Materials for organic electroluminescent devices

Abstract

The present invention relates to materials for use in organic electroluminescent devices. In particular, the present invention relates to compounds of formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and electronic devices comprising these compounds.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / EP2016 / 002010, international application date of November 28, 2016, application number 201680073470.8 that entered the Chinese national phase, and invention title "Materials for Organic Electroluminescent Devices". Technical Field

[0002] This invention relates to materials for use in organic electroluminescent devices. Specifically, this invention relates to materials suitable for use in electronic devices, particularly organic electroluminescent devices, and to electronic devices comprising these materials. Background Technology

[0003] For example, structures of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials are described in US 4,539,507, US 5,151,629, EP 0676461, and WO 98 / 27136. The luminescent materials used here are increasingly organometallic complexes that exhibit phosphorescence rather than fluorescence (MA Baldo et al., Appl. Phys. Lett. (Applied Physics Letters) 1999, 75 , 4-6).

[0004] According to existing technology, hole transport materials used in hole transport layers or hole injection layers, particularly triarylamine derivatives, typically contain at least two triarylamino groups or at least one triarylamino group and at least one carbazole group. These compounds are generally derived from diarylamino-substituted triphenylamines (TPA type), diarylamino-substituted biphenyl derivatives (TAD type), or combinations of these base compounds. Furthermore, for example, spirodifluorene derivatives substituted with one to four diarylamino groups are used (e.g., according to EP 676461, US 7,714,145, EP2814906). Further improvements are needed in the case of these compounds, both in the case of fluorescent OLEDs and phosphorescent OLEDs, particularly in terms of efficiency, lifetime, and operating voltage when used in organic electroluminescent devices.

[0005] Simultaneously, it is important that the compounds processed by vacuum evaporation exhibit high temperature stability in order to obtain OLEDs with reproducible properties. The compounds used in OLEDs should also exhibit low crystallinity and high glass transition temperature to obtain OLEDs with satisfactory lifetimes. Summary of the Invention

[0006] The object of the present invention is to provide compounds suitable for use in fluorescent or phosphorescent OLEDs, particularly phosphorescent OLEDs, for example, as hole transport materials in hole transport or exciton blocking layers or as matrix materials in light-emitting layers.

[0007] It has now been found that specific compounds, described in more detail below, achieve this objective and produce significant improvements in organic electroluminescent devices, particularly in lifetime, efficiency, and operating voltage. This applies to phosphorescent and fluorescent electroluminescent devices, especially when using compounds according to the invention as hole transport materials or as matrix materials. Furthermore, the compounds described below comprise rigid planar spirocyclic units and flexible structural elements on the periphery, thereby reducing the flexibility of the molecular center and increasing solubility through substituents, resulting in easier cleaning and handling of these compounds. Finally, the compounds of the invention generally possess high thermal stability and can therefore sublimate without decomposition and without residue. Therefore, the present invention relates to these compounds and electronic devices comprising such compounds.

[0008] Therefore, this invention relates to compounds of formula (1):

[0009] The following definitions apply to the symbols and markings used: Ar 1 It is a group of formula (Ar1-1).

[0010] Ar 2 It is a group of formula (Ar2-1) or (Ar2-2).

[0011] V, Z, T, and Q are either N or CR each time they appear. 1 The condition is that each 6-membered ring contains at most three N atoms; Or V is C and is connected via bridge base E. 1 It is connected to an adjacent group Z, which is also C; Or V is C and is connected via bridge base E. 1 It is attached to an adjacent group T, which is also C; Or V is C and is connected via bridge base E. 1 It is connected to an adjacent group Q, which is also C; Alternatively, groups represented by two adjacent groups V (VV or V=V), two adjacent groups T (TT or T=T), two adjacent groups Z (ZZ or Z=Z), and / or two adjacent groups Q (QQ or Q=Q) may be represented by formula (E-1).

[0012] The dashed lines represent connections to the remaining portions of the 6-membered ring containing the group V, the remaining portions of the 6-membered ring containing the group T, the remaining portions of the 6-membered ring containing the group Z, or the remaining portions of the 6-membered ring containing the group Q, respectively. E 1 E 2 Each time it appears, it is either the same or different from B(R). 0 ), C(R 0 )2、Si(R 0 2. C=O, C=NR 0 C=C(R) 0 )2、O、S、S=O、SO2、N(R 0 ), P(R 0 ) and P(=O)R 0 The two-valent bridge foundation; Ar L It is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be converted by one or more groups R 1 replace; R, R 0 R 1 Each occurrence is selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, either identically or differently. 3 , P(=O)(Ar 3 )2,S(=O)Ar 3 S(=O)2Ar 3 NO2, Si(R) 2 3, B(OR) 2 )2, OSO2R 2 A straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, each of which may be further classified by one or more groups R. 2 Substitution, wherein in each case 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、Sn(R 2 )2. C=O, C=S, C=Se, P(=O)(R 2 ), SO, SO2, O, S or CONR 2An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and said aromatic or heteroaromatic ring system may in each case be replaced by one or more R groups. 2 The aryloxy group having 5 to 40 aromatic ring atoms is substituted, said aryloxy group being substituted by one or more groups R 2 Substitution, wherein two adjacent substituents R, two adjacent substituents R 0 and / or two adjacent substituents R 1 It may optionally form a monocyclic or polycyclic aliphatic or aromatic ring system, wherein the monocyclic or polycyclic aliphatic or aromatic ring system may be formed by one or more groups R 2 replace; R 2 Each occurrence is selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, either identically or differently. 3 , P(=O)(Ar 3 )2,S(=O)Ar 3 S(=O)2Ar 3 NO2, Si(R) 3 3, B(OR) 3 )2, OSO2R 3 A straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, each of which may be further classified by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and said aromatic or heteroaromatic ring system may in each case be replaced by one or more R groups. 3 The aryloxy group having 5 to 60 aromatic ring atoms is substituted, and the aryloxy group may be replaced by one or more groups R. 3 Substitution, in which two adjacent substituents R 2 It may optionally form a monocyclic or polycyclic aliphatic or aromatic ring system, wherein the monocyclic or polycyclic aliphatic or aromatic ring system may be formed by one or more groups R3 replace; R 3 Each time it appears, it is selected from H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and one or more H atoms may be replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar 3 It is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may in each case be further divided by one or more groups R. 3 replace; i is either 0 or 1 each time it appears; m and n are either the same or different 0 or 1; s, p, and r are the same or different from 0, 1, 2, 3, or 4; where r + n ≤ 4 and p + m ≤ 4; q is 0, 1, or 2.

[0013] For the purposes of this application, the following definitions of chemical groups apply: In the context of this invention, an aryl group contains 6 to 60 aromatic ring atoms; a heteroaryl group contains 5 to 60 aromatic ring atoms, wherein at least one ring atom is a heteroatom. The heteroatom is preferably selected from N, O, and S. This represents the basic definition. If other preferred embodiments are indicated in the description of this invention, such as regarding the number of aromatic ring atoms or heteroatoms present, those preferred embodiments apply.

