Materials for electronic devices

Abstract

The present application relates to triarylamine compounds of the defined formula. The application further relates to methods for making the compounds, the use of the compounds in electronic devices, and electronic devices comprising the compounds.

Description

[Technical Field]

[0001] This application relates to triarylamine compounds of formula (I) as defined below. These compounds are suitable for use in electronic devices. This application further relates to a method for preparing the compounds mentioned and to electronic devices containing the compounds mentioned.

[0002] The electronic devices relating to this application are understood to mean so-called organic electronic devices that contain organic semiconductor materials as functional materials. More specifically, these are understood to mean OLEDs (organic electroluminescent devices). The term OLED is understood to mean an electronic device having one or more layers containing organic compounds that emits light when a voltage is applied. The general principles of the structure and function of OLEDs are known to those skilled in the art.

[0003] In electronic devices, particularly OLEDs, there is strong interest in improving performance data, especially lifespan, efficiency, and operating voltage. However, satisfactory solutions in these areas have yet to be found.

[0004] The performance data of electronic devices is greatly influenced by the light-emitting layer and the layer with hole transport function. Novel compounds for use in these layers, particularly hole transport compounds, and compounds that can function as matrix materials, especially for phosphorescent materials, in the light-emitting layer are also needed.

[0005] In the prior art, various triarylamine compounds are known as hole transport materials for electronic devices. Similarly, the use of certain triarylamine compounds as matrix materials in light-emitting layers is also well known.

[0006] However, there is still a need for alternative compounds suitable for use in electronic devices.

[0007] Regarding performance data in the use of electronic devices, especially regarding operating voltage, lifespan, and efficiency, improvements are needed. Furthermore, regarding the processability of materials, their glass transition temperatures, solubility, stability in solution, and refractive indices, improvements are needed.

[0008] It has now been found that certain triarylamine compounds are extremely suitable for use in electronic devices, especially for use in OLEDs, particularly especially for use as hole transport materials in OLEDs and for use as matrix materials for phosphorescent emitters.

[0009] Therefore, the present application relates to formula (I)

[0010]

Chemical formula

[0011] (wherein the variable groups that appear are as follows: Z , is the same or different in each case, and is selected from CR 1 and N, where Z 1 is C when an Ar 1 or a T group is bonded thereto; Ar 1 is the same or different in each case, and is an aromatic ring system having 6 to 30 aromatic ring atoms and optionally substituted by one or more R 2 radicals; Ar 2 corresponds to formula (A) or (B) <图> <图> <图> <图>(A)

Chemical formula

[0014] The aryl group according to the present invention contains 6 to 40 aromatic ring atoms, none of which are heteroatoms. The aryl group according to the present invention is understood to mean a single aromatic ring, i.e., benzene, or a fused aromatic polycycle, such as naphthalene, phenanthrene, or anthracene. The fused aromatic polycycle according to the present invention consists of two or more single aromatic rings fused to each other. Inter-ring condensation is understood here to mean that the rings share at least one edge with each other.

[0015] The heteroaryl group according to the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O, and S. The heteroaryl group according to the present invention is either a single heteroaromatic ring, e.g., pyridine, pyrimidine, or thiophene, or a condensed heteroaromatic polycycle, e.g., quinoline or carbazole. The condensed heteroaromatic polycycle according to the present invention consists of two or more single heteroaromatic rings fused to each other. Interring condensation is understood here to mean that the rings share at least one edge with each other.

[0016] Each of the aryl or heteroaryl groups may be substituted with the radicals mentioned above and may be bonded to an aromatic or heteroaromatic system via any desired position, but in particular, benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluorantene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzoth Ophen, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthidine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalinimidazole, oxy Sazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-ox This is understood to mean groups derived from sadiazole, 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, tetrazol, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purines, pteridines, indoridines, and benzothiadiazoles.

[0017] The aromatic ring systems according to the present invention contain 6 to 40 carbon atoms in the ring system and do not contain any heteroatoms as aromatic ring atoms. Therefore, the aromatic ring systems according to the present invention do not contain any heteroaryl groups. The aromatic ring systems according to the present invention are not necessarily limited to those containing only aryl groups, and are naturally understood to mean systems in which multiple aryl groups are bonded by single bonds or non-aromatic units, for example, one or more optionally substituted C, Si, N, O, or S atoms. In this case, the non-aromatic units preferably contain less than 10% of non-H atoms based on the total number of non-H atoms in the system. For example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamines, diaryl ethers, and stilbenes are also considered aromatic ring systems according to the present invention, as are systems in which two or more aryl groups are bonded by, for example, linear or cyclic alkyl, alkenyl or alkynyl groups, or silyl groups. In addition, systems in which two or more aryl groups are bonded to each other via single bonds are also considered aromatic ring systems according to the present invention, such as the systems biphenyl and terphenyl.

[0018] The heteroaromatic ring system according to the present invention contains 5 to 40 aromatic ring atoms, of which at least one is a heteroatom. The heteroatom of the heteroaromatic ring system is preferably selected from N, O, and / or S. The heteroaromatic ring system corresponds to the definition of an aromatic ring system as described above, but has at least one heteroatom as one of the aromatic ring atoms. In this way, the heteroaromatic ring system is different from an aromatic ring system in the sense of the definition of this application, and according to this definition, an aromatic ring system cannot contain any heteroatoms as aromatic ring atoms.

[0019] Aromatic ring systems having 6 to 40 aromatic ring atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms, are understood to mean, in particular, groups derived from the groups previously mentioned under aryl and heteroaryl groups, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, torxene, isotorxene, spirotorxene, spiroisotorxene, indenocarbazole, or combinations thereof.

[0020] In relation to the present invention, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, and alkenyl or alkynyl groups having 2 to 40 carbon atoms may have individual hydrogen atoms or CH2 groups substituted with groups previously mentioned in the definition of radicals, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl This is understood to mean n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethinyl, propynyl, butynyl, pentynyl, hexynyl, or octinyl radical.

[0021] Alkoxy or thioalkyl groups having 1 to 20 carbon atoms may have individual hydrogen atoms or CH2 groups replaced by groups previously mentioned in the definition of radicals, preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i- This is understood to mean butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, etenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethinylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octinylthio.

[0022] The expression that two or more radicals may together form a ring is, in the context of this application, naturally understood to mean, in particular, that the two radicals are bonded to each other by chemical bonds. However, in addition to this, the above expression is also naturally understood to mean that if one of the two radicals is hydrogen, the second radical will bond to the position where the hydrogen atom is bonded to form a ring.

[0023] Preferably, Z 1 CR 1 And here, Z 1 Ar 1 Or, if a T group is attached to it, it is C.

