking function may also be introduced between the two light-emitting layers. However, it should be noted that each of these layers does not necessarily need to be present. In this case, the organic electroluminescent device may contain one light-emitting layer, or it may contain multiple light-emitting layers. If multiple light-emitting layers are present, then preferably these light-emitting layers have multiple emission peaks between 380nm and 750nm in total, so that the overall result is white light emission; in other words, a variety of light-emitting compounds that can emit fluorescence or phosphorescence are used in the light-emitting layer. A system with three light-emitting layers is particularly preferred, wherein the three layers emit blue, green and orange or red light. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, in particular a white light-emitting OLED.

[0213] The compounds of the present invention can be used in different layers according to the exact structure. Preferably, the organic electroluminescent device comprises a compound of formula (I) or the above-mentioned preferred embodiment in the light-emitting layer as a host material for a fluorescent light emitter, a phosphorescent light emitter or a light emitter showing TADF (thermally activated delayed fluorescence), especially a host material for a phosphorescent light emitter. In addition, the compounds of the present invention can also be used in an electron transport layer, an electron injection layer and / or a hole transport layer, a hole injection layer and / or an exciton blocking layer and / or a hole blocking layer. More preferably, the compounds of the present invention are used as a host material for a phosphorescent light emitter in the light-emitting layer, especially a host material for a red phosphorescent, orange phosphorescent, green phosphorescent, yellow phosphorescent or blue phosphorescent light emitter, in an electron transport layer or a hole blocking layer as an electron transport material or a hole blocking material, or in a hole transport layer or an electron blocking layer as a hole transport material or an electron blocking material. The applicability of the compounds of various formulas (I) has been shown above in conjunction with preferred uses.

[0214] When the compounds according to the invention are used as matrix materials for phosphorescent compounds in an emitting layer, they are preferably used in combination with one or more phosphorescent materials (triplet emitters).

[0215] In the context of the present invention, phosphorescence is understood to mean luminescence from excited states with a high spin multiplicity, i.e., spin states > 1, in particular luminescence from excited triplet states. In the context of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

[0216] The mixture of the compound according to the invention and the emitting compound contains between 99% and 1% by volume, preferably between 98% and 10% by volume, more preferably between 97% and 60% by volume, and in particular between 95% and 80% by volume of the compound according to the invention, based on the overall mixture of emitter and matrix material. Correspondingly, the mixture contains between 1% and 99% by volume, preferably between 2% and 90% by volume, more preferably between 3% and 40% by volume, and in particular between 5% and 20% by volume of emitter, based on the overall mixture of emitter and matrix material.

[0217] In one embodiment of the invention, the compounds according to the invention are employed here as sole matrix material (“single host”) for the phosphorescent emitter.

[0218] A further embodiment of the present invention is the use of the compounds according to the invention in combination with other matrix materials as matrix materials for phosphorescent emitters. Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, for example CBP (N,N-dicarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indenocarbazole derivatives, for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; triazine derivatives, for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; siladiazacyclopentaine or silatetraazacyclopentaine derivatives, for example according to WO 2010 / 054729; phosphadiazacyclopentaine derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives, for example according to WO 2012 / 048781; dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565; or bicarbazoles, for example according to JP 3139321 B2.

[0219] In a preferred configuration, the compound containing formula (I) or the structure / compound of the preferred embodiment detailed above as the host material is preferably combined with one or more phosphorescent materials (triplet emitters) and / or TADF (thermally activated delayed fluorescence) host materials. Here, preferably, a superfluorescent system as described in WO 2012 / 133188 and / or a superphosphorescent system as described in US 2017271611 is formed. This combination is a preferred embodiment according to the present invention.

[0220] WO 2015 / 091716 A1 and WO 2016 / 193243 A1 disclose OLEDs containing both a phosphorescent compound and a fluorescent emitter in the light-emitting layer, wherein energy is transferred from the phosphorescent compound to the fluorescent emitter (superphosphorescence). In this case, the phosphorescent compound accordingly acts as a host material. As known to those skilled in the art, the host material has higher singlet and triplet energies than the emitter, so that energy from the host material is transferred to the emitter with maximum efficiency. The systems disclosed in the prior art exhibit precisely this energy relationship.