[0014] Here, aryl or heteroaryl groups refer to simple aromatic rings, i.e., benzene, or simple heteroaryl rings, such as pyridine, pyrimidine, or thiophene, or fused (enhanced) aromatic or heteroaryl polycyclic rings, such as naphthalene, phenanthrene, quinoline, or carbazole. Fused (enhanced) aromatic or heteroaryl polycyclic rings in the sense of this application consist of two or more simple aromatic or heteroaryl rings fused together.

[0015] Specifically, in each case, the aryl or heteroaryl group that can be substituted by the aforementioned groups and can be linked to the aromatic or heteroaryl ring system via any desired position refers to a group derived from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, etc. Perylene, fluoranthene, benzo[a]anthene, benzo[a]phenanthrene, tetraphenylene, pentaphenylene, benzo[a]pyrene, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzo[a]thiophene, isobenzo[a]thiophene, dibenzo[a]thiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridinium imidazoles, pyrazinium imidazoles, quinoxaline imidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthidine, azacarbazole, benzocarbline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indene, and benzothiadiazole.

[0016] According to the present invention, an aryl group is defined as an aryl group as defined above, bonded via an oxygen atom. A similar definition applies to heteroaryl groups. An aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms. A heteroaromatic ring system in the sense of the present invention contains 5 to 60 aromatic ring atoms, wherein at least one ring atom is a heteroatom. The heteroatom is preferably selected from N, O, and / or S. An aromatic or heteroaromatic ring system in the sense of the present invention is intended to refer to a system that does not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups are also connected by non-aromatic units (preferably less than 10% of non-H atoms), such as sp... 3 -Hybridized C, Si, N, or O atoms, sp 2-Hybridized C or N atoms, or sp-hybridized C atoms, are connected. Therefore, systems in which two or more aryl groups are connected, for example, by straight-chain or cyclic alkyl, alkenyl, or alkynyl groups or by silyl groups, such as 9,9'-spirodifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also considered aromatic ring systems in the sense of this invention. In addition, systems in which two or more aryl or heteroaryl groups are connected to each other by single bonds, such as biphenyl, terphenyl, or diphenyltriazine, are also considered aromatic or heteroaromatic ring systems in the sense of this invention.

[0017] Specifically, an aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which can be substituted by groups as defined above and can be attached to the aromatic or heteroaromatic group at any desired position, refers to groups derived from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, etc. Perylene, fluoranthene, tetraphenylene, pentaphenylene, benzo[a]pyrene, biphenyl, azobenzene, terphenyl, triphenylene, tetraphenylene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indo[a]fluorene, trimerin, isotrimerinin, spirotrimerinin, spiroisotrimerinin, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzo[a]thiophene, isobenzo[a]thiophene, dibenzo[a]thiophene, pyrrole, indole, isoindole, carbazole, indole[a]carbazole, indo[a]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridinium imidazoles, pyrazinium imidazoles, quinoxaline imidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazoles, benzo[a]triazoles, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 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, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indene and benzothiadiazole, or combinations of these groups.

[0018] For the purposes of this invention, each H atom or CH2 group may be substituted by a straight-chain alkyl group having 1 to 40 C atoms, or a branched or cyclic alkyl group having 3 to 40 C atoms, or an alkenyl or alkynyl group having 2 to 40 C atoms, preferably a group containing: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methyl Butyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, or ocynyl. The alkoxy or thioalkyl group having 1 to 40 carbon atoms is preferably methyl methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio Thioyl, tert-butylthioyl, n-pentylthioyl, sec-pentylthioyl, n-hexylthioyl, cyclohexylthioyl, n-heptylthioyl, cycloheptylthioyl, n-octylthioyl, cyclooctylthioyl, 2-ethylhexylthioyl, trifluoromethylthioyl, pentafluoroethylthioyl, 2,2,2-trifluoroethylthioyl, ethylene thioyl, propylene thioyl, butene thioyl, pentene thioyl, cyclopentene thioyl, hexene thioyl, cyclohexene thioyl, heptene thioyl, cycloheptene thioyl, octene thioyl, cyclooctene thioyl, ethynylthioyl, propynylthioyl, butynylthioyl, pentynylthioyl, hexynylthioyl, heptynylthioyl, or octyynylthioyl.

[0019] For the purposes of this application, the statement that two groups can form a ring with each other specifically refers to two groups being connected to each other by chemical bonds. This is illustrated by the following scheme:

[0020] However, the above statement also indicates that, when one of the two groups represents hydrogen, the second group is bonded at the position where the hydrogen atom is bonded, thus forming a ring. This is illustrated by the following scheme:

[0021] According to a preferred embodiment, m + n = 1. More preferably, m + n = 0.

[0022] Ar group L Each occurrence is identical or different from an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 14 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may in each case be further influenced by one or more R groups. 1 replace.

[0023] More preferably, Ar L Selected from benzene, biphenyl, fluorene, dibenzofuran, dibenzothiophene, and carbazole, wherein the group may in each case be replaced by one or more groups R. 1 Replacement. More preferably, Ar L Selected from benzene, the group may be converted by one or more groups R 1 It can be replaced, but it is preferable that it is not replaced.

[0024] Suitable group Ar L For example, the following formula (Ar) L -1) to (Ar L -37) group:

[0025] The dashed bonds represent bonds connected to spirodifluorene and bonds connected to amines, and the groups (Ar) in the dashed lines represent bonds connected to spirodifluorene and amines. L -1) to (Ar L -37) can be affected by group R at each free position. 1 It can be replaced, but it is preferable that it is not replaced.

[0026] In the groups of formulas (ArL-1) to (ArL-37), the group (Ar L -1), (Ar L -2) and (Ar L -3) is the preferred option.

[0027] According to a preferred embodiment, the marker i is equal to 0, such that the group -NAr 1 Ar 2 It bonds directly to the spirodifluorene skeleton.

[0028] According to a preferred embodiment, Ar 3It is an aryl group having 6 to 18 carbon atoms or a heteroaryl group having 5 to 18 aromatic ring atoms, and in each case, the group may also be replaced by one or more R groups. 4 replace.

[0029] According to a preferred embodiment, the group Ar 2 Groups selected from formulas (Ar2-3) to (Ar2-6),

[0030] The symbols Z, V, T, and Q have the same meaning as defined above.

[0031] More preferably, the Ar group 2 Groups selected from formulas (Ar2-7) to (Ar2-10),

[0032] Where the symbol E 1 R 1 It has the same meaning as above, and in which

[0033] a, b, c, and d are either the same or different from 0 or 1; x, z, and g are the same or different from 0, 1, 2, 3, 4, or 5; wherein in equation (Ar2-7) a + b + x ≤ 5 and z + c ≤ 5, in equation (Ar2-8) a + x ≤ 5 and z + c ≤ 5, in equation (Ar2-9) a + b + x ≤ 5 and z + c + d ≤ 5, and in equation (Ar2-10) g + c + d ≤ 5; y is 0, 1, 2 or 3; where in equation (Ar2-7) y + a + b + c ≤ 3, in equation (Ar2-8) y + a + c ≤ 3, and in equation (Ar2-9) y + a + b + c + d ≤ 3; e and f are the same or different from 0, 1, 2, 3 or 4; where e + a + b ≤ 4 and f + a + b + c + d ≤ 4.

[0034] More preferably, in equations (Ar2-7), (Ar2-9) and (Ar2-10) a + b ≤ 1, and in equations (Ar2-9) and (Ar2-10) c + d ≤ 1.