[0024] Preferably, Ar in each case 1 These are aryl groups that are the same or different and have 6 to 16 aromatic ring atoms. More preferably, Ar 1 In each case, these are the same or different and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, fluorenyl, indenofluorenyl and phenantrenyl, where each of the groups mentioned herein is one or more R 2 It may be substituted with a radical.

[0025] Preferably, the compound of formula (I) contains only one or only two Ar groups. 1 Each group is present. This means that the compound of formula (I) has two or fewer Ar groups. 1 This means that the group is present. The compound of formula (I) has only one Ar group. 1 If a group is present, it is desirable that this group be linked to the 6-membered ring to which it is attached via a divalent Y group. Preferably, in this case, Ar 1 The base is one or more R 2 A phenyl group which may be substituted with a radical. Preferably, in this case, Ar 1 Base, Y-bridge and Y-bridge and Ar 1 The 6-membered ring to which the group is bonded is a 6-membered ring and Ar 1 Inserted between the group and the 6-membered ring and Ar 1 It forms a five-membered ring that forms a condensation unit with the group. This condensation unit is preferably selected from fluorene, spirobifluorene, carbazole, dibenzofuran, and dibenzothiophene.

[0026] A preferred embodiment of formula (A) is formulas (A-1) to (A-10).

[0027] [ka]

[0028] (In the formula, the variable groups appearing are defined as above, and each carbazole unit has one or more R groups at the free positions of its two benzene rings.) 3 (May be substituted with radicals) That is the case.

[0029] A preferred embodiment of formula (B) is formulas (B-1) to (B-7).

[0030] [ka]

[0031] [ka]

[0032] (In the formula, the variable groups appearing are defined as above, and each carbazole unit has one or more R groups at the free positions of its two benzene rings.) 3 (May be substituted with radicals) That is the case.

[0033] Ar 2 This preferably corresponds to formula (A) above, and more preferably to one of formulas (A-1) to (A-3).

[0034] Ar 2 A preferred embodiment of the base is illustrated in the table below:

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038]

Chem.

[0039]

Chem.

[0040]

Chem.

[0041] Z 2 is preferably the same in each case and is CR 3 where Z 2 is C when an L 1 group is attached thereto.

[0042] L 1 is preferably selected from aromatic ring systems having 6 to 30 aromatic ring atoms. L 1 is more preferably a single bond, benzene, naphthalene, para-biphenyl, meta-biphenyl, ortho-biphenyl, terphenyl, dibenzofuran, carbazole, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, triazine and fluorene, and very preferably selected from a single bond and phenyl, where the groups described may each be substituted by one or more R 3 radicals.

[0043] Preferred L 1 groups are illustrated in the following table:

[0044]

Chem.

[0045]

Chem.

[0046] Ar 3 preferably has 6 to 30 aromatic ring atoms and is an aromatic ring system optionally substituted by one or more R 4 radicals. Ar 3 is more preferably phenyl, biphenyl, terphenyl, fluorenyl, fluorenyl-phenyl, naphthyl, naphthyl-phenyl, spirobifluorenyl, spirobifluorenyl-phenyl, pyridyl, pyrimidyl, triazinyl, dibenzofuranyl, dibenzofuranyl-phenyl, benzo-fused dibenzofuranyl, dibenzothiophenyl, dibenzothiophenyl-phenyl, benzo-fused dibenzothiophenyl, carbazolyl, carbazolyl-phenyl and benzo-fused carbazolyl, and combinations of two, three or four of these groups, where the groups mentioned may each be optionally substituted by one or more R 4 radicals.

[0047] Ar 3 groups preferably do not correspond to one of formulas (A) and (B).

[0048] Ar 3 Preferred embodiments of are illustrated below:

[0049]

Chemical formula

[0050]

Chemical formula

[0051]

Chemical formula

[0052]

Chemical formula

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] These are, in their free positions, one or more R 4 It may be substituted with a radical.

[0063] R 1 , R 2 , R 3 and R 4Preferably, in each case, they are the same or different, and H, D, F, CN, Si(R 5 )3, N(R 5 )2, selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned are each one or more R 5 They may be substituted with radicals; one or more CH2 groups in the mentioned alkyl groups are -C≡C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 -This may be replaced by:

[0064] Comfortable, R 1 H is H, but C(R 1 )2 or NR 1 The R is bonded to the T group. 1 The base is an exception. In this case, R 1 These are preferably selected from alkyl groups having 1 to 20 carbon atoms and aromatic ring systems having 5 to 40 aromatic ring atoms, where each of the alkyl groups and aromatic ring systems mentioned is one or more R 5 It may be substituted with a radical. More preferably, R 2 is H. More preferably, R 3 is H. More preferably, R 4 H is H.

[0065] R 5 Preferably, in each case, they are the same or different. H, D, F, CN, Si(R 6 )3, N(R 6)2, selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned are each one or more R 6 They may be substituted with radicals; one or more CH2 groups in the mentioned alkyl groups are -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 - may be replaced by R. More preferably, 5 H is H.

[0066] R 6 Preferably, in each case, the same or different, and selected from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R 6 Radicals may be bonded to each other or form rings; the alkyl groups, aromatic ring systems, and heteroaromatic ring systems mentioned may be substituted with F or CN.

[0067] Preferably, m is 0.

[0068] Preferably, i is 0 or 1.

[0069] Preferably, k is 0 or 1.

[0070] Preferably, the sum of i and k is 1 or 2, more preferably 1.

[0071] A preferred secondary unit of formula (I) that conforms to formula (IA)

[0072] [ka]

[0073] (In the equation, the dashed line indicates joining to the remainder of the equation.) The following structure is selected

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] (In the formula, the dashed line represents the bond to the nitrogen atom in formula (I).)

[0082] A preferred embodiment of formula (I) is formula (I-1) shown below.

[0083] [ka]

[0084] (The variable groups that appear in the formula are as follows: i is either 0 or 1. k is either 0 or 1. Here, the sum of k and i is 1 or 2, preferably 1. The free positions on the benzene ring are R 1 They may be substituted with radicals. Ar 1 ~Ar 3 The base is defined as described above, and preferably corresponds to those preferred embodiments as shown earlier. Ar 1 Preferably, in each case, the same or different, selected from phenyl and naphthyl, each of which contains one or more R 2 (It may be substituted with a radical, and there are no divalent Y groups.) It corresponds to.

[0085] Similarly, a preferred alternative form of formula (I) is formula (I-2) shown below.

[0086] [ka]

[0087] (The variable groups appearing in the formula are as follows: Y is C(R 1 )2, Si(R 1 )2, NR 1 From O and S, preferably C(R 1 )2, NR 1 Selected from O and S; The free positions on the benzene ring are R 1 They may be substituted with radicals. Other variable groups that appear are defined as described above and preferably correspond to their preferred embodiments as previously shown. It corresponds to.

[0088] A preferred embodiment of formula (I-2) is formula (I-2A) shown below.

