indenoazanaphthalene

Abstract

The present invention relates to indenonaphthazenes, in particular the use in electronic devices. The present invention also relates to a process for the manufacture of indenonaphthazenes according to the invention, and to electronic devices comprising the same.

Description

[0001] This invention describes the use of indozanaphthalene, particularly in electronic devices. The invention also relates to a method for preparing the compounds of this invention and electronic devices comprising these compounds.

[0002] The structures of organic light-emitting diodes (OLEDs) using organic semiconductors as functional materials are described, for example, in US4539507, US 5151629, EP 0676461, WO 98 / 27136, JP 2007-161934 A, and JP 2008-010649 A. The luminescent materials used are typically organometallic complexes exhibiting phosphorescence. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can increase energy efficiency and power efficiency by up to four times. Generally, improvements in OLEDs, especially phosphorescent OLEDs, are still needed, for example, in terms of efficiency, operating voltage, and lifetime.

[0003] The performance of organic electroluminescent devices is determined not only by the light emitter used. In particular, other materials used are also crucial, such as host and matrix materials, hole-blocking materials, electron transport materials, and electron or exciton-blocking materials. Improvements in these materials can lead to significant improvements in electroluminescent devices.

[0004] According to existing technology, aromatic or heteroaromatic compounds, such as triarylamine derivatives or carbazole derivatives, are commonly used as matrix materials for phosphorescent compounds and as hole transport materials. In addition, triazine derivatives or pyrimidine derivatives are also used as matrix materials and electron transport materials.

[0005] Generally speaking, improvements are still needed in the case of these materials, such as when they are used as matrix materials, especially in terms of device lifespan, efficiency, operating voltage, and color purity.

[0006] Therefore, one object of the present invention is to provide compounds suitable for organic electronic devices, especially organic electroluminescent devices, and to achieve good device performance when used in such devices, as well as to provide corresponding electronic devices.

[0007] More specifically, the problem addressed by this invention is to provide compounds that result in long lifetimes, good efficiency, and low operating voltages. In particular, the properties of the matrix material also have a significant impact on the lifetime and efficiency of organic electroluminescent devices.

[0008] Another problem addressed by this invention can be seen as providing compounds suitable for phosphorescent or fluorescent OLEDs, particularly compounds as matrix materials. A specific problem addressed by this invention is providing matrix materials suitable for red and green phosphorescent OLEDs, and also applicable to blue phosphorescent OLEDs.

[0009] Furthermore, the compounds, especially when used as matrix materials, hole-conducting materials or electron-transmitting materials in organic electroluminescent devices, will result in devices with excellent color purity.

[0010] Furthermore, the compound should be easily processed, and in particular, exhibit good solubility and film-forming properties. For example, the compound should exhibit improved oxidative stability and an improved glass transition temperature.

[0011] Another issue could be the availability of electronic devices with excellent performance at a very low cost and with constant quality.

[0012] Furthermore, the electronic device should be usable or adaptable for a variety of purposes. More specifically, the performance of the electronic device should be maintained over a wide temperature range.

[0013] Surprisingly, certain compounds, detailed below, solve these problems. The use of these compounds results in organic electronic devices, particularly organic electroluminescent devices, exhibiting excellent performance, especially in terms of lifetime, color purity, efficiency, and operating voltage. Therefore, the present invention provides electronic devices, particularly organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.

[0014] Therefore, the present invention provides a compound comprising at least one structure of formula (Ia) and / or (Ib), preferably a compound of formula (Ia) and / or (Ib):

[0015]

[0016] The symbols used are as follows:

[0017] X may be the same or different in each case and is either N or CR, with CR being preferred;

[0018] X a The same or different in each case and whether it is N or CR a CR is preferred a ;

[0019] R a The same or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar) a )2, N(R)2, C(=O)Ar a C(=O)R 2 , P(=O)(Ar a )2, P(Ar a )2, B(Ar a )2, B(OR)2, Si(Ar a)3, Si(R)3, Ge(R)3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R groups, wherein one or more non-adjacent CH2 groups may be -RC=CR-, -C≡C-, Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, -O-, -Se-, -S-, C=Se, -C(=O)O-, -C(= O)NR-, C=NR, NR, P(=O)(R), SO or SO2 are substituted, wherein one or more hydrogen atoms may be substituted by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, or an aralkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, or a combination of these systems; wherein two or more preferably adjacent R groups are substituted by one or more R groups. a The groups can form cyclic systems with each other or with the R group;