[0035] Particularly preferred are that a + b ≤ 1 and c = 0 in equation (Ar2-6), and a + b ≤ 1 and c = d = 0 in equations (Ar2-9) and (Ar2-10).

[0036] Among the groups of formulas (Ar2-7) to (Ar2-10), groups (Ar2-7) and (Ar2-8) are preferred. More particularly, groups (Ar2-7a) and (Ar2-8a) as shown below are preferred:

[0037] Where the symbol R 1 and E 1 It has the same meaning as above, and wherein: a and b are either 0 or 1, and a + b ≤ 1; x and z are the same or different from 0, 1, 2, 3, 4 or 5; where a + b + x ≤ 5; y is 0, 1, 2, or 3; where y + a + b ≤ 3; A particularly preferred feature is the Ar group. 2 Groups selected from formulas (Ar2-7-1) to (Ar2-10-1),

[0038] Where the symbol R 1 It has the same meaning as described above, and

[0039] x, z, and g are 0, 1, 2, 3, 4, or 5; y is 0, 1, 2, or 3; and e and f are 0, 1, 2, 3 or 4.

[0040] Among the groups of formulas (Ar2-7-1) to (Ar2-10-1), groups (Ar2-7-1) and (Ar2-8-1) are preferred. More particularly, groups (Ar2-7a-1) and (Ar2-8a-1) as shown below are preferred:

[0041] Suitable group Ar 2 For example, the groups shown below (Ar2-13) to (Ar2-469):

[0042] The dashed bonds in Ar2-13 to Ar2-469 represent bonds connected to nitrogen atoms.

[0043] Among the groups Ar2-13 to Ar2-469, the following groups are preferred: Ar2-13 to Ar2-27, Ar2-100 to Ar2-103, Ar2-105, Ar2-106, Ar2-118, Ar2-131 to Ar2-133, Ar2-136, Ar2-138, Ar2-142 to Ar2-144, Ar2-148, Ar2-152 to Ar2-154, Ar2-159, Ar2-162 to Ar2-164, Ar2-170 to Ar2-174, Ar2-178, and Ar2-182 to Ar2-185. Ar2-192 to Ar2-194, Ar2-199, Ar2-207 to Ar2-214, Ar2-219, Ar2-243 to Ar2-245, Ar2-251, Ar2-261, Ar2-266, Ar2-267, Ar2-274, Ar2-298, Ar2-302, Ar2-311, Ar2-317 to Ar2-319, Ar2-383 to Ar2-385, Ar2-391 to Ar2-410, Ar2-414, Ar2-419 to Ar2-421, and Ar2-424 to Ar2-427.

[0044] According to a preferred embodiment of the present invention, the group Ar 1 Groups selected from formula (Ar1-2),

[0045] Where R 1 It has the same meaning as above, and in which

[0046] E 3 It is selected from B(R) 0 ), C(R 0 )2、Si(R 0 2. C=O, C=NR 0 C=C(R) 0 )2、O、S、S=O、SO2、N(R 0 ), P(R 0 ) and P(=O)R 0 The bivalent bridge foundation, where R 0 It has the same meaning as above; and

[0047] t is 0 or 1; where t is 0 means that the binary bridge base E does not exist; u is 0, 1, 2, 3, or 4; where u + t ≤ 4. v is 0, 1, 2, 3, 4 or 5; where v + t ≤ 5.

[0048] Furthermore, it is preferable that the label t equals 1, and the group Ar... 1 Groups selected from formula (Ar1-2a):

[0049] Where the symbol E 3 and R 1 It has the same meaning as above, and wherein: u is 0, 1, or 3; v can be 0, 1, 2, 3, or 4.

[0050] Particularly preferred is the Ar group. 1 Groups selected from formulas (Ar1-3) to (Ar1-6):

[0051] Where the symbol R 0 and R 1 The symbols u and v have the same meaning as described above.

[0052] Suitable group Ar 1 Examples are the groups Ar1-7 to Ar1-51 shown below:

[0053] Among the groups of formulas Ar1-7 to Ar1-51, groups Ar1-7, Ar1-8, Ar1-9, Ar1-13, Ar1-14 and Ar1-16 are preferred.

[0054] According to a preferred embodiment, group E 1 E 2 and / or E 3 Selected from C(R) in the same or different ways 0 )2, O, S or N (R) 0 ).

[0055] Preferably, R 0 Each occurrence is selected from H, D, F, CN, Si(R) in the same or different manner. 2 )3, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of said groups being capable of being coupled with one or more groups R 2 Substitution, wherein in each case one or more H atoms may be replaced by F, or an aryl or heteroaryl group having 5 to 40 aromatic ring atoms, wherein in each case the group may be replaced by one or more groups R. 2 Substitution, in which two adjacent substituents R 0 It can form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be formed by one or more groups R. 2 replace.

[0056] Furthermore, it is preferred that groups R and R are present. 1 Each occurrence thereof is identical or different from H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be represented by one or more groups R. 2 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by O and one or more H atoms can be replaced by F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be replaced by one or more R groups. 2 replace.

[0057] Furthermore, R is preferred. 2 Each occurrence thereof is identical or different from H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be represented by one or more groups R.3 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by O and one or more H atoms can be replaced by F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be replaced by one or more R groups. 3 replace.

[0058] According to a preferred embodiment of the present invention, the compound of formula (1) is selected from compounds of formulas (1-1) to (1-30).

[0059] The symbols and markings used have the meanings given above.

[0060] According to another preferred embodiment of the invention, the compound of formula (1) is selected from compounds of formulas (1-31) to (1-60).

[0061] Of the formulas (1-1) to (1-60), formulas (1-1) to (1-12) and (1-31) to (1-42) are preferred. Formulas (1-1) to (1-4) and (1-31) to (1-34) are particularly preferred. Formulas (1-1), (1-2), (1-31), and (1-32) are very particularly preferred.

[0062] Compounds of formulas (1) and (1-1) to (1-60) are particularly preferred, wherein the above-described preferred embodiments are present simultaneously. Therefore, compound of formula (1) is particularly preferred, wherein: Ar 1 Groups selected from formula (Ar1-2a),

[0063] Where the symbol E 3 and R 1 It has the same meaning as above, and wherein: u is 0, 1, or 3; v can be 0, 1, 2, 3, or 4.

[0064] E 3 It is C(R) 0 )2, O, S or N (R) 0 ); Ar 2Groups selected from formula (Ar2-6a) or (Ar2-7a),

[0065] in

[0066] a and b are 0 or 1, where a + b ≤ 1; x and z are the same or different from 0, 1, 2, 3, 4 or 5; where a + b + x ≤ 5 in equation (Ar2-7a) and a + x ≤ 5 in equation (Ar2-8a); y is 0, 1, 2 or 3, where y + a + b ≤ 3 in equation (Ar2-7a) and a + x ≤ 3 in equation (Ar2-8a); E 1 It is C(R) 0 )2, O, S or N (R) 0 ); Ar L It is a phenyl group, which can be replaced by group R at each free position. 1 replace; R 0 Each occurrence is selected from H, D, F, CN, Si(R) in the same or different manner. 2 )3, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of said groups being capable of being coupled with one or more groups R 2 Substitution, wherein in each case one or more H atoms may be replaced by F, or an aryl or heteroaryl group having 5 to 40 aromatic ring atoms, wherein in each case the aryl or heteroaryl group may be replaced by one or more groups R. 2 Substitution, in which two adjacent substituents R 0 It can form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be formed by one or more groups R. 2 replace.