[0221] Preferred emitters which can be used in combination with the compounds according to the invention are described, inter alia, in Sungho Nam et al., Adv. Sci. 2021, 2100586 and Eungdo Kin et al., Sci. Adv. 2022, 8, 1641. Preferred triplet emitters or triplet emitter classes, also referred to as sensitizers associated with superfluorescent systems, are also described in EP 3 435 438 A2, wherein emitter 2 and emitter 3 on page 21 are preferred; in CN 109111487, the compounds shown on pages 76 and 77 are preferred; in US2020 / 0140471, the compounds shown on pages 166 to 175 are preferred; in KR2020108705, the compounds shown on pages 8 to 14 are preferred; in US2019 / 0119312, the compounds shown on pages 114 to 121 are preferred; and in US2020 / 0411775, the compounds shown on pages 123 to 128 are preferred. In addition, preferred fluorescent emitters or fluorescent emitters are described in the following documents: in WO 2021 / 090932, wherein the compounds shown on pages 129 to 133, 157 to 166, 171 to 187, 200 to 211, 222 to 227, 236 to 252, 255 are preferred; in WO 2020 / 054676, wherein the compounds shown on pages 44 to 104 are preferred; in WO 2020 / 017931, wherein the compounds shown on pages 17 to 39 are preferred; in WO 2020 / 218079, wherein the compounds shown on pages 64 to 258 are preferred; in WO 2018 / 212169, wherein the compounds shown on pages 33 to 42 are preferred; in WO 2019 / 235452, wherein the compounds shown on pages 46 to 168 are preferred; in US 10,249,832, wherein the compounds shown on pages 19 to 106 are preferred; and in WO 2021 / 014001, wherein the compounds shown on pages 107 to 129 are preferred.

[0222] It is also possible that further phosphorescent emitters which emit at a shorter wavelength than the wavelength of the actual emitter are present in the mixture as co-hosts. Particularly good results are achieved when the emitter used is a red phosphorescent emitter and the co-host used in combination with the compounds according to the invention is a yellow phosphorescent emitter.

[0223] In addition, the co-host used may be a compound that participates in charge transport, but not to a significant extent, as described, for example, in WO 2010 / 108579. Particularly suitable as a co-host material in combination with the compounds of the present invention are compounds that have a large band gap and that themselves participate in charge transport in the light-emitting layer, but at least not to a significant extent. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680. In this context, it should be emphasized that the compounds of the present invention have advantageous properties in the absence of specific functional groups such as hole transport groups and / or electron transport groups.

[0224] Suitable phosphorescent compounds (=triplet emitters) are, in particular, compounds which, when suitably excited, emit light, preferably in the visible region, and further contain at least one atom, in particular a metal, having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

[0225] Examples of such emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439 and WO 2018 / 011186. In general, all phosphorescent complexes for phosphorescent electroluminescent devices according to the prior art and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without inventive step.

[0226] Examples of phosphorescent dopants are listed in the table below:

[0227]

[0228]

[0229]

[0230]

[0231]

[0232] The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described, for example, in WO 98 / 24271, US 2011 / 0248247 and US 2012 / 0223633. In these multicolor display components, an additional blue-emitting layer is applied by vapor deposition over the entire area to all pixels, including those with non-blue colors.

[0233] In another embodiment of the present invention, the organic electroluminescent device according to the invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, meaning that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. In addition, metal complexes that are identical or similar to the metal complexes in the light-emitting layer can be used as hole transport or hole injection materials directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0234] In other layers of the organic electroluminescent device of the present invention, any material commonly used according to the prior art can be used. Therefore, those skilled in the art will be able to use any known material for organic electroluminescent devices in combination with the compounds of the present invention of formula (I) or the above-mentioned preferred embodiments without paying creative work.

[0235] Furthermore, an organic electroluminescent device is preferred, characterized in that one or more layers are applied by a sublimation process. In this case, the organic electroluminescent device is applied by sublimation in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, the initial pressure can also be even lower, for example less than 10 -7 millibar.

[0236] Likewise preferred is an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (Organic Vapor Phase Deposition) method or by means of carrier gas sublimation. -5 The material is applied at a pressure between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thereby structured.