[0089] [ka]

[0090] (The variable groups appearing in the formula are as follows: The free positions on the benzene ring are R 1 They may be substituted with radicals. Other variable groups that appear are defined as described above and preferably correspond to their preferred embodiments as previously shown. It corresponds to.

[0091] A preferred embodiment of equation (I-1) is given by equations (I-1-1) to (I-1-3) below.

[0092] [ka]

[0093] (The variable groups appearing in the formula are as follows: i is either 0 or 1. k is either 0 or 1. Here, the sum of k and i is 1 or 2, preferably 1. The free positions on the benzene ring are R 1 They may be substituted with radicals. Ar 1 and Ar 3 The base is defined as described above, and preferably corresponds to those preferred embodiments as shown earlier. Ar 1 Preferably, in each case, the same or different, selected from phenyl and naphthyl, each of which contains one or more R 2 (The group may be substituted with a radical, and the divalent group Y is not present.) It corresponds to.

[0094] A preferred embodiment of equation (I-2) is given by equations (I-2-1) to (I-2-3) below.

[0095] [ka]

[0096] [ka]

[0097] (The variable groups appearing in the formula are as follows: Y is C(R 1 )2, Si(R 1 )2, NR 1 From O and S, preferably C(R 1 )2, NR 1 Selected from O and S; The free positions on the benzene ring are R 1 They may be substituted with radicals. Other variable groups that appear are defined as described above and preferably correspond to their preferred embodiments as previously shown. It corresponds to.

[0098] A preferred embodiment of formula (I-2A) is shown below in formulas (I-2A-1) to (I-2A-3):

[0099] [ka]

[0100] [ka]

[0101] (The variable groups appearing in the formula are as follows: The free positions on the benzene ring are R 1 They may be substituted with radicals. Other variable groups that appear are defined as described above and preferably correspond to their preferred embodiments as previously shown. It corresponds to.

[0102] Preferred specific compounds of formula (I) are shown in the table below:

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] The compound of formula (I) may be prepared using known organic chemical reactions, and more specifically, using metal-catalyzed coupling reactions, such as Suzuki coupling and Buchwald coupling.

[0114] A preferred method for preparing the compound of formula (I) is described in more detail below (Scheme 1). Those skilled in the art can modify and improve this method as needed, within the scope of their general knowledge of organic synthesis chemistry.

[0115] According to Scheme 1, in the first step, a biphenyl derivative substituted with two reactive groups X and Y (the X group is in the ortho position relative to the bond between the two phenyl groups) is reacted with an aromatic or heteroaromatic ring system Ar substituted with a boronic acid group in a Suzuki reaction. In this reaction, the ring system Ar is introduced at the position of the reactive Y group. In the second step, the resulting intermediate is reacted with an amine compound of formula HNAr2 in a Buchwald coupling reaction. In this reaction, the -NAr2 group is introduced at the position of the reactive X group, and therefore is in the ortho position relative to the bond between the two phenyl groups.

[0116] [ka]

[0117] The resulting compound may be further modified as desired.

[0118] Therefore, the subject of this application is a method for preparing a compound of formula (I), characterized in that, in a first step i), a biphenyl derivative substituted with reactive groups X and Y (where group X is in the ortho position relative to the bond between the two phenyl groups) is reacted with an aromatic or heteroaromatic ring system substituted with a boronic acid group, thereby introducing the aromatic or heteroaromatic ring system to the position of the Y group, and in a second step ii), the intermediate obtained in step i) is reacted with a compound of formula HNAr2 (wherein Ar is selected from an aromatic ring system and a heteroaromatic ring system), in which the -NAr2 group is introduced to the position of the X group.

[0119] The reaction in step i) is preferably a Suzuki coupling reaction. The reaction in step ii) is preferably a Buchwald coupling reaction.

[0120] The intermediate formed in step i) is preferably of formula (I-Int-1)

[0121] [ka]

[0122] (In the formula, the variable groups appearing are defined as above, where X is a reactive group, preferably Cl, Br, I, or a triflate or tosylate group, more preferably Cl or Br.) It corresponds to.

[0123] The compound of formula HNAr2 used in step ii) is preferably of formula (I-Int-2)

[0124] [ka]

[0125] (The variable groups appearing in the formula are as defined above.) It corresponds to.

[0126] Compounds of formula (I) above, in particular those substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid, or boronic acid esters, can find applications as monomers for producing the corresponding oligomers, dendrimers, or polymers. Suitable reactive leaving groups include, for example, bromine, iodine, chlorine, boronic acid, boronic acid esters, amines, alkenyl or alkynyl groups having terminal CC double or CC triple bonds, oxiranes, oxetanes, groups involved in cycloaddition, such as 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0127] Therefore, the present invention further provides oligomers, polymers, or dendrimers containing one or more compounds of formula (I), wherein the bonding (or number of bondings) to the polymer, oligomer, or dendrimer is R in formula (I). 1 , R 2 , R 3 or R 4 It may be localized at any desired position substituted by . Depending on the bonding of the compound of formula (I), the compound becomes part of the side chain or part of the main chain of an oligomer or polymer. The oligomer according to the present invention is understood to mean a compound formed from at least three monomer units. The polymer according to the present invention is understood to mean a compound formed from at least ten monomer units. The polymers, oligomers, or dendrimers of the present invention may be conjugated, partially conjugated, or unconjugated. The oligomers or polymers of the present invention may be linear, branched, or dendritic. In a linear bonded structure, the units of formula (I) may be directly bonded to each other, or bonded to each other via divalent groups, for example, via substituted or unsubstituted alkylene groups, via heteroatoms, or via divalent aromatic or heteroaromatic groups. In branched and dendritic structures, for example, three or more units of formula (I) may be bonded via trivalent or higher groups, for example, via trivalent or higher aromatic or heteroaromatic groups, to form a branched or dendritic oligomer or polymer.

[0128] The same preferences described for compounds of formula (I) apply to the repeating units of formula (I) in oligomers, dendrimers, and polymers.

[0129] For the preparation of oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers. Suitable preferred comonomers include fluorene (e.g., according to EP842208 or WO2000 / 22026), spirobifluorene (e.g., according to EP707020, EP894107 or WO2006 / 061181), paraphenylene (e.g., according to WO1992 / 18552), carbazole (e.g., according to WO2004 / 070772 or WO2004 / 113468), thiophene (e.g., according to EP1028136), Dihydrophenanthrene (e.g., according to WO2005 / 014689 or WO2007 / 006383), cis- and trans-indenofluorene (e.g., according to WO2004 / 041901 or WO2004 / 113412), ketones (e.g., according to WO2005 / 040302), phenanthrene (e.g., according to WO2005 / 104264 or WO2007 / 017066), or a selection of these units. Polymers, oligomers, and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, e.g., vinyltriarylamines (e.g., according to WO2007 / 068325) or phosphorescent metal complexes (e.g., according to WO2006 / 003000), and / or charge transport units, particularly those based on triarylamines.