[0067] R and R 1 Each occurrence thereof is identical or different from H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be represented by one or more groups R. 2 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by O and one or more H atoms can be replaced by F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be replaced by one or more R groups. 2 replace.

[0068] R 2 Each occurrence thereof is identical or different from H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be represented by one or more groups R. 3 Substitution, wherein one or more non-adjacent CH2 groups can be replaced by O and one or more H atoms can be replaced by F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be replaced by one or more R groups. 3 replace.

[0069] R 3 Each time it appears, it is selected from H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and one or more H atoms may be replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar 3 It is an aryl group having 6 to 18 carbon atoms or a heteroaryl group having 5 to 18 aromatic ring atoms, and in each case, the group may also be replaced by one or more R groups. 3 replace; i is 0 or 1; and m and n are equal to 0.

[0070] For compounds processed by vacuum evaporation, the alkyl group preferably has no more than 4 carbon atoms, and particularly preferably no more than 1 carbon atom. For compounds processed from solution, suitable compounds also include those substituted with straight-chain, branched, or cyclic alkyl groups having up to 10 carbon atoms, or those substituted with oligomeric aryl groups such as ortho, meta, para, or branched terphenyl or tetraphenyl groups.

[0071] Examples of preferred structures of compounds according to formula (1) are compounds of formula (1-1) or (1-31), wherein: R is H Ar L In equation (1-1), it is equation (Ar) L -1), (Ar L -2) or (Ar L -3) phenyl group; and Ar 1 and Ar 2 Combine the items listed in the table below;

[0072] Other examples of suitable compounds according to the invention are those shown in the table below:

[0073] The compounds according to the invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, borylation, Ullmann arylation, Hartwig-Buchwald coupling, and Suzuki coupling, as shown in Scheme 1 or Scheme 2 below.

[0074] Option 1:

[0075] Option 2

[0076] X is a halogen or other leaving group.

[0077] Ar 1 Ar 2 It is a arabess or hybrid arabess ring system.

[0078] Therefore, the present invention also relates to a method for preparing a compound of formula (1), characterized in that a diarylamino group is introduced by a CN coupling reaction between 1-, 3-, or 4-halospirofluorene and a diarylamine.

[0079] The compounds described above according to the invention, particularly those substituted with reactive leaving groups such as chlorine, bromine, iodine, toluenesulfonate, trifluoromethanesulfonate, boric acid, or borate esters, can be used as monomers to prepare the corresponding oligomers, dendritic macromolecules, or polymers. The oligomerization or polymerization is preferably carried out via halogen or boric acid functionality.

[0080] Therefore, the present invention also relates to oligomers, polymers, or dendritic macromolecules comprising one or more compounds of formula (1), wherein the bonds bonded to the polymer, oligomer, or dendritic macromolecule may be located at any desired position in formula (1) where R is substituted. Depending on the linkage of the compounds of formula (1), the compounds may be part of the side chain of the oligomer or polymer or part of the main chain. An oligomer, in the sense of the present invention, refers to a compound constructed of at least three monomer units. A polymer, in the sense of the present invention, refers to a compound constructed of at least ten monomer units. Polymers, oligomers, or dendritic macromolecules according to the present invention may be conjugated, partially conjugated, or non-conjugated. Oligomers or polymers according to the present invention may be linear, branched, or dendritic. In a linearly linked structure, the units of formula (1) may be directly linked to each other or may be linked 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, three or more units of formula (1) may be linked, for example, via trivalent or polyvalent groups, such as via trivalent or polyvalent aromatic or heteroaromatic groups, to obtain branched or dendritic oligomers or polymers. The same preferred mode as described above for compounds of formula (1) applies to repeating units of formula (1) in oligomers, dendritic macromolecules and polymers.

[0081] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorene (e.g., according to EP 842208 or WO 00 / 22026), spirodifluorene (e.g., according to EP 707020, EP 894107 or WO 06 / 061181), p-phenylene (e.g., according to WO 92 / 18552), carbazole (e.g., according to WO 04 / 070772 or WO 04 / 113468), thiophene (e.g., according to EP 1028136), dihydrophenanthrene (e.g., according to WO 05 / 014689 or WO 07 / 006383), cis- and trans-indenofluorene (e.g., according to WO 04 / 041901 or WO 04 / 113412), ketones (e.g., according to WO 05 / 040302), phenanthrene (e.g., according to WO 00 / 22026), and phenanthrene (e.g., according to WO 00 / 22026). The polymers, oligomers, and dendritic macromolecules typically also contain other units, such as luminescent (fluorescent or phosphorescent) units like vinyltriarylamines (e.g., according to WO 07 / 068325) or phosphorescent metal complexes (e.g., according to WO 06 / 003000), and / or charge transport units, particularly those based on triarylamines.

[0082] The polymers and oligomers according to the invention are generally prepared by polymerization of one or more types of monomers, at least one of which produces a repeating unit of formula (1) in the polymer. Suitable polymerization reactions are known to those skilled in the art and described in the literature. Particularly suitable and preferred polymerization reactions leading to CC or CN linkages are the following reactions: (A) SUZUKI polymerization; (B)YAMAMOTO aggregation; (C) STILLE aggregation; and (D)HARTWIG-BUCHWALD polymerization.

[0083] The methods by which polymerization can be carried out and the methods by which the polymer can subsequently be separated from the reaction medium and purified are known to those skilled in the art and are described in detail in the literature, such as WO 2003 / 048225, WO 2004 / 037887 and WO 2004 / 037887.

[0084] Therefore, the present invention also relates to a method for preparing polymers, oligomers, and dendritic macromolecules according to the invention, characterized in that they are prepared by SUZUKI polymerization, YAMAMOTO polymerization, STILLE polymerization, or HARTWIG-BUCHWALD polymerization. The dendritic macromolecules according to the invention can be prepared by methods known to those skilled in the art or similar methods. The appropriate methods are described in the literature, for example, Frechet, Jean MJ; Hawker, Craig J., “Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers”, Reactive & Functional Polymers (1995), 26(1-3), 127-36; Janssen, HM; Meijer, EW, “The synthesis and characterization of dendritic molecules”, Materials Science and Technology (1999), 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995), 272(5), 62-6; WO 02 / 067343 A1 and WO 2005 / 026144 A1.

[0085] The compounds according to the invention are suitable for use in electronic devices. Electronic devices herein refer to devices comprising at least one layer, said at least one layer containing at least one organic compound. However, the components herein may also comprise inorganic materials or layers constructed entirely of inorganic materials.

[0086] Therefore, the present invention also relates to the use of the compounds according to the invention in electronic devices, particularly in organic electroluminescent devices.

[0087] The present invention also relates to an electronic device comprising at least one compound according to the invention. The above-described preferred embodiments also apply to the electronic device.

[0088] The electronic devices are preferably selected from organic electroluminescent devices (organic light-emitting diodes, OLEDs), 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 dye-sensitized solar cells (ODSSCs), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasma emitting devices (DM Koller, etc.). Nature Photonics (Natural Photonics) 2008, 1-4), but organic light-emitting devices (OLEDs) are preferred, and phosphorescent OLEDs are particularly preferred.