[0237] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (light-induced thermography, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds, obtained for example by suitable substitution, are required.

[0238] The formulations using the compounds of formula (I) or the preferred embodiments thereof detailed above are novel. Therefore, the present invention also provides a formulation comprising at least one solvent and a compound according to formula (I) or the preferred embodiments thereof detailed above.

[0239] Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0240] The person skilled in the art is generally aware of these processes and can apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

[0241] The compounds of the present invention and the organic electroluminescent devices of the present invention particularly have improved efficiency and / or operating voltage characteristics relative to the prior art. In addition, these compounds and the organic electroluminescent devices obtainable therefrom show improved lifespan. In a special variant, the compounds of the present invention and the organic electroluminescent devices of the present invention particularly have a low refractive index (RI) compared to the prior art. In addition, preferred compounds of the present invention show high triplet T1 energy levels, so these compounds are particularly suitable as host materials for triplet emitters of blue light emission.

[0242] The electronic device of the present invention, in particular the organic electroluminescent device, has one or more of the following surprising advantages compared to the prior art:

[0243] 1. Electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (I) or of the preferred embodiments described above and below, in particular as matrix materials, as electron-conducting materials or as hole-conducting materials, have excellent efficiency. In this case, the compounds of the invention of formula (I) or of the preferred embodiments described above and below, when used in electronic devices, result in low operating voltages.

[0244] 2. Electronic devices, in particular organic electroluminescent devices, comprising compounds of the formula (I) or according to the preferred embodiments described above and below, in particular as matrix materials, as electron-conducting materials or as hole-conducting materials, have very good lifetimes. In this case, these compounds bring about, in particular, a low roll-off, i.e., a low drop in the power efficiency of the device at high luminous densities.

[0245] 3. The compounds of the invention of formula (I) or of the preferred embodiments described above and below exhibit very high stability and longevity.

[0246] 4. Electronic devices, especially organic electroluminescent devices, comprising the compounds of the formula (I) or of the preferred embodiments described above and below, especially as matrix material, as electron-conducting material or as hole-conducting material have a high T1 level.

[0247] 5. The compounds of formula (I) or the preferred embodiments described above and below can be used to avoid the formation of optical loss channels in electronic devices, in particular organic electroluminescent devices. As a result, these devices are characterized by high PL efficiency of the emitter and, therefore, high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0248] 6. The compounds of formula (I) or of the preferred embodiments described above and below have excellent glass film formation.

[0249] 7. The compounds of formula (I) or of the preferred embodiments described above and below form very good films from solution.

[0250] These aforementioned advantages are not accompanied by a very serious degradation of other electronic properties.

[0251] It should be noted that the scope of the present invention encompasses variations of the embodiments described herein. Unless any feature disclosed herein is explicitly excluded, it may be replaced with an alternative feature having the same purpose or an equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed herein should be considered an example of a general series or an equivalent or similar feature.

[0252] Unless specific features and / or steps are mutually exclusive, all features of the present invention can be combined with each other in any way. This is especially true for the preferred features of the present invention. Similarly, features of non-essential combinations can be used individually (rather than in combination).

[0253] It should also be noted that many features of the present invention, particularly those of the preferred embodiments, should be considered inventive in their own right, and not merely as embodiments of the present invention, and for which independent protection may be sought as a supplement to or alternative to any presently claimed invention.

[0254] The technical teachings disclosed in this invention can be refined and combined with other embodiments.

[0255] The present invention is illustrated in detail by the following examples, but it is in no way intended to be limited thereby. Those skilled in the art will be able, without inventive effort, to use the information provided to implement the present invention within the entire scope disclosed, to prepare other compounds of the present invention and to use them in electronic devices, or to employ the methods of the present invention. Example

[0256] Unless otherwise stated, the following syntheses were performed in dry solvents under a protective gas atmosphere. Metal complexes require additional handling under light-protection or yellow light. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers cited for individual compounds are related to the CAS numbers of the compounds known from the literature. In the case of compounds that can have multiple enantiomers, diastereomers or tautomer forms, one form is shown in a representative manner.