[0130] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, of which at least one monomer gives rise to a repeating unit of formula (I) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that result in the formation of CC or CN bonds are Suzuki polymerization, Yamamoto polymerization, Still polymerization, and Hartwig-Buchwald polymerization.

[0131] To process the compounds of the present invention from a liquid phase, for example by spin coating or printing, a preparation of the compounds of the present invention is required. These preparations may be, for example, solutions, dispersions, or emulsions. For this purpose, the use of a mixture of two or more solvents may be preferred. Suitable preferred solvents include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fencone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidine, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexano These are cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, NMP, p-cymene, phenethole, 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, or mixtures of these solvents.

[0132] Accordingly, the present invention further provides preparations, in particular solutions, dispersions, or emulsions comprising at least one compound of formula (I) and at least one solvent, preferably an organic solvent. Methods for preparing such solutions are known to those skilled in the art and are described, for example, in WO2002 / 072714, WO2003 / 019694 and the literature cited herein.

[0133] The compounds of the present invention are suitable for use in electronic devices, particularly organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds can be used in a variety of functions and layers.

[0134] Accordingly, the present invention further provides the use of compounds of formula (I) in electronic devices. These electronic devices are preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quenched devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and more preferably organic electroluminescent devices (OLEDs).

[0135] As already stated above, the present invention further provides an electronic device comprising at least one compound of formula (I). This electronic device is preferably selected from the devices mentioned above.

[0136] The electronic device is more preferably an organic electroluminescent device (OLED) comprising an anode, a cathode, and at least one light-emitting layer, characterized in that the at least one organic layer, which may be a light-emitting layer, a hole transport layer, or another layer, contains at least one compound of formula (I).

[0137] In addition to the cathode, anode, and light-emitting layer, the organic electroluminescent device may further include additional layers. These are selected in each case from, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers (IDMC2003, Taiwan; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer), and / or organic or inorganic p / n junctions.

[0138] The preferred layer order for an organic electroluminescent device containing the compound of formula (I) is as follows: anode - hole injection layer - hole transport layer - any further hole transport layer(s) - any electron blocking layer - light-emitting layer - any hole blocking layer - electron transport layer - electron injection layer - cathode. In addition, further layers may be present in the OLED.

[0139] The organic electroluminescent device of the present invention may contain two or more light-emitting layers. More preferably, these light-emitting layers in this case have several emission maxima in total between 380 nm and 750 nm and produce white light as a whole; in other words, various light-emitting compounds that can emit fluorescence or phosphorescence and emit blue, green, yellow, orange, or red light are used for the light-emitting layers. Particularly preferred is a three-layer system, i.e., a system having three light-emitting layers, where the three layers exhibit blue, green, and orange or red light emission (see, for example, WO2005 / 011013 for the basic configuration). The compounds of the present invention are here preferably present as a matrix material in the hole transport layer, hole injection layer, electron blocking layer, light-emitting layer, hole blocking layer and / or electron transport layer, more preferably in the light-emitting layer, in the hole blocking layer and / or electron transport layer.

[0140] According to the present invention, it is preferable that the compound of formula (I) is used in an electronic device comprising one or more phosphorescent compounds. In this case, the compounds may be present in different layers, preferably a hole transport layer, an electron blocking layer, a hole injection layer, an emissive layer, a hole blocking layer and / or an electron transport layer. More preferably, the compound is present in the electron blocking layer or in combination with the phosphorescent compound in the emissive layer.

[0141] The term "phosphorescent compound" typically encompasses compounds in which light emission occurs through spin-forbidden transitions from, for example, an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0142] Suitable phosphorescent compounds (=triplet emitters) are, in particular, compounds that, when properly excited, preferably emit light in the visible region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and more preferably greater than 56 and less than 80. It is preferable to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium as phosphorescent compounds, and especially compounds containing iridium, platinum, or copper. For the purposes of this invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds.

[0143] Examples of the above-mentioned luminescent compounds can be found in applications WO00 / 70655, WO01 / 41512, WO02 / 02714, WO02 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, and US2005 / 0258742. In general, all phosphorescent complexes used in phosphorescent OLEDs by prior art and known to those skilled in the art in the field of organic electroluminescent devices are suitable. Those skilled in the art can also use further phosphorescent complexes in combination with compounds of formula (I) in organic electroluminescent devices without requiring original creativity. Further examples are listed in the table below:

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148]

change

[0149]

change

[0150]

change

[0151]

change

[0152]

change

[0153]

change

[0154]

change

[0155] In a preferred embodiment of the present invention, the compound of formula (I) is used as a hole transport material. In this case, the compound is preferably present in a hole transport layer. Preferred embodiments of the hole transport layer include a hole transport layer, an electron blocking layer, and a hole injection layer. Particularly preferably, at least one compound of formula (I) is present in the electron blocking layer of the device.

[0156] The hole transport layer according to this invention is a layer that has a hole transport function between the anode and the light-emitting layer. More specifically, it is a hole transport layer that is neither a hole injection layer nor an electron blocking layer.

[0157] In the context of this application, the hole injection layer and the electron blocking layer are understood to be specific embodiments of the hole transport layer. The hole injection layer is a hole transport layer that is directly adjacent to the anode or separated from the anode by a single coating on the anode, when there are multiple hole transport layers between the anode and the light-emitting layer. The electron blocking layer is a hole transport layer that is directly adjacent to the light-emitting layer on the anode side, when there are multiple hole transport layers between the anode and the light-emitting layer. Preferably, the OLED of the present invention includes two, three, or four hole transport layers between the anode and the light-emitting layer, of which at least one preferably contains a compound of formula (I), and more preferably only one or two contain a compound of formula (I).

[0158] When the compound of formula (I) is used as a hole transport material in a hole transport layer, hole injection layer, or electron blocking layer, the compound may be used as a pure material, i.e., in a 100% proportion, in the hole transport layer, or in combination with one or more further compounds.

[0159] In a preferred embodiment, the hole transport layer containing the compound of formula (I) additionally contains one or more further hole transport compounds. These further hole transport compounds are preferably selected from triarylamine compounds, more preferably from monotriarylamine compounds. Particularly preferably, they are selected from the preferred embodiments of the hole transport materials shown later. In the preferred embodiments described, the compound of formula (I) and one or more further hole transport compounds are preferably present in a proportion of at least 20% each, more preferably in a proportion of at least 30% each.

[0160] In a preferred embodiment, the hole transport layer containing the compound of formula (I) additionally contains one or more p-dopants. The p-dopants used according to the present invention are preferably organic electron acceptor compounds capable of oxidizing one or more of the other compounds in the mixture.