[0089] The organic electroluminescent devices and luminescent electrochemical cells can be used in a variety of applications, such as for monochrome or multicolor displays, for lighting applications, or for medical and / or cosmetic applications, such as for phototherapy.

[0090] The organic electroluminescent device comprises a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also include other layers, such as 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, exciton blocking functionality may also be introduced between the two light-emitting layers. However, it should be noted that each of these layers is not necessarily required.

[0091] The organic electroluminescent device described herein may comprise one or more emissive layers. If multiple emissive layers are present, they preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in white emission overall, i.e., using multiple luminescent compounds capable of fluorescence or phosphorescence in the emissive layers. A system having three emissive layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission (for the basic structure, see, for example, WO 2005 / 011013). It is permissible here for all emissive layers to be fluorescent, or for all emissive layers to be phosphorescent, or for one or more emissive layers to be fluorescent and one or more other layers to be phosphorescent.

[0092] Here, depending on the specific structure, the compounds of the present invention according to the above embodiments can be used in different layers. Preferably, organic electroluminescent devices contain the compounds of formula (1) or preferred embodiments as hole transport materials in hole transport or hole injection or exciton blocking layers, or as matrix materials for fluorescent or phosphorescent emitters, particularly for phosphorescent emitters. The preferred embodiments described above are also applicable to the use of said materials in organic electronic devices.

[0093] In a preferred embodiment of the present invention, the compound of formula (1) or the preferred embodiment is used as a hole transport or hole injection material in a hole transport or hole injection layer. The luminescent layer here may be fluorescent or phosphorescent. In the context of the present invention, the hole injection layer is the layer directly adjacent to the anode. In the context of the present invention, the hole transport layer is the layer located between the hole injection layer and the luminescent layer.

[0094] In another preferred embodiment of the invention, the compound of formula (1) or the preferred embodiment is used in the exciton blocking layer. The exciton blocking layer is a layer directly adjacent to the light-emitting layer on the anode side.

[0095] The compound of formula (1) or preferred embodiment is particularly preferred for use in hole transport or exciton blocking layers.

[0096] If the compound of formula (1) is used as a hole transport material in a hole transport layer, hole injection layer, or exciton blocking layer, then the compound of formula (1) can be used as a single material, i.e., in 100% of such a layer, or the compound of formula (1) can be used in combination with one or more other compounds in such a layer. According to a preferred embodiment, the organic layer containing the compound of formula (1) further contains one or more p-type dopants. Preferred p-type dopants of the present invention are organic compounds that can accept electrons (electron acceptors) and can oxidize one or more other compounds present in the mixture.

[0097] Particularly preferred embodiments of p-type dopant are described in WO 2011 / 073149, EP 1968131, EP2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US8057712, WO 2009 / 003455, WO 2010 / 094378, WO 2011 / 120709, US 2010 / 0096600, WO 2012 / 095143 and DE 102012209523.

[0098] As p-type dopants, particularly preferred are quinone dimethane compounds, azidoindronefluorene dione, azidobenznaphthalene, azidobenzphenanthrene, I2, metal halides (preferably transition metal halides), metal oxides (preferably metal oxides containing at least one transition metal or a Group III metal), and transition metal complexes (preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a binding site). Transition metal oxides are also preferred as dopants, with oxides of rhenium, molybdenum, and tungsten being particularly preferred, especially Re2O7, MoO3, WO3, and ReO3.

[0099] The p-type dopant is preferably distributed substantially uniformly within the p-type doped layer. This can be achieved, for example, through the co-evaporation of the p-type dopant and the hole-transporting material matrix.

[0100] Particularly preferred p-type dopants are selected from compounds (D-1) to (D-13):

[0101] In one embodiment of the invention, the compound of formula (1) or a preferred embodiment is combined with a layer comprising a hexaazabenzophenanthrene derivative, particularly hexacyanohexaazabenzophenanthrene (e.g., according to EP 1175470), for use in a hole transport or hole injection layer. Thus, for example, a preferred combination is: anode-hexaazabenzophenanthrene derivative-hole transport layer, wherein the hole transport layer comprises one or more compounds of formula (1) or a preferred embodiment. Multiple consecutive hole transport layers can also be used in this structure, wherein at least one hole transport layer comprises at least one compound of formula (1) or a preferred embodiment. Another preferred combination is: anode-hole transport layer-hexaazabenzophenanthrene derivative-hole transport layer, wherein at least one of the two hole transport layers comprises one or more compounds of formula (1) or a preferred embodiment. Multiple consecutive hole transport layers can also be used in this structure instead of a single hole transport layer, wherein at least one hole transport layer comprises at least one compound of formula (1) or a preferred embodiment.

[0102] In another preferred embodiment of the invention, the compound of formula (1) or the preferred embodiment is used as a matrix material for fluorescent or phosphorescent compounds in the light-emitting layer, particularly a matrix material for phosphorescent compounds. The organic electroluminescent device herein may comprise one or more light-emitting layers, wherein at least one light-emitting layer comprises at least one compound according to the invention as a matrix material.

[0103] If the compound of formula (1) or the preferred embodiment is used as the matrix material of the luminescent compound in the luminescent layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of this invention refers to emission from an excited state with spin multiplicity > 1, particularly from an excited triplet state. For the purposes of this application, all luminescent complexes containing transition metals or lanthanides, particularly all luminescent iridium, platinum, and copper complexes, are considered phosphorescent compounds.

[0104] Based on the entire mixture comprising the luminescent material and the matrix material, the mixture comprising the matrix material (containing a compound of formula (1) or a preferred embodiment) and the luminescent compound comprises 99.9% to 1% by weight, preferably 99% to 10% by weight, particularly preferably 97% to 60% by weight, and especially 95% to 80% by weight of the matrix material. Accordingly, based on the entire mixture comprising the luminescent material and the matrix material, the mixture comprises 0.1% to 99% by weight, preferably 1% to 90% by weight, particularly preferably 3% to 40% by weight, and especially 5% to 20% by weight of the luminescent material. The above limitations apply particularly to the application of the layer from solution. If the layer is applied by vacuum evaporation, the same values ​​apply, in which case the percentages are expressed in volume% in each case.

[0105] A particularly preferred embodiment of the present invention is to use the compound of formula (1) or the preferred embodiment as the matrix material of the phosphorescent luminescent material in combination with other matrix materials. Particularly suitable matrix materials that can be used in combination with compounds of formula (1) or preferred embodiments are aromatic ketones; aromatic phosphine oxides or aromatic sulfoxides or sulfones, such as those according to WO2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl), m-CBP or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP2004 / 288381, EP 1205527 or WO 2008 / 086851; indolecarbazole derivatives, such as those according to WO 2007 / 063754 or WO 2008 / 056746; indocarbazole derivatives, such as those according to WO 2010 / 136109 or WO 2011 / 000455; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160; bipolar matrix materials, such as those according to WO 2007 / 137725; silanes, such as those according to WO 2005 / 111172; azaborane cyclopentadiene or borate esters, such as those according to WO 2006 / 117052; triazine derivatives, such as those according to WO 2010 / 015306, WO 2007 / 063754 or WO 08 / 056746; zinc complexes, such as those according to EP 652273 or WO 2009 / 062578; fluorene derivatives, such as those according to WO The following are applicable: 2009 / 124627; diazasiloxane or tetraazasiloxane derivatives, such as those according to WO 2010 / 054729; diazaphosphonoxane derivatives, such as those according to WO 2010 / 054730; or bridged carbazole derivatives, such as those according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, or WO 2011 / 088877. Additionally, electronically neutral co-substrate lacking both hole and electron transport properties, as described, for example, in WO 2010 / 108579, may be used.