[0257] A) Preparation of Synthon S

[0258] Example S1:

[0259]

[0260] 11.6 g (100 mmol) of 2,3-diamino-2,3-dimethylbutane [20485-44-3] and 9.9 g (100 mmol) of 2,2,3,3-tetramethylaziridine [5910-14-5] were added to 200 ml of distilled water. 200 ml of 1 M dihydrochloric acid in HCl was added dropwise to the mixture in oxane. The mixture was stirred in an autoclave at 110°C for 8 hours. After cooling, most of the dioxane was removed under reduced pressure. The residue was dissolved in 50 ml of methanol, 300 ml of 1N aqueous ammonia solution was added, and the mixture was extracted five times with 100 ml of dichloromethane (DCM). The combined organic phases were dried over potassium carbonate, the DCM was removed under reduced pressure, and the residue was fractionally distilled under reduced pressure. Yield: 5.1 g (23 mmol), 23%; Purity: about 97%, according to 1 H-NMR.

[0261] Example S10:

[0262] a) S10a:

[0263]

[0264] The procedure was similar to that of P. Zhang et al., J. Med. Chem., 2009, 52(18), 5703.

[0265] A well-stirred mixture of 11.6 g (100 mmol) of 2,3-diamino-2,3-dimethylbutane [20485-44-3], 7.1 g (50 mmol) of 2-fluoronitrobenzene [1493-27-2] and 200 ml of dimethylformamide (DMF) was stirred at 30° C. for 16 hours. Most of the DMF was removed under reduced pressure, and the residue was dissolved in 300 ml of ethyl acetate (EA), washed three times with 100 ml of water each time, once with 100 ml of saturated sodium chloride solution, and dried over sodium sulfate. The desiccant was filtered off, the filtrate was concentrated to dryness, and the residue was chromatographed (Torrent automated column system from A. Semrau). Yield: 8.8 g (38 mmol), 76%; purity: about 97%, according to 1 H-NMR.

[0266] When 2-chloronitrobenzene is used, the reaction is carried out at 60°C to 80°C.

[0267] b)S10b

[0268]

[0269] The procedure was similar to that of P. Zhang et al., J. Med. Chem., 2009, 52(18), 5703.

[0270] A well-stirred solution of 23.7 g (100 mmol) of S10a in 200 ml of methanol and 100 ml of THF was hydrogenated over 5 g of Pd / C, 5 wt. %, at 30° C. / approximately 4 bar until hydrogen uptake ceased (approximately 8 hours). The catalyst was filtered off as a THF slurry using a celite bed, and the filtrate was concentrated to dryness. Yield: 20.6 g (100 mmol), quantitative; purity: approximately 97%, according to 1 H-NMR.

[0271] Alternatively, the nitro function can be reduced with tin or zinc in aqueous hydrochloric acid medium.

[0272] c) S10:

[0273]

[0274] Process is similar to MT Blázquez et al., Heterocycles, 2006, 69, 73 and WO 2012130709. To 20.7g (100mmol) of S1b in 500ml of DCM, a fully stirred solution of phosgene and 20% by weight of toluene was added dropwise. The reaction mixture was gradually warmed to room temperature and heated to reflux for 12 hours (note: HCl escaped!). Subsequently, the solvent was completely distilled off, 100g of polyphosphoric acid was added, the mixture was heated to 100°C and homogenized by stirring (precision glass tower), the reaction mixture was heated to 220°C, and stirred for 1 hour. The mixture was stirred at 220°C for 3 hours, and allowed to cool to 80°C, then 500ml of water was gradually added (note: exothermic!). After cooling, the solid was filtered off with suction, washed three times with water, 100ml each time, washed once with 50ml of methanol, and dried by suction. The solid was suspended in 150 ml of methanol, 50 ml of concentrated aqueous ammonia was added, and the mixture was stirred for 30 minutes. The solid was filtered off, washed twice with 30 ml of methanol each time, and dried under reduced pressure. Yield: 17.5 g (80 mmol), 80%; Purity: about 97%, according to 1 H-NMR.