[0161] Particularly preferred embodiments of the p-dopant are the compounds disclosed in WO2011 / 073149, EP1968131, EP2276085, EP2213662, EP1722602, EP2045848, DE102007031220, US8044390, US8057712, WO2009 / 003455, WO2010 / 094378, WO2011 / 120709, US2010 / 0096600, WO2012 / 095143 and DE102012209523.

[0162] Particularly preferred as p-dopants are quinodimethane compounds, azaindenofluoradione, azaphenalene, azatriphenylene, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt having ligands containing at least one oxygen atom as a binding site. Further preferred as dopants are transition metal oxides, more preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. (III) Complexes of oxidized bismuth, more particularly bismuth(III) complexes having electron-deficient ligands, and even more particularly carboxylate ligands are preferred.

[0163] The p-dopant is preferably distributed substantially uniformly in the p-doped layer. This can be achieved, for example, by the simultaneous deposition of the p-dopant and the hole transport material matrix.

[0164] Preferred p-dopant compounds include, in particular, the following:

[0165] [ka]

[0166] In a further preferred embodiment of the present invention, the compound of formula (I) is used as a hole transport material in OLEDs in combination with a hexaazatriphenylene derivative, such as those described in US2007 / 0092755. Here, it is particularly preferred that the hexaazatriphenylene derivative be used in a separate layer.

[0167] In a preferred embodiment of the present invention, the compound of formula (I) is used as a matrix material in the light-emitting layer in combination with one or more light-emitting compounds, preferably phosphorescent compounds.

[0168] In this case, the proportion of matrix material in the light-emitting layer is 50.0% to 99.9% by volume, preferably 80.0% to 99.5% by volume, and more preferably 85.0% to 97.0% by volume.

[0169] Accordingly, the proportion of the luminescent compound is 0.1% to 50.0% by volume, preferably 0.5% to 20.0% by volume, and more preferably 3.0% to 15.0% by volume.

[0170] The light-emitting layer of an organic electroluminescent device may contain a system comprising multiple matrix materials (mixed matrix system) and / or multiple light-emitting compounds. In this case as well, the light-emitting compound is generally the compound with the lower proportion in the system, and the matrix material is the compound with the higher proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be lower than the proportion of a single light-emitting compound.

[0171] The compound of formula (I) is preferably used as a component of a mixed matrix system for a phosphorescent emitter. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material having hole transport properties, and the other material is a material having electron transport properties. The compound of formula (I) is preferably a matrix material having hole transport properties. Correspondingly, the compound of formula (I) is used as a matrix material for a phosphorescent emitter in the light-emitting layer of an OLED, and a second matrix compound having electron transport properties is present in the light-emitting layer. The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. More specific details relating to the mixed matrix system are described in particular in application WO2010 / 108579, and its corresponding technical teachings are incorporated by reference in this context.

[0172] However, the desired electron and hole transport properties of the mixed matrix components may be primarily or entirely possessed by a single mixed matrix component, in which case additional mixed matrix components may perform other functions.

[0173] The mixed matrix system may contain one or more luminescent compounds, preferably one or more phosphorescent compounds. Generally, the mixed matrix system is preferably used in phosphorescent organic electroluminescent devices.

[0174] Particularly suitable matrix materials that can be used as matrix components in a mixed matrix system in combination with the compounds of the present invention are selected from the preferred matrix materials defined below with respect to phosphorescent compounds, in particular those having electron transport properties.

[0175] Preferred embodiments of different functional materials in electronic devices are listed below.

[0176] Preferred fluorescent compounds are selected from the class of arylamines. The arylamines or aromatic amines of the present invention are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system and more preferably has at least 14 aromatic ring atoms. These preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines, or aromatic chrysendiamines. Aromatic anthraceneamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at position 9. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably at positions 9 and 10. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysendiamines are similarly defined, where the diarylamino group is bonded to pyrene, preferably at position 1 or position 1 and 6. Further preferred luminescent compounds include, for example, indenofluorenamines or diamines according to WO2006 / 108497 or WO2006 / 122630, benzoindenofluorenamines or diamines according to WO2008 / 006449, and dibenzoindenofluorenamines or diamines according to WO2007 / 140847, as well as indenofluorene derivatives having a condensed aryl group as disclosed in WO2010 / 012328. Equally preferred are pyrenearylamines as disclosed in WO2012 / 048780 and WO2013 / 185871. Equally preferred are benzoindenofluorenamine disclosed in WO2014 / 037077, benzofluorenamine disclosed in WO2014 / 106522, extended benzoindenofluorene disclosed in WO2014 / 111269 and unpublished application EP15182993.4, phenoxazine disclosed in unpublished applications EP15181178.3 and EP15181177.5, and fluorene derivatives bound to furan units or thiophene units disclosed in WO2016 / 150544.

[0177] Preferably, useful matrix materials for fluorescent compounds include materials from various classes of substances. Preferred matrix materials include oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP676461), oligoarylenes containing condensed aromatic groups in particular, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi according to EP676461), polypodal metal complexes (e.g., according to WO2004 / 081017), hole-conducting compounds (for example) The materials are selected from the classes of electron-conducting compounds, particularly ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO2005 / 084081 and WO2005 / 084082), atrop isomers (e.g., according to WO2006 / 048268), boronic acid derivatives (e.g., according to WO2006 / 117052), or benzoanthracenes (e.g., according to WO2008 / 145239). Particularly preferred matrix materials are selected from the classes of naphthalene, anthracene, benzoanthracene and / or pyrene-containing oligoarylenes or atrop isomers of these compounds, oligoarylene vinylenes, ketones, phosphine oxides, and sulfoxides. Particularly preferred matrix materials are selected from the class of oligoarylenes, including anthracene, benzoanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. It is naturally understood that the oligoarylenes in this invention mean compounds in which at least three aryl or arylene groups are bonded to one another.Furthermore, anthracene derivatives disclosed in WO2006 / 097208, WO2006 / 131192, WO2007 / 065550, WO2007 / 110129, WO2007 / 065678, WO2008 / 145239, WO2009 / 100925, WO2011 / 054442 and EP1553154, pyrene compounds disclosed in EP1749809, EP1905754 and US2012 / 0187826, benzoanthracenylanthracene compounds disclosed in WO2015 / 158409, indenobenzofuran disclosed in unpublished application EP15180777.3, and phenanthrylanthracene disclosed in unpublished application EP15182962.9 are preferred.