[0106] Two or more phosphorescent emitters can also be used in mixture form. In this case, the emitter emitting a shorter wavelength acts as the common host in the mixture.

[0107] Suitable phosphorescent compounds (= triplet emitters) are particularly compounds that emit light upon appropriate excitation, preferably 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, particularly preferably greater than 56 and less than 80, especially a metal having that atomic number. The phosphorescent emitter used is preferably a compound containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium, platinum, or copper.

[0108] Examples of the aforementioned luminescent materials are disclosed in the following applications: WO 2000 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 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 / 157339, or WO 2012 / 007086. Generally speaking, all phosphorescent complexes known to a person skilled in the art in the field of organic electroluminescence are suitable for use in phosphorescent OLEDs, and other phosphorescent complexes will be available to a person skilled in the art without inventive effort.

[0109] In another embodiment of the invention, the organic electroluminescent device according to the invention does not include a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer; that is, the light-emitting layer is directly adjacent to the hole injection layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO 2005 / 053051. Furthermore, a metal complex identical or similar to the metal complex in the light-emitting layer can be used as the hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0110] Furthermore, compounds of formula (1) or preferred embodiments can be used in the hole transport layer or exciton blocking layer, and compounds of formula (1) or preferred embodiments can be used as a matrix in the light-emitting layer.

[0111] In the other layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, those skilled in the art will be able to combine all known materials for organic electroluminescent devices with compounds according to formula (1) or preferred embodiments of the invention without any inventive effort.

[0112] Furthermore, the following organic electroluminescent device is preferred, characterized by applying one or more layers by a sublimation method, wherein in a vacuum sublimation unit, in a typically less than 10 -5 millibars, preferably less than 10 -6 The material is vapor-deposited at an initial pressure of millibars. However, the initial pressure can also be lower, for example, less than 10. -7 millibar.

[0113] Also preferred are organic electroluminescent devices characterized by applying one or more layers by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation, wherein in 10 -5 The material is applied at a pressure of millibar to 1 bar. A particular example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and is therefore structured (e.g., MS Arnold et al.). Appl. Phys. Lett. (Applied Physics Letters) 2008, 92 , 053301).

[0114] Furthermore, the preferred organic electroluminescent device is characterized by producing one or more layers from a solution, for example by spin coating, or by any desired printing method such as LITI (photoinduced thermal imaging, thermal transfer printing), inkjet printing, screen printing, flexographic printing, offset printing, or nozzle printing. For this purpose, a soluble compound is required, which is obtained, for example, through suitable substitution. These methods are also particularly suitable for the compounds according to the invention, because the compounds of the invention generally have very good solubility in organic solvents.

[0115] Hybrid processes are also feasible, for example, in which one or more layers are applied from a solution and one or more additional layers are applied by vapor deposition. Thus, for example, a light-emitting layer can be applied from a solution and an electron transport layer can be applied by vapor deposition.

[0116] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices containing compounds according to the present invention without requiring inventive effort from those skilled in the art.

[0117] Processing the compounds of the present invention from a liquid phase, such as by spin coating or printing, requires formulations of the compounds of the present invention. These formulations can be, for example, solutions, dispersions, or microemulsions. For this purpose, a mixture of two or more solvents may be preferred. Suitable and preferred solvents include, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, dimethyl anisole, mesitylene, tetrahydronaphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethyl benzoate, etc. Alkane or mixtures of these solvents.

[0118] Therefore, the present invention also relates to a formulation, particularly a solution, dispersion, or microemulsion, said formulation comprising at least one compound of formula (1) or a preferred embodiment described above and at least one solvent, particularly an organic solvent. Methods for preparing this type of solution are known to those skilled in the art and are described, for example, in WO 2002 / 072714, WO2003 / 019694, and the documents cited therein.

[0119] The present invention also relates to mixtures comprising at least one compound of formula (1) or a preferred embodiment described above and at least one other compound. If the compound according to the invention is used as a matrix material, the other compound may be, for example, a fluorescent or phosphorescent dopant. The mixture may then further comprise other materials as additional matrix materials. Detailed Implementation

[0120] The invention is explained in more detail by way of the following examples, but is not intended to limit the invention thereto. Those skilled in the art will be able to practice the invention throughout the scope of the disclosure using the specification, and prepare other compounds according to the invention without inventive effort, and use them in electronic devices or with the methods according to the invention.

[0121] Example: A) Synthetic Example Unless otherwise stated, the following synthesis was performed under a protective gas atmosphere. The raw materials are available from ALDRICH or ABCR. Where the raw materials are known from the literature, the numbers in square brackets are the corresponding CAS numbers.

[0122] Example 1

[0123] Synthesis of biphenyl-4-yl-([1,1';3',1'']terphenyl-4'-yl-9,9'-spirodifluorene-4-yl)amine (1-1) and derivatives (1-2) to (1-25)

[0124] a) Synthesis of the intermediate biphenyl-4-yl-[1,1';3',1'']terphenyl-4'-yl-amine (I-1)

[0125] 1,1'-bis(diphenylphosphino)ferrocene (0.9 g, 1.67 mmol), palladium acetate (360 mg, 1.67 mmol), and sodium tert-butoxide (10.1 g, 105 mmol) were added to a solution of biphenyl-4-ylamine (13.7 g, 80.8 mmol) and 4'-bromo-[1,1';3',1'']terphenyl (25 g, 80.8 mmol) in degassed toluene (400 ml), and the mixture was heated under reflux for 20 hours. The reaction mixture was cooled to room temperature, diluted with toluene, and filtered through diatomaceous earth. The filtrate was diluted with water, extracted again with toluene, and the combined organic phases were dried and evaporated under vacuum. The residue was filtered through silica gel (heptane / dichloromethane) and crystallized from isopropanol. Biphenyl-4-yl-[1,1';3',1'']terphenyl-4'-yl-amine (27 g, 85% of theoretical value) was obtained as a light yellow solid.

[0126] b) Synthesis of biphenyl-4-yl-([1,1';3',1'']terphenyl-4'-yl-9,9'-spirodifluorene-4-yl)amine (1-1)

[0127] Tri-tert-butylphosphine (2.5 ml of 1.0 M toluene solution, 2.5 mmol), palladium acetate (284 mg, 1.26 mmol), and sodium tert-butoxide (9.12 g, 95 mmol) were added to a solution of biphenyl-4-yl-[1,1';3',1'']terphenyl-4'-yl-amine (25.2 g, 63 mmol) and 4-bromo-9,9'-spirodifluorene (25 g, 63 mmol) in degassed toluene (500 ml), and the mixture was heated under reflux for 3 hours. The reaction mixture was cooled to room temperature, diluted with toluene, and filtered through diatomaceous earth. The filtrate was evaporated under vacuum, and the residue was crystallized from toluene / heptane. The crude product was extracted in a Soxhlet extractor (toluene) and purified by recrystallization from heptane / toluene (23 g, 51% of theoretical value). After sublimation under vacuum, the product was separated as a grayish-white solid.