[0020] Ar a In each case, they may be the same or different and are aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms that can be substituted by one or more preferred non-aromatic R groups; simultaneously, two Ar atoms bonded to the same silicon, nitrogen, phosphorus, or boron atom. a Groups can also be linked together via bridging groups through single bonds or bridging groups selected from B(R), C(R)2, Si(R)2, Ge(R)2, C=O, C=NR, C=C(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R;

[0021] R is the same or different in each case and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R) 1 )2, C(=O)Ar, C(=O)R 1 ,P(=O)(Ar)2,P(Ar)2,B(Ar)2,B(OR 1 )2, Si(Ar)3, Si(R) 1 )3,Ge(R) 1 )3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be generated by one or more R2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by –R 1 C = CR 1 -、-C≡C-、Si(R 1 )2、Ge(R 1 )2、Sn(R 1 )2. C=O, C=S, C=Se, -C(=O)O-, -C(=O)NR 1 -、C=NR 1 NR 1 P(=O)(R) 1 ), -O-, -S-, -Se-, SO or SO2, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R 1 Group substitution, or having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 1 A group-substituted aryloxy or heteroaryloxy group, or a group having 5 to 60 aromatic ring atoms and being substituted with one or more R groups. 1 The substituted aralkyl or heteroaralkyl groups, or combinations thereof; at the same time, two or more preferably adjacent R groups may form a cyclic system together;

[0022] Ar may be the same or different in each case and is a ring of 5 to 30 aromatic atoms and may be one or more preferred non-aromatic R. 1 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two Ar groups bonded to the same silicon, nitrogen, phosphorus, or boron atom can also be connected via a bridging group through a single bond or selected from B(R) 1 ), C(R 1 )2、Si(R 1 )2、Ge(R 1 2. C=O, C=NR 1 C = C(R) 1 )2, O, S, Se, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 The bridge foundations are connected together;

[0023] R 1 The same or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar) 1 )2,N(R 2 )2, C(=O)Ar 1 C(=O)R 2 , P(=O)(Ar1 )2, P(Ar 1 )2, B(Ar 1 )2, B(OR 2 )2, Si(Ar 1 )3,Si(R 2 )3,Ge(R) 2 )3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can 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, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 ), -O-, -S-, -Se-, SO or SO2, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be replaced by one or more R 2 Group substitution, or having 5 to 40 aromatic ring atoms and being substituted by one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group, or a group having 5 to 40 aromatic ring atoms and being substituted with one or more R groups. 2 Group-substituted aralkyl or heteroaralkyl groups, or combinations thereof; wherein, two or more preferably adjacent R groups 1 Groups can form ring systems together;

[0024] Ar 1 In each case, they may be the same or different and are of 5 to 30 aromatic ring atoms and may be one or more preferred non-aromatic R 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two Ar atoms bonded to the same silicon, nitrogen, phosphorus, or boron atom. 1 The group can also be connected via a bridging group through a single bond or selected from B(R) 2 ), C(R 2 )2、Si(R 2 )2、Ge(R 2 2. C=O, C=NR 2 C = C(R)2 )2, O, S, Se, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 The bridge bases are connected to each other;

[0025] R 2 The same or different in each case and are H, D, F, Cl, Br, I, CN, B (OR) 3 )2, NO2, C(=O)R 3 CR 3 =C(R) 3 )2, C(=O)OR 3 C(=O)N(R) 3 )2,Si(R 3 )3,Ge(R) 3 )3, P(R) 3 )2, B(R) 3 )2,N(R 3 )2, NO2, P(=O)(R 3 )2, OSO2R 3 OR 3 S(=O)R 3 S(=O)2R 3 A straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R 3 Group substitution, wherein one or more non-adjacent CH2 groups can 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=NR 3 -C(=O)O-, -C(=O)NR 3 -、NR 3 P(=O)(R) 3 The hydrogen atoms can be replaced by -O-, -S-, -Se-, SO or SO2, wherein one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO2, or have 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R 3 Aromatic or heteroaromatic ring systems with substituted groups, or having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 3 A group-substituted aryloxy or heteroaryloxy group, or a combination of these systems; simultaneously, two or more preferably adjacent substituents R 2They can form a ring system with each other;

[0026] R 3 In each case, the same or different aliphatic hydrocarbon groups selected from H, D, F, CN, having 1 to 20 carbon atoms, and aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, or CN and may be replaced by one or more alkyl groups, each having 1 to 4 carbon atoms; and two or more preferably adjacent R 3 Substituents can form ring systems with each other.