[0178] Preferred matrix materials for phosphorescent compounds include, in addition to the compound of formula (I), aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones according to, for example, WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 006680, and triarylamines disclosed in WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527 or WO2008 / 086851. N, carbazole derivatives, e.g., CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives, e.g., indolocarbazole derivatives by WO2007 / 063754 or WO2008 / 056746, e.g., indenocarbazole derivatives by WO2010 / 136109, WO2011 / 000455 or WO2013 / 041176, e.g., azacarbazole derivatives by EP1617710, EP1617711, EP1731584, JP2005 / 347160 Diazacin derivatives, e.g., bipolar matrix materials according to WO2007 / 137725; silanes, e.g., according to WO2005 / 111172; azabolol or boronic acid esters, e.g., according to WO2006 / 117052; triazine derivatives, e.g., according to WO2010 / 015306, WO2007 / 063754, or WO2008 / 056746; zinc complexes, e.g., according to EP652273, or WO2009 / 062578; diazacin, e.g., according to WO2010 / 054729. These are lol or tetraazacilol derivatives, for example, diazaphosphorol derivatives according to WO2010 / 054730, crosslinked carbazole derivatives according to US2009 / 0136779, WO2010 / 050778, WO2011 / 042107, WO2011 / 088877, or WO2012 / 143080, triphenylene derivatives according to WO2012 / 048781, or lactams according to WO2011 / 116865 or WO2011 / 137951.

[0179] Suitable charge transport materials usable in the hole injection or hole transport layer or electron blocking layer, or in the electron transport layer, of the electronic devices of the present invention include, in addition to the compound of formula (I), compounds disclosed in, for example, Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0180] Preferably, the OLED of the present invention comprises two or more different hole transport layers. The compound of formula (I) may be used in one or more, or all, of the hole transport layers. In a preferred embodiment, the compound of formula (I) is used in only one or two of the hole transport layers, and other compounds, preferably aromatic amine compounds, are used in any further hole transport layers present. Further compounds preferably used in the hole transport layers of the OLED of the present invention together with the compound of formula (I) include, among others, indenofluoreneamine derivatives (e.g., according to WO06 / 122630 or WO06 / 100896), amine derivatives disclosed in EP1661888, hexaazatriphenylene derivatives (e.g., according to WO01 / 049806), amine derivatives including condensed aromatic compounds (e.g., according to US5,061,569), and according to WO95 / 09147. Disclosed amine derivatives, monobenzoindenofluorenamine (e.g., according to WO08 / 006449), dibenzoindenofluorenamine (e.g., according to WO07 / 140847), spirobifluorenamine (e.g., according to WO2012 / 034627 or WO2013 / 120577), fluorenamine (e.g., according to WO2014 / 015937, WO2014 / 015938, WO2014 / 015935 and WO2015 / 082056) ), spirodibenzopyranamine (e.g., according to WO2013 / 083216), dihydroacridine derivatives (e.g., according to WO2012 / 150001), spirodibenzofuran and spirodibenzothiophene (e.g., according to WO2015 / 022051 and unpublished applications PCT / EP2015 / 002475 and PCT / EP2016 / 000084), phenantrediarylamine (e.g., according to WO2015 / 131976), e.g. unpublished applications These include spirotribenzotropolone according to PCT / EP2015 / 002225, spirobifluorene with a metaphenyldiamine group according to the unpublished application PCT / EP2015 / 002112, spirobisacridine according to WO2015 / 158411, xanthenediarylamine according to WO2014 / 072017, and 9,10-dihydroanthracenic pyrocompounds with a diarylamino group according to WO2015 / 086108.

[0181] The material used in the electron transport layer may be any material used as an electron transport material in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes, e.g., Alq3; zirconium complexes, e.g., Zrq4; lithium complexes, e.g., Liq; benzimidazole derivatives; triazine derivatives; pyrimidine derivatives; pyridine derivatives; pyrazine derivatives; quinoxaline derivatives; quinoline derivatives; oxadiazole derivatives; aromatic ketones; lactams; boranes; diazaphosphole derivatives; and phosphine oxide derivatives. Further suitable materials are derivatives of the above compounds, as disclosed in JP2000 / 053957, WO2003 / 060956, WO2004 / 028217, WO2004 / 080975, and WO2010 / 072300.

[0182] A preferred cathode for electronic devices is a multilayer structure composed of a metal, metal alloy, or various metals with a low work function, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In addition, alloys composed of alkali metals or alkaline earth metals with silver, such as magnesium and silver, are also suitable. For multilayer structures, in addition to the metals mentioned, further metals with relatively high work functions, such as Ag or Al, can also be used; in this case, metal combinations such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly used. It is sometimes preferable to introduce a thin interlayer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose include alkali metal or alkaline earth metal fluorides, as well as their corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0183] A preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with a high redox potential are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are suitable. x Al / PtO x ) may also be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent to allow either irradiation (organic solar cell) or emission (OLED, O-LASER) of an organic material. Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, in particular conductive doped polymers, are preferred. In addition, the anode may consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0184] The device is properly structured (depending on the application), the contacts are connected, and it is finally sealed to eliminate the damaging effects of water and air.

[0185] In one preferred embodiment, the electronic device is characterized by having one or more layers coated by a sublimation process. In this case, the material is subjected to a vacuum sublimation system. -5 Less than mbar, preferably 10 -6 The initial pressure is applied by deposition at a pressure of less than mbar. However, in this case, the initial pressure can be further reduced, for example, 10 -7 It is also possible to set it to less than mbar.

[0186] Similarly, electronic devices characterized by having one or more layers coated by OVPD (organic vapor deposition) or with the assistance of carrier gas sublimation are preferred. In this case, the material is 10 -5The material is applied at a pressure of mbar to 1 bar. A special case of this method is OVJP (organic vapor jet printing), in which the material is applied directly by the nozzle and thus structured (e.g., MSArnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0187] In addition, an electronic device is preferred in which one or more layers are formed from a solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing, or offset printing, more preferably by LITI (photo-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, a soluble compound of formula (I) is required. High solubility can be achieved by appropriate substitution of the compound.

[0188] The electronic device of the present invention is more preferably manufactured by applying one or more layers from a solution and one or more layers by a sublimation process.

[0189] According to the present invention, an electronic device comprising one or more compounds of formula (I) can be used as a light source for illumination applications, as a light source for medical and / or cosmetic applications (e.g., phototherapy), and in a display device.

[0190] [example] A) Synthesis example Synthesis of the compound biphenyl-4-yl(9-phenyl-9H-carbazole-2-yl)-[1,1';3',1”]terphenyl-2-ylamine (1-1) and compounds (1-2)~(1-22)

[0191] [ka]

[0192] Synthesis of intermediate I-1:2-bromo-[1,1';3',1”]-terphenyl 14.3 g (117 mmol) of phenylboronic acid, 40 g (111.4 mmol) of 2-bromo-3'-iodobiphenyl, and 84 ml of 2 M aqueous solution of K2CO3 (168 mmol) were suspended in 400 ml of toluene. To this suspension, 1.2 g (1.2 mmol) of tetrakis(triphenyl)phosphine palladium (0) was added. The reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was removed, filtered through silica gel, washed three times with 150 ml of water, and then concentrated until dry. The crude product was filtered through silica gel with heptane / ethyl acetate to obtain 29 g (85%) of 2-bromo-[1,1';3',1”]-terphenyl.