[0128] Similarly, the following compounds were obtained:

[0129] Example 2

[0130] Synthesis of (9,9-dimethyl-9H-fluorene-2-yl)-[1,1';3',1'']terphenyl-4'-yl-[4-(9,9'-spiro-difluorene-4-yl)-phenyl]-amine (2-1) and derivatives (2-2) to (2-4)

[0131] a) Synthesis of 4-chloro-4-[(9,9'-spiro-difluorene)]. Intermediate II-1

[0132] 49 g (320 mmol) of 4-chlorophenylboronic acid, 120 g (304 mmol) of 4-bromospirofluorene, 3.51 g (3.04 mmol) of Pd(PPh3)4, and 122 g (1 mol) of potassium carbonate were dissolved in 700 mL of toluene. The reaction mixture was refluxed and stirred under an argon atmosphere for 12 hours, and after cooling to room temperature, the mixture was filtered through diatomaceous earth. The filtrate was evaporated under vacuum, and the residue was crystallized from heptane. The product (110 g, 85% of the theoretical value) was separated as a white solid.

[0133] b) (9,9-Dimethyl-9H-fluorene-2-yl)-[1,1';3',1'']terphenyl-4'-yl-[4-(9,9'-spiro-difluorene-4-yl)-phenyl]-amine (2-1)

[0134] As described for the synthesis of intermediate I-1 and compound 1-1, the synthesis of intermediate III and compounds 2-1 to 2-4 is carried out similarly.

[0135]

[0136] Similarly, comparative examples ST1 to ST8 were obtained:

[0137] B) Device Examples

[0138] The OLEDs of the present invention and those of the prior art are manufactured by means of the general method according to WO 2004 / 058911, with the method adjusted for the situations described herein (layer thickness variation, material).

[0139] Data for various OLEDs are presented in the examples below (see Tables 1 and 2). The substrate used is a glass plate coated with a 50 nm thick structured ITO (indium tin oxide). The OLED essentially has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) and finally, a cathode. The cathode is formed of a 100 nm thick aluminum layer. The specific structure of the OLED is shown in Table 1. The materials required to manufacture the OLED are shown in Table 3.

[0140] All materials are applied in a vacuum chamber via thermal vapor deposition. The luminescent layer here always consists of at least one matrix material (host material) and a luminescent dopant (emitting agent), said luminescent dopant being mixed with one or more matrix materials in a specific volume ratio via co-evaporation. For example, the expression H1:SEB (5%) means that material H1 is present in the layer at a volume ratio of 95%, while SEB is present in the layer at a ratio of 5%. Similarly, other layers may also consist of mixtures of two or more materials.

[0141] The OLED was characterized using standard methods. For this purpose, the electroluminescence spectrum and external quantum efficiency (EQE, expressed as a percentage) as a function of luminescent density were determined from the current / voltage / luminescent density characteristic line (IUL characteristic line) under assumed Lambertian light emission characteristics, and the lifetime was determined. The statement "at 10 mA / cm²" is used. 2 "EQE" indicates that at 10 mA / cm 2 The external quantum efficiency at the operating current density. "At 60 mA / cm² 2 The "LT80" refers to the OLED's initial brightness (i.e., 5000 cd / m²) without using any acceleration factors. 2 Reduced to 80% of the initial strength (i.e., reduced to 4000 cd / m²) 2 The lifespan of various OLEDs containing the materials of this invention and comparative materials is summarized in Table 2.

[0142] Use of the compound according to the invention as a hole transport material in fluorescent OLEDs

[0143] In particular, the compounds according to the invention are suitable as matrix materials in HIL, HTL, EBL, or EML of OLEDs. The compounds are suitable as monolayers, and also as mixed components in HIL, HTL, EBL, or EML. Compared with prior art components (V1 to V9), samples containing compounds according to the invention exhibit higher efficiency and / or improved lifetime in singlet blue light and triplet green light.

[0144]

[0145] Example

[0146] OLED devices with the structures shown in Table 1 were fabricated. Table 2 shows the performance data of the embodiments. The devices are fluorescent blue light devices, in which HTMV1 and HTM1, as materials in the electron blocking layer (EBL), are compared. It can be seen that the lifetime of device E1 is better than that of comparative example V1. Material HTM4 shows lower voltage and higher efficiency in device (E4) compared to comparative example V1. Materials HTM10 and HTM11 show at least higher efficiency in devices (E10, E11) compared to comparative example V1. Material HTM12 shows better efficiency and better lifetime in device (E12) compared to comparative example V1.

[0147] Compared to the reference material HTMV2, the materials HTM2, HTM8, and HTM9 of this invention exhibit better lifetime (V2 vs. E2, E8, E9). Material HTM15 exhibits better efficiency than the reference material HTMV2 (E15 vs. V2). Material HTM5 has lower voltage and better efficiency than HTMV2 (E5 vs. V2). Material HTM14 exhibits better efficiency and better lifetime in the device (E14) compared to the reference device V2.

[0148] Compared to reference material HTMV3 and reference device V3, the present invention material HTM3 exhibits a longer lifetime in device E3, material HTM15 demonstrates significantly higher efficiency in device E5, and material HTM6 exhibits lower voltage and longer lifetime in device E6. Material HTM11 shows better lifetime than reference material HTMV4 (E11 vs. V4). Compared to reference material HTMV6, the present invention material HTM1 exhibits better efficiency (E1 vs. E6).

[0149] Compared to the reference material HTMV5, the device with material HTM16 (E16) exhibits lower voltage and better lifetime compared to the reference device (V5). Material HTM17 shows better lifetime compared to the reference device (V5 vs. E17). Material HTM18 shows better efficiency and lifetime compared to the reference device (E18 vs. V5).

[0150] Compared to reference material HTMV7, the present invention material HTM13 exhibits lower voltage, better efficiency, and better lifetime (V7 vs. E13). Compared to reference material HTMV8, the present invention materials HTM19, HTM20, and HTM21 have similar or better voltage and better lifetime (V8 vs. E19, E20, and E21).

[0151] Compared to the reference material HTMV9, material HTM7 exhibits better voltage, better efficiency, and better lifetime.