[0275] The following compounds can be prepared similarly:

[0276]

[0277]

[0278]

[0279]

[0280]

[0281] B) Synthesis Examples B1a and B1b of the Compounds of the Invention:

[0282] Variant 1: Ullmann coupling

[0283] The procedure is similar to WO 2012 / 130709. A well-stirred mixture of 21.5 g (100 mmol) of S10, 24.5 g (120 mmol) of iodobenzene [591-50-4], 65.2 g (200 mmol) of cesium carbonate, 3.8 g (20 mmol) of copper (I) iodide, 4.6 g (40 mmol) of L-proline, 100 g of glass beads (3 mm diameter) and 500 ml of dimethyl sulfoxide (DMSO) was stirred at 100 ° C for 16 hours (reaction at 130 ° C to 160 ° C using aryl / heteroaryl bromides or at 200 ° C in N-methyl-2-pyrrolidone). While still warm, the mixture was filtered through a bed of celite as a DMSO slurry. The filtrate was poured into 2000 ml of water while stirring. The precipitated solid was filtered, washed three times with 100 ml of water, twice with 100 ml of ethanol, and dried under reduced pressure. The solid was dissolved in dichloromethane and filtered through a bed of silica gel as a DCM slurry. The filtrate was gradually concentrated on a rotary evaporator, continuously replacing the distilled DCM with ethanol. The crystalline product was filtered off with suction, washed twice with 50 ml of ethanol, and dried under reduced pressure. Further separation and purification of isomers B1a and B1b were carried out by chromatographic separation (Torrent automated column system from Semrau), by repeated hot extractive crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1, volume:volume) and by fractional sublimation or heat treatment under high vacuum.

[0284] Yield:

[0285] B1a: 15.7 g (53 mmol), 53%; purity: about 99.9% according to HPLC.

[0286] B1b: 5.1 g (17 mmol), 17%; purity: about 99.9% according to HPLC.

[0287] Variant 2: Ullmann coupling

[0288] 24 ml (200 mmol) of trans-1,2-diaminocyclohexane can be used instead of L-proline. Instead of DMSO.

[0289] Yield:

[0290] B1a: 16.7 g (57 mmol), 57%; purity: about 99.9% according to HPLC.

[0291] B1b: 4.5 g (15 mmol), 15%; purity: about 99.9% according to HPLC.

[0292] Examples B2a and B2b:

[0293]

[0294] Variant 3: S N Ar reaction

[0295] The procedure is similar to WO 2012 / 130709. A well-stirred mixture of 21.5 g (100 mmol) of S10, 14.5 g (120 mmol) of 4-fluorobenzonitrile [1194-02-1], 41.5 g (300 mmol) of potassium carbonate, 100 g of glass beads (3 mm diameter) and 500 ml of dimethylacetamide (DMAc) was stirred at 160 ° C for 16 hours. While still warm, the mixture was filtered through a diatomaceous earth bed as a DMAc slurry. The filtrate was poured into 2000 ml of water while stirring. The precipitated solid was filtered, washed three times with water, 100 ml each time, and twice with ethanol, 100 ml each time, and dried under reduced pressure. The solid was dissolved in dichloromethane and filtered through a silica gel bed as a DCM slurry. The filtrate was gradually concentrated on a rotary evaporator, continuously replacing the distilled DCM with ethanol. The crystalline product was filtered off with suction, washed twice with 50 ml of ethanol and dried under reduced pressure. Further purification was carried out as described in B1a / B1b.

[0296] Yield:

[0297] B2a: 14.7 g (47 mmol), 47%; purity: about 99.9% according to HPLC.

[0298] B2b: 4.4 g (14 mmol), %; purity: about 99.9% according to HPLC.

[0299] Examples B200a and B200b:

[0300]

[0301] Variant 4: S N Ar reaction

[0302] To a solution of 22.6 g (105 mmol) of S10 in 300 ml of DMF, 2.4 g (100 mmol) of sodium hydride was added portionwise (caution: hydrogen evolution!). Subsequently, 37.8 g (110 mmol) of 2-[1,1'-biphenyl]-4-yl-4-chloro-6-phenyl-1,3,5-triazine [1472062-94-4] was added, and the mixture was stirred at room temperature for 5 hours. While stirring, 2000 ml of water was added dropwise. The precipitated solid was filtered, washed three times with 100 ml of water, twice with 100 ml of ethanol, and dried under reduced pressure. The solid was dissolved in dichloromethane and filtered through a bed of silica gel as a DCM slurry. The filtrate was gradually concentrated on a rotary evaporator, continuously replacing the distilled DCM with ethanol. The crystalline product was filtered off with suction, washed twice with 50 ml of ethanol, and dried under reduced pressure. Further purification was performed as described in B1.