[0193] The following compounds are prepared using a similar method:

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] Synthesis of intermediate I-13: 5-chloro-9,9-dimethyl-2-phenylfluorene

[0198] [ka]

[0199] Intermediate II-1 8.3 g of phenylboronic acid (68 mmol) and 20 g of dibromodicarboxylic acid derivative (68 mmol) are suspended in 400 ml of toluene, 160 ml of ethanol, and 80 ml of water. 14.4 g of sodium carbonate is added to this. The solution is degassed and saturated with N2. Then, 0.79 g (0.68 mmol) of Pd(Ph3P)4 is added. The reaction mixture is heated under a protective atmosphere for 4 hours (80°C). Subsequently, the mixture is fractionated between toluene and water, the organic phase is washed three times with water, dried over Na2SO4, and concentrated by rotary evaporation. The crude product is filtered through silica gel with heptane / ethyl acetate, and the remaining residue is recrystallized from EtOH. The yield is 11.0 g (55% of the theoretical value).

[0200] 5.9 g of 2-chlorophenylboronic acid (38 mmol) and 11 g of bromine derivative (38 mmol) are suspended in 200 ml of toluene and 70 ml of water. 7.2 g of sodium carbonate (67.6 mmol) is added. The solution is degassed and saturated with N2. Then, 140 mg (0.15 mmol) of Pd2(dba)3 and 250 mg of SPhos (0.3 mmol) are added. The reaction mixture is heated to a boil under a protective atmosphere for 12 hours. Subsequently, the mixture is fractionated between toluene and water, the organic phase is washed three times with water, dried over Na2SO4, and concentrated by rotary evaporation. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from EtOH. The yield is 10.4 g (85% of the theoretical value).

[0201] The following compounds are prepared using a similar method:

[0202] [ka]

[0203] Intermediate I-13 Dissolve 10.4 g (32.2 mmol) of intermediate II-1 in 100 ml of dry THF in a calcined flask. Saturate the solution with N2. Cool the clear solution to -5°C, then add 32.2 ml (96.7 mmol) of 3 M methylmagnesium chloride solution. Gradually warm the reaction mixture to room temperature, then quench with ammonium chloride. Subsequently, fractionate the mixture between ethyl acetate and water, wash the organic phase three times with water, dry over Na2SO4, and concentrate by rotary evaporation. Dissolve the concentrated solution in toluene and add 8 g of Amberlyst 15. Heat the mixture to 110°C and maintain at this temperature for 4 hours. During this time, a white solid will precipitate. Cool the mixture to room temperature, filter the precipitated solid by suction, and wash with heptane. Dry the residue under reduced pressure at 40°C. The crude product was filtered through silica gel with heptane:ethyl acetate in a 1:1 ratio to obtain 9.3 g of the product (90% of the theoretical value).

[0204] The following compounds are prepared using a similar method:

[0205] [ka]

[0206] Synthesis of biphenyl-4-yl(9-phenyl-9H-carbazole-2-yl)-[1,1';3',1”]terphenyl-2-ylamine) (compound 1-1) and compounds (1-2) to (1-14) Dissolve 16.2 g of biphenyl-4-yl(9-phenyl-9H-carbazole-2-yl)amine (48.5 mmol) and 15 g of 2-bromo-[1,1';3',1”]-terphenyl (48.5 mmol) in 300 ml of toluene. Degas the solution and saturate with N2. Then, add 1.94 ml (1.94 mmol) of 1 M tri-tert-butylphosphine solution and 0.89 g (0.97 mmol) of Pd2(dba)3. Subsequently, Add 7.0 g of sodium tert-butoxide (72.8 mmol). Heat the reaction mixture under a protective atmosphere for 5 hours until boiling. Subsequently, the mixture is fractionated between toluene and water, the organic phase is washed three times with water, dried over Na2SO4, and concentrated by rotary evaporation. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from heptane / toluene. 22.3 g (72% of the theoretical value) of the residue is finally sublimated under high vacuum.

[0207] The following compounds are prepared using a similar method:

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] B) Device examples An exemplary OLED is manufactured according to the following general method: The substrate used is a glass plaque coated with a 50 nm thick layer of structured ITO (indium tin oxide). The following layer structure is applied to it: hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emissive layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode. The cathode consists of a 100 nm thick aluminum layer. Table 1 shows the materials used for the corresponding layers of an exemplary OLED, and Table 3 lists the chemical structures of these materials.

[0214] The material is deposited by hot vapor deposition in a vacuum chamber. The luminescent layer here always consists of two matrix materials (hosts) and a luminescent dopant (luminescent element) added to the matrix materials in a specific volume ratio by co-evaporation. Therefore, the percentages of material should be understood as volume percentages. The same applies to layers other than the luminescent layer. These layers may similarly contain two or more materials in corresponding proportions.

[0215] OLEDs are characterized using standard methods. For this purpose, the electroluminescence spectrum and the external quantum efficiency (EQE, measured in %) as a function of luminance, calculated from the current-voltage-luminance characteristics (IUL characteristics), are determined. This is done assuming Lambertian emission characteristics. In addition, the operating voltage is determined (in U, V).

[0216] EQE@1000cd / m 2 is 1000 cd / m² 2 This is the external quantum efficiency at the operating luminous flux density. EQE@10mA / cm 2 It is 10mA / cm 2 This is the external quantum efficiency at the current density. Use of compounds in EBL for green phosphorescent OLEDs OLED examples C1 to I12 have the layer structure shown in Table 1a, and in each case, the EBL contains one of the compounds 1-1, 1-2, 1-3, 1-4, 1-6, 1-7, 1-10, 1-14, 1-15, 1-16, 1-17, and 1-18 of the present invention.

[0217] In all cases, the OLED of the present invention achieves good results with respect to operating voltage and EQE (Table 2a). Furthermore, the OLED of the present invention has a good lifespan.

[0218] Even when using compounds containing N-linked carbazoles, such as compound 1-13, it is possible to obtain OLEDs with comparable power data, as shown in Table 2a.

[0219] [Table 1]

[0220] [Table 2]

[0221] Use of compounds in HIL and HTL of blue fluorescent OLEDs OLED examples I13 to I15 have the layer structure shown in Table 1b, and the hole transport layers HIL and HTL each contain one of the compounds 1-15, 1-17, and 1-18 of the present invention.

[0222] In all cases, the OLED of the present invention achieves good results with respect to operating voltage and EQE (Table 2b). Furthermore, the OLED of the present invention has a good lifespan.