Claims

1. A compound of any one of formulas (1-1) to (1-60), The following definitions apply to the symbols and markings used: Ar 1 It is a group of formula (Ar1-1). Ar 2 It is a group of formula (Ar2-1) or (Ar2-2). V, Z, T, and Q are either N or CR each time they appear. 1 The condition is that each 6-membered ring contains at most three N atoms; Or V is C and is connected via bridge base E. 1 It is connected to an adjacent group Z, which is also C; Or V is C and is connected via bridge base E. 1 It is attached to an adjacent group T, which is also C; Or V is C and is connected via bridge base E. 1 It is connected to an adjacent group Q, which is also C; Alternatively, groups represented by two adjacent groups V (VV or V=V), two adjacent groups T (TT or T=T), two adjacent groups Z (ZZ or Z=Z), and / or two adjacent groups Q (QQ or Q=Q) may be represented by formula (E-1). The dashed lines represent connections to the remaining portions of the 6-membered ring containing the group V, the remaining portions of the 6-membered ring containing the group T, the remaining portions of the 6-membered ring containing the group Z, or the remaining portions of the 6-membered ring containing the group Q, respectively. E 1 E 2 Each time it appears, it is either the same or different from B(R). 0 ), C(R 0 )2、Si(R 0 2. C=O, C=NR 0 C=C(R) 0 )2、O、S、S=O、SO2、N(R 0 ), P(R 0 ) and P(=O)R 0 The two-valent bridge foundation; Ar L It is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system can be converted by one or more groups R 1 replace; R, R 0 R 1 Each occurrence is selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, either identically or differently. 3 , P(=O)(Ar 3 )2,S(=O)Ar 3 S(=O)2Ar 3 NO2, Si(R) 2 3, B(OR) 2 )2, OSO2R 2 A straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, each of which may be further classified by one or more groups R. 2 Substitution, wherein in each case 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、Sn(R 2 )2. C=O, C=S, C=Se, P(=O)(R 2 ), SO, SO2, O, S or CONR 2 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and said aromatic or heteroaromatic ring system may in each case be replaced by one or more R groups. 2 Substitution, and an aryloxy group having 5 to 40 aromatic ring atoms, said aryloxy group may be replaced by one or more groups R 2 Substitution, in which two adjacent substituents R 0 It can form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be formed by one or more groups R. 2 replace; R 2 Each occurrence is selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, either identically or differently. 3 , P(=O)(Ar 3 )2,S(=O)Ar 3 S(=O)2Ar 3 NO2, Si(R) 3 3, B(OR) 3 )2, OSO2R 3 A straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 40 carbon atoms, each of which may be further classified by one or more groups R. 3 Substitution, wherein in each case one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 C≡C, Si(R) 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=Se, P(=O)(R 3 ), SO, SO2, O, S or CONR 3 An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and said aromatic or heteroaromatic ring system may in each case be replaced by one or more R groups. 3 Substitution, and an aryloxy group having 5 to 60 aromatic ring atoms, said aryloxy group may be replaced by one or more groups R 3 replace; R 3 Each time it appears, it is selected from H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and one or more H atoms may be replaced by D, F, Cl, Br, or I, and an aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar 3 It is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which in each case may also be converted by one or more groups R. 3 replace.

2. The compound according to claim 1, characterized in that... Ar 2 Groups selected from formulas (Ar2-3) to (Ar2-6), The symbols Z, V, T, and Q have the same meaning as defined in claim 1.

3. The compound according to one or more of the preceding claims, characterized in that... The group Ar 1 Groups selected from formula (Ar1-2), Where R 1 It has the same meaning as in claim 1, and wherein E 3 It is selected from B(R) 0 ), C(R 0 )2、Si(R 0 2. C=O, C=NR 0 C=C(R) 0 )2、O、S、S=O、SO2、N(R 0 ), P(R 0 ) and P(=O)R 0 The bivalent bridge foundation, where R 0 It has the same meaning as in claim 1; t is 0 or 1; where t is 0 means that the binary bridge base E 3 It does not exist; u is 0, 1, 2, 3, or 4; where u + t ≤ 4 v is 0, 1, 2, 3, 4 or 5; Where v + t ≤ 5.

4. The compound according to one or more of the preceding claims, characterized in that... The group Ar 2 Groups selected from formulas (Ar2-7) to (Ar2-10) Where the symbol E 1 R 1 It has the same meaning as in claim 1, and wherein a, b, c, and d are either the same or different from 0 or 1; x, z, and g are the same or different from 0, 1, 2, 3, 4, or 5; wherein in equation (Ar2-7) a + b + x ≤ 5 and z + c ≤ 5, in equation (Ar2-8) a + x ≤ 5 and z + c ≤ 5, in equation (Ar2-9) a + b + x ≤ 5 and z + c + d ≤ 5, and in equation (Ar2-10) g + c + d ≤ 5; y is 0, 1, 2 or 3; where in equation (Ar2-7) y + a + b + c ≤ 3, in equation (Ar2-8) y + a + c ≤ 3, and in equation (Ar2-9) y + a + b + c + d ≤ 3; e and f are the same or different from 0, 1, 2, 3 or 4; where e + a + b ≤ 4 and f + a + b + c + d ≤ 4.

5. The compound according to claim 4, characterized in that... a + b ≤ 1 and c + d ≤ 1.

6. The compound according to claim 4 or 5, characterized in that... c = d = 0.

7. The compound according to one or more of the preceding claims, characterized in that... E 1 E 2 and / or E 3 Selected from C(R) in the same or different ways 0 )2, O, S and N(R) 0 ).

8. The compound according to one or more of the preceding claims, characterized in that... R 0 Each occurrence is selected from H, D, F, CN, Si(R) in the same or different manner. 2 3, a straight-chain 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 substituted by one or more groups R 2 Substitution, wherein in each case one or more H atoms may be replaced by F, and an aryl or heteroaryl group having 5 to 40 aromatic ring atoms, wherein in each case the aryl or heteroaryl group may be replaced by one or more groups R. 2 Substitution, in which two adjacent substituents R 0 It can form monocyclic or polycyclic aliphatic or aromatic ring systems, which can be formed by one or more groups R. 2 replace.

9. The compound according to one or more of the preceding claims, characterized in that... The group Ar 2 Groups selected from formulas (Ar2-7-1) to (Ar2-10-1), Where the symbol R 1 It has the same meaning as in claim 1, and x, z, and g are 0, 1, 2, 3, 4, or 5; y is 0, 1, 2, or 3; and e and f are 0, 1, 2, 3 or 4.

10. The compound according to one or more of the preceding claims, characterized in that... Ar L Selected from aromatic or heteroaromatic ring systems having 5 to 14 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may in each case be further divided by one or more R groups. 2 replace.

11. The compound according to one or more of the preceding claims, characterized in that... R, R 1 Each occurrence thereof is identical or different from H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be represented by one or more groups R. 2 Substitution, wherein one or more non-adjacent CH2 groups may be replaced by O and one or more H atoms may be replaced by F, and an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein in each case the aromatic or heteroaromatic ring system may be replaced by one or more R groups. 2 replace.

12. A method for preparing a compound according to one or more of the preceding claims, characterized in that... A diarylamino group is introduced through a CN coupling reaction between 1-, 3-, or 4-halospirofluorene and a diarylamine or triarylamine.

13. A formulation comprising at least one compound according to one or more of claims 1 to 11 and at least one solvent.

14. Use of the compound according to one or more of claims 1 to 11 in electronic devices, particularly in organic electroluminescent devices.

15. An electronic device comprising at least one compound according to one or more of claims 1 to 11, wherein the electronic device is preferably selected from organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitized organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, luminescent electrochemical cells, organic laser diodes, and organic plasma emitting devices.

16. The electronic device according to claim 15, wherein the electronic device is an organic electroluminescent device, characterized in that... The compounds according to one or more of claims 1 to 11 are used as hole transport materials in hole transport or hole injection or exciton blocking or electron blocking layers, or as matrix materials for fluorescent or phosphorescent emitters.

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