[0303] Yield:

[0304] B200a: 31.2 g (60 mmol), 60%; purity: about 99.9% according to HPLC.

[0305] B200b: 6.2 g (12 mmol), 12%; purity: about 99.9% according to HPLC.

[0306] The following compounds can be prepared analogously, wherein the stoichiometry is adjusted to the corresponding number of bonds to be formed.

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354] Example: OLED Manufacturing

[0355] 1) Vacuum-treated devices:

[0356] The OLEDs according to the invention and the OLEDs according to the prior art are produced by the general process according to WO 2004 / 058911, which is adapted to the circumstances described there (layer thicknesses, variation of materials used).

[0357] In the examples that follow, the results for various OLEDs are presented. Clean glass plates coated with 50 nm thick structured ITO (indium tin oxide) (cleaned in a Miele laboratory glasswasher, Merck Extran detergent) were pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). These coated glass plates formed the substrates for the application of the OLEDs.

[0358] 1a) Blue Fluorescent OLED Component - BF:

[0359] The compounds of the present invention can be used in hole-injection layers (HILs), hole-transport layers (HTLs), and electron-transport layers (ETLs). All materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer (EML) here always consists of at least one matrix material (host material) SMB (see Table 1) and a luminescent dopant (dopant, emitter) D, which is added to one or more matrix materials in a specific volume ratio by coevaporation. Details given in the form of SMB:D (97:3%) mean that the material SMB is present in the layer in a volume ratio of 97% and the dopant D in a volume ratio of 3%. Similarly, the electron-transport layer can also consist of a mixture of two materials; see Table 1. The materials used to produce OLEDs are shown in Table 5 or in conjunction with the synthesis examples detailed above.

[0360] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum was determined, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were calculated as a function of the luminous density from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence behavior, and the lifetime was also determined. 2 The EQE in (%) and the voltage in (V) are reported at a luminous density of .

[0361] OLEDs have the following layer structure:

[0362] base

[0363] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm

[0364] Hole transport layer (HTL), see Table 1

[0365] Electron blocking layer (EBL), see Table 1

[0366] Emission layer (EML), see Table 1

[0367] Electron transport layer (ETL), see Table 1

[0368] Electron injection layer (EIL) composed of ETM2, 1nm

[0369] Aluminum cathode, 100nm

[0370] Table 1: Structure of blue fluorescent OLED components

[0371]

[0372]

[0373] Table 2: Results of blue fluorescent OLED components

[0374] Example EQE (%) Voltage (V) BF1 8.6 3.8 BF2 8.0 3.9 BF3 8.3 3.8 BF4 8.7 3.7 BF5 8.3 3.8

[0375] 1b) Phosphorescent OLED components:

[0376] Compound A according to the present invention can be used in the hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), and as a matrix material (host material) M (see Table 5) or A (see materials according to the present invention) in the emission layer (EML). For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. The emission layer here always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is added to the matrix material or materials by co-evaporation in specific volume ratios. Details given in the form of M1:M2:Ir (55%:35%:10%) mean that the material M1 is present in the layer in a volume ratio of 55%, M2 in a volume ratio of 35%, and Ir in a volume ratio of 10%. Similarly, the electron transport layer can also consist of a mixture of the two materials. The exact structure of the OLED can be found in Table 3. The materials used to produce the OLED are shown in Table 5 or in conjunction with the synthesis examples detailed above.

[0377] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum was determined, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) were calculated as a function of the luminous density from the current-voltage-luminous density characteristic (IUL characteristic) assuming Lambertian luminescence characteristics, and the lifetime was also determined. 2 The EQE in (%) and the voltage in (V) are reported at a luminous density of .