[0223] [Table 3]

[0224] [Table 4]

[0225] Use of compounds in EBL for blue fluorescent OLEDs OLED examples I16 and I17 have the layer structure shown in Table 1c, and in each case the EBL contains one of the compounds 1-15 and 1-16 of the present invention.

[0226] In all cases, the OLED of the present invention achieves good results with respect to operating voltage and EQE (Table 2c). Furthermore, the OLED of the present invention has a good lifespan.

[0227] [Table 5]

[0228] [Table 6]

[0229] [Table 7-1]

[0230] [Table 7-2]

Claims

1. Equation (I) 【Chemistry 1】 (The variable groups appearing in the formula are as follows: Z １ In each case, they may be the same or different, CR １ Selected from, here, Z １ Ar １ Or it is C if a T group is attached to it; Ar １ In each case, these are the same or different, selected from phenyl or biphenyl, and each of the groups mentioned herein is one or more R ２ They may be substituted with radicals. Ar ２ is formula (A) or (B) 【Chemistry 2】 Corresponding to; Z ２ is the same or different in each case, and is CR ３ where Z ２ is L １ is C when the group is attached thereto; L １ is selected from benzene, para-biphenyl, meta-biphenyl, ortho-biphenyl, or terphenyl, where each of the groups described is one or more R ３ It may also be substituted with radicals; Ar ３ The group is selected from phenyl, biphenyl, terphenyl, fluorenyl, fluorenyl-phenyl, naphthyl, naphthyl-phenyl, spirobifluorenyl, spirobifluorenyl-phenyl, dibenzofuranyl, dibenzofuranyl-phenyl, dibenzothiophenyl, dibenzothiophenyl-phenyl, carbazolyl, and carbazolyl-phenyl, where each of the aforementioned groups is one or more R ４ It may also be substituted with radicals; T is C(R １ ) ２ Selected from O and S; R １ In each case, they are the same or different, H, D, CN, N(R ５ ) ２ , selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl groups, as well as the aromatic ring systems and heteroaromatic ring systems mentioned herein, each contain one or more R ５ It may also be substituted with radicals; R ２ , R ４ In each case, they are the same or different, H, D, F, CN, N(R ５ ) ２ , selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl groups, as well as the aromatic ring systems and heteroaromatic ring systems mentioned herein, each contain one or more R ５ It may also be substituted with radicals; R ３ In each case, they are the same or different, H, D, F, CN, N(R ５ ) ２ , selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms; each of the alkyl groups mentioned is one or more R ５ It may also be substituted with radicals; R ５ In each case, they are the same or different, H, D, F, CN, N(R ６ ) ２ , selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the alkyl groups, as well as the aromatic ring systems and heteroaromatic ring systems mentioned herein, each contain one or more R ６ It may also be substituted with radicals; R ６ These are the same or different in each case and are selected from H, D, F, CN, and alkyl groups having 1 to 20 carbon atoms; the alkyl groups mentioned herein may be substituted with F or CN; m is either 0 or 1; i is 0, 1, or 2; k is 0, 1, or 2; Here, the sum of k and i is at least 1; Ar １ The groups may also be linked to the six-membered ring to which they are attached via divalent groups Y. Y is the same or different in each case, and C(R １ ) ２ (Selected from O and S) A compound of [unclear].

2. Z １ CR １ And here, Z １ Ar １ Or, if a T group is bonded to it, it is C, and Z ２ CR ３ And here, Z ２ is, L １ The compound according to claim 1, characterized in that the group is carbon when bonded to it.

3. The aforementioned compound contains two or fewer Ar １ The compound according to claim 1 or 2, characterized in that a group is present.

4. The aforementioned compound contains one or fewer Ar １ A base exists, and this Ar １ The base is one or more R ２ A phenyl group which may be substituted with a radical, and this group Ar １ It is connected to the six-membered ring to which it is bonded via a base Y, where the Ar １ Base, Y-bridge, and the Y-bridge and the Ar １ The six-membered ring to which the group is bonded is the six-membered ring and the Ar １ It is inserted between the base and the six-membered ring and the Ar １ The compound according to any one of claims 1 to 3, characterized in that it forms a five-membered ring that forms a condensation unit together with a group.

5. The condensation unit is selected from fluorene, dibenzofuran, and dibenzothiophene, each of which is R １ and R ２ The compound according to claim 4, characterized in that it may be substituted with [another compound].

6. Ar ２ However, the group of the following equations 【Transformation 3】 A compound according to any one of claims 1 to 5, characterized in that it is selected from among the following.

7. R １ However, in each case they may be the same or different, H, D, CN, N(R ５ ) ２ , selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned herein each contain one or more R ５ It may also be substituted with radicals; R ２ and R ４ However, in each case they may be the same or different, H, D, F, CN, N(R ５ ) ２ Selected from linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups, aromatic ring systems, and heteroaromatic ring systems mentioned herein may each be substituted with one or more R5 radicals; R ３ However, in each case they may be the same or different, H, D, F, CN, N(R ５ ) ２ The compound according to any one of claims 1 to 6, characterized in that it is selected from a linear alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms; wherein each of the alkyl groups mentioned herein may be substituted with one or more R5 radicals.

8. Formulas (I-1-1), (I-1-3), (I-2-1), and (I-2-3) 【Chemistry 4-1】 【Chemistry 4-2】 (The following applies to equations (I-1-1) and (I-1-3): i is either 0 or 1, k is either 0 or 1, The sum of k and i is 1 or 2, preferably 1. The free positions on the benzene ring are R １ It may be substituted with a radical, and the divalent group Y does not exist; The following applies to equations (I-2-1) and (I-2-3): Y is C(R １ ) ２ Selected from O and S; The free positions on the benzene ring are R １ The compound according to any one of claims 1 to 7, characterized in that it corresponds to one of (which may be substituted with a radical).

9. In the first step i), a biphenyl derivative substituted with reaction groups X and Y (where group X is in the ortho position relative to the bond between the two phenyl groups) is reacted with an aromatic or heteroaromatic ring system substituted with a boronic acid group, resulting in the aromatic or heteroaromatic ring system being introduced at the position of group Y, and in the second step ii), the intermediate obtained in step i) is given the formula HNAr ２ The compound is reacted with (wherein Ar is selected from aromatic ring systems and heteroaromatic ring systems), and in this reaction, -NAr ２ A method for preparing the compound according to any one of claims 1 to 8, characterized in that the group is introduced at the position of the X group.

10. A preparation comprising at least one compound according to any one of claims 1 to 8 and at least one solvent.

11. An electronic device comprising at least one compound according to any one of claims 1 to 8.

12. An organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer, wherein at least one organic layer of the device may contain the at least one compound, which may be the light-emitting layer or the hole transport layer.

13. The device according to claim 12, characterized by comprising at least one electron blocking layer comprising at least one compound of formula (I).

14. Use of the compound according to any one of claims 1 to 8 in an electronic device.

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