[0027] In the context of this invention, adjacent carbon atoms are carbon atoms that are directly bonded to each other. Furthermore, the term "adjacent group" in the definition of a group means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply, accordingly, particularly to the terms "adjacent group" and "adjacent substituent".

[0028] In the context of this specification, the phrase "two or more groups can form a ring together" should be understood to specifically mean that two groups are connected to each other by chemical bonds by the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0029]

[0030] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group binds to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0031]

[0032] In the context of this invention, a fused aryl group, fused aromatic ring system, or fused heteroaromatic ring system is a group in which two or more aromatic groups are fused together along a common edge, i.e., ring-enhanced, such that, for example, two carbon atoms belong to at least two aromatic or heteroaromatic rings, as in, for example, naphthalene. In contrast, for example, fluorene is not a fused aryl group in the context of this invention because the two aromatic groups in fluorene do not share a common edge. The corresponding definition applies to heteroaromatic groups and fused ring systems that may, but do not necessarily, also contain heteroatoms.

[0033] In the context of this invention, an aryl group contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms; a heteroaryl group contains 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. Here, aryl group or heteroaryl group is understood to mean a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0034] In the context of this invention, aromatic ring systems contain 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms. Heteroaromatic ring systems in the context of this invention contain 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, aromatic or heteroaromatic ring systems should be understood to mean systems that do not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups are also linked by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon, nitrogen, or oxygen atoms, or carbonyl groups. For example, systems in the context of this invention, such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, and piracene, should therefore be considered aromatic ring systems in the context of this invention. Systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl groups or by silyl groups should also be considered aromatic ring systems. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, should also be considered aromatic ring systems or heteroaromatic ring systems.

[0035] In the context of this invention, cyclic alkyl, alkoxy, or thioalkoxy groups are understood to mean monocyclic, bicyclic, or polycyclic groups.

[0036] In the context of this invention, individual hydrogen atoms or CH2 groups may also be replaced by the C1 to C2 groups described above. 20Alkyl groups should be understood to mean, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl Cycloheptayl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl 1,1-dimethyl-n-octyl-1-yl, 1,1-dimethyl-n-dodecane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexyl-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octyl-1-yl, 1,1-diethyl-n- Dec-1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)cyclohexyl-1-yl, 1-(n-butyl)cyclohexyl-1-yl, 1-(n-hexyl)cyclohexyl-1-yl, 1-(n-octyl)cyclohexyl-1-yl and 1-(n-decyl)cyclohexyl-1-yl groups. Alkenyl groups should be understood to mean, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Alkynyl groups should be understood to mean, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl or octynyl. C1 to C 40 The alkoxy group should be understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0037] An aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, aromatic ring atoms, and in each case potentially substituted by the aforementioned groups and linked to the aromatic or heteroaromatic system via any desired position, should be understood to mean, for example, groups derived from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, leucine, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, terphenylidene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene. cis or trans indofluorene, cis or trans monobenzoindofluorene, cis or trans dibenzoindofluorene, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthridine 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, indoleazine, and benzothiadiazole.

[0038] The preferred case is R. a At least one, preferably at least two, of the groups are aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms and in each case being substituted by one or more R groups.

[0039] In another configuration, the possible case is R. a At least one, preferably at least two, of the groups are straight-chain alkyl, alkoxy, or thioalkoxy groups having 1 to 40 carbon atoms, or branched or cyclic alkyl, alkoxy, or thioalkoxy groups having 3 to 40 carbon atoms, or alkenyl or alkynyl groups having 2 to 40 carbon atoms, each of which may be substituted by one or more R groups. Preferably, two methyl groups are present on the fluorene-bridged group, such that adjacent R groups in formula (Ia) or (Ib) a Each group represents a methyl group.

[0040] In a preferred embodiment, the compounds of the present invention may contain at least one structure of formula (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15) and / or (II-16), wherein the compounds may preferably be represented by a structure of formula (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15) and / or (II-16):

[0041]

[0042]

[0043]

[0044] The symbols R and X used herein have the definitions given above, especially for formulas (Ia) and / or (Ib), p is 0 or 1, Y is B(R), C(R)2, Si(R)2, Ge(R)2, C=O, C=NR, C=C(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R, preferably B(R), C(R)2, Si(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R, more preferably O or N(R), wherein when p=0, there is a bond between the aromatic or heteroaromatic rings shown. Here, the structures of (II-5), (II-6), (II-7), (II-8), (II-13), (II-14), (II-15) and (II-16) are preferred, and the structures of (II-13), (II-14), (II-15) and (II-16) are particularly preferred.