[0378] OLEDs have the following layer structure:

[0379] base

[0380] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm

[0381] Hole transport layer (HTL), see Table 3

[0382] Electron blocking layer (EBL), see Table 3

[0383] Emission layer (EML), see Table 3

[0384] Hole blocking layer (HBL), see Table 3

[0385] Electron transport layer (ETL), composed of ETM1:ETM2 (50%:50%), 30nm

[0386] Electron injection layer (EIL) composed of ETM2, 1nm

[0387] Aluminum cathode, 100nm

[0388] Table 3: Structure of phosphorescent OLED components

[0389]

[0390]

[0391]

[0392]

[0393] Table 4: Results for phosphorescent OLED components

[0394]

[0395]

[0396] Table 5: Structural formulas of materials used

[0397]

[0398]

[0399]

[0400]

Claims

1. A compound comprising at least one structure of formula (I), The symbols are as follows: Z is identical or different in each case and is Ar or R; W 1 are the same or different in each case and are -C(R a )2-(Y) n -C(R b )2-group, -C(R c )=C(R c )-group or an ortho-attached aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and substituted by one or more R d group substitution; W 2 are the same or different in each case and are -C(R a )2-(Y) n -C(R b )2-group, -C(R c )=C(R c )-group or an ortho-attached aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and substituted by one or more R d group substitution; R is identical or different in each case and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R e )2,C(=O)N(Ar)2,C(=O)N(R e )2,C(Ar)3,C(R e )3,Si(Ar)3,Si(R e )3,B(Ar)2,B(R e )2,C(=O)Ar,C(=O)R e , P(=O)(Ar)2, P(=O)(R e )2,P(Ar)2,P(R e )2,S(=O)Ar,S(=O)R e , S(=O)2Ar, S(=O)2R e , OSO2Ar, OSO2R e , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R e group, wherein one or more non-adjacent CH2 groups may be replaced by R e C=CR e 、C≡C、Si(R e )2. C=O, C=S, C=Se, C=NR e 、-C(=O)O-、-C(=O)NR e -、NR e 、P(=O)(R e ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R e An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group and which may be replaced by one or more R e an aralkyl or heteroaralkyl group substituted with a group; and the R group may form a ring system with other groups; Ar is identical or different in each case and is a cyclic aromatic hydrocarbon having 5 to 60 aromatic ring atoms and may be replaced by one or more R e At the same time, the two Ar groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond or selected from B(R e )、C(R e )2、Si(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) and P(=O)R e The bridge is connected to the base bridge; R a 、R b are in each case identical or different and are OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、-C(=O)O-、-C(=O)NR 1 -、NR 1 、P(=O)(R 1 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R a 、R b The groups may also form ring systems with each other or with other groups; n is 0 or 1, where When n=0, the Y group is absent and the two -C(R a )2- and -C(R b )2-groups are directly bonded to each other; Y is identical or different in each case and is C(R c )2、C(R c )2-C(R c )2、C(R c )=C(R c ); R c 、R d 、R e are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,Ge(Ar')3,Ge(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2、Ge(R 1 )2. C=O, C=S, C=Se, C=NR 1 、-C(=O)O-、-C(=O)NR 1 -、NR 1 、P(=O)(R 1 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R c 、R d 、R e The groups may also form ring systems with each other or with other groups; Ar' is identical or different in each case and is an aromatic ring having 5 to 60 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be separated by a single bond or selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging bases are connected to each other; R 1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2,C(=O)Ar”,C(=O)R 2 ,P(=O)(Ar”)2,P(Ar”)2,B(Ar”)2,B(R 2 )2,C(Ar”)3,C(R 2 )3,Si(Ar”)3,Si(R 2 )3, Ge(Ar”)3, Ge(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2、Ge(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2 and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted arylalkyl or heteroarylalkyl groups, or combinations of these systems; at the same time, two or more R 1 The groups may form a ring system with each other; at the same time, one or more R 1 The group may form a ring system with another part of the compound; Ar" are identical or different in each case and are aromatic rings having 5 to 30 atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group, wherein two Ar" groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be separated by a single bond or selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging bases are connected to each other; R 2 are identical or different in each case and are selected from H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more substituents R 2 Together they can form a ring system; It is characterized in that W 1 、W 2 At least one of the groups is -C(R a )2-(Y) n -C(R b )2-group.

2. The compound according to claim 1, comprising at least one structure of formula (I-1) to (I-18), The symbols Z and R a 、R b and R c Having the definition given in claim 1, V is B(R d )、C(R d )2、Si(R d )2、N(R d ), O, S, and X is N or C (R d ).

3. The compound according to claim 1 or 2, characterized in that Ar or R groups are aromatic groups having 5 to 13 aromatic ring atoms and may be replaced by one or more R e Aromatic or heteroaromatic ring systems substituted with radicals.

4. Compounds according to one or more of claims 1 to 3, comprising at least one structure of formula (II-1) to (II-8), The symbol R a 、R b 、R c and R d The definitions given in claim 1 are given, and other symbols used are as follows: Y e are identical or different in each case and are B(R e )、C(R e )2、Si(R e )2、Ge(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) or P(=O)R e , where R e has the meaning given in claim 1, or if there is a group bonded to the structure, then Y e For B, C (R e )-、Si(R e )-; X e are identical or different in each case and are N, CR e , or if there is a group bonded to the structure, then X e is C, provided that there are no more than three X in the ring e The group is N, where R e Having the definition given in claim 1; m is 0, 1, 2, 3 or 4.

5. Compounds according to one or more of claims 1 to 4, comprising at least one structure of formula (III-1) to (III-32), The symbol R a 、R b 、R c 、R d and R e The definitions given in claim 1 are given, and other symbols used are as follows: Y e are identical or different in each case and are B(R e )、C(R e )2、Si(R e )2、Ge(R e )2. C=O, C=NR e 、C=C(R e )2, O, S, S=O, SO2, N(R e )、P(R e ) or P(=O)R e ; j is 0, 1, or 2; n is 0, 1, 2, or 3; m is 0, 1, 2, 3 or 4; l is 0, 1, 2, 3, 4 or 5.

6. Compound according to one or more of claims 1 to 5, characterized in that At least one R c 、R d 、R e The radicals are identical or different in each case and are selected from H, D, branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 20 carbon atoms or aromatic or heteroaromatic ring systems selected from the radicals of the following formulae Ar-1 to Ar-76, or R c 、R d 、R e The groups are identical or different in each case and are selected from H, D or an aromatic or heteroaromatic ring system selected from the group consisting of the following formulae Ar-1 to Ar-76, and / or the Ar' groups are identical or different in each case and are selected from the group consisting of the following formulae Ar-1 to Ar-76: where R 1 Having the definitions given above, a dotted bond represents a bond to the corresponding group, and in addition: Ar 1 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a group; A is identical or different in each case and is C(R 1 )2、NR 1 , O or S; p is 0 or 1, wherein p=0 means Ar 1 The group is not present and the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding group; q is 0 or 1, wherein q=0 means that no A group is bonded to this position, and R 1 The groups are bonded to the corresponding carbon atoms.

7. Compound according to at least one of the preceding claims, characterized in that R bonded to a carbon atom a The group is selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 1 Group substitution, wherein two or more substituents R a Together they can form a ring system.

8. Compound according to at least one of the preceding claims, characterized in that R bonded to a carbon atom b The group is selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be replaced by one or more R 1 Group substitution, wherein two or more substituents R a Together they can form a ring system.

9. The compound according to at least one of the preceding claims, characterized in that The compound comprises at least one electron transporting group and / or electron withdrawing group.

10. The compound according to at least one of the preceding claims, characterized in that The compound comprises at least one hole transporting group.

11. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 10, wherein One or more bonds of the compound to the polymer, oligomer or dendrimer are present in place of a hydrogen atom or a substituent.

12. A preparation comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 and at least one further compound, wherein the further compound is selected from one or more solvents.

13. A composition comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

14. A process for preparing a compound according to one or more of claims 1 to 10, characterized in that A basic skeleton having an amino group is synthesized, and at least one aromatic or heteroaromatic group is introduced.

15. Use of a compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 in an electronic device. 16 . An electronic device comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 .

17. The electronic device according to claim 16, wherein the electronic device is an organic electroluminescent device, characterized in that The compound according to one or more of claims 1 to 10 or the oligomer, polymer or dendrimer according to claim 11 is used as a host material, electron transport material, electron injection material, hole conducting material, hole injection material, electron blocking material, hole blocking material.

Images