[0045] Furthermore, the structures of particularly preferred formulas (II-9) and (II-13) (preferred compounds) are:

[0046]

[0047] The symbols R and X used may have the definitions given above, especially for formulas (Ia) and / or (Ib), where p is 0 or 1, and Y is B(R), C(R)2, Si(R)2, Ge(R)2, C=O, C=NR, C=C(R)2, O, S, Se, S=O, SO2, N(R), P(R), and P(=O)R, preferably B(R), C(R)2, Si(R)2, O, S, Se, S=O, SO2, N(R), P(R), and P(=O)R, more preferably O or N(R), wherein when p=0, there is a bond between the aromatic or heteroaromatic rings shown. With respect to formulas (II-9) and (II-13), the structure with p=0 is preferred (preferably the compound), thus forming a bond between the two rings.

[0048] In a preferred embodiment, in formulas (Ia), (Ib) and / or (II-1) to (II-16), no more than two X groups in each ring are N; preferably at least one, more preferably at least two, of the X groups in each ring are selected from CH and CD.

[0049] Preferably, in formulas (Ia), (Ib) and / or (II-1) to (II-16), no more than four, preferably no more than two, X groups are N; more preferably, all X groups are CR, wherein at most four, more preferably at most three, and especially preferably at most two of the CR groups represented by X are not CH groups.

[0050] Alternatively, the compounds of the present invention may comprise at least one structure of formula (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), and / or (III-16), wherein the compounds may preferably be represented by a structure of formula (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), and / or (III-16).

[0051]

[0052]

[0053] Wherein R has the definition given above, especially with respect to formulas (Ia) and / or (Ib), the symbols Y and p have the definition given above, especially with respect to formulas (II-1) to (II-16), l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is the same or different in each case and is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. Herein are preferred structures of formulas (III-5), (III-6), (III-8), (III-13), (III-14) and (III-16).

[0054] Furthermore, the structures of particularly preferred formulas (III-9) and (III-13) (preferred compounds) are:

[0055]

[0056] Wherein R has the definition given above, especially with respect to formulas (Ia) and / or (Ib), the symbols Y and p have the definitions given above, especially with respect to formulas (II-1) to (II-16), l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is the same or different in each case and is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. With respect to formulas (III-9) and (III-13), the structure p=0 is preferred (preferred compounds), thus forming a bond between the two rings.

[0057] Preferably, in the structures of formulas (III-1) to (III-16), and in preferred compounds, the sum of the designations l and m does not exceed 6, more preferably not more than 4, and even more preferably not more than 2.

[0058] Alternatively, the compound may contain a hole-transporting group, wherein preferably, the structure / compound of formula (Ia), (Ib), (II-1) to (II-16) and / or (III-1) to (III-16) is preferred. a At least one of the groups and / or R groups contains a hole transport group, and is preferably a hole transport group.

[0059] Hole transport groups are known in the art, and they preferably include triarylamine or carbazole groups.

[0060] In another embodiment, the compound that can be used to produce the functional layer of an electronic device may contain a group containing an electron transport group.

[0061] Alternatively, the compound may contain a group with an electron transport group, wherein in the structures / compounds of formulas (Ia), (Ib), (II-1) to (II-16) and / or (III-1) to (III-16), R is preferred. a At least one of the groups or R groups contains a group containing an electron transport group, and preferably a group containing an electron transport group.

[0062] Electron transport groups are well known in the technical field and enhance the ability of compounds to transport and / or conduct electrons.

[0063] Furthermore, compounds used to fabricate functional layers for electronic devices exhibit surprising advantages, comprising at least one structure selected from: pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole, and / or benzimidazole, with pyrimidine, triazine, and quinazoline being particularly preferred. These structures generally enhance the compound's ability to transport and / or conduct electrons.

[0064] In a preferred embodiment of the invention, the group containing the electron transport group may be a group that can be represented by formula (QL).

[0065]

[0066] Where L 1 It represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and can be expressed by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups, where Q is an electron-transporting group, and R... 1 With the definitions given above, especially for equations (Ia) and / or (Ib), the dashed key marks the connection position.

[0067] Preferably, L 1 The group can be with the Q group and with the L group of formula (QL). 1 The atoms bonded by the functional groups (preferably carbon or nitrogen atoms) form complete conjugation. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, complete conjugation of the aromatic or heteroaromatic system is achieved. Another bond between the aforementioned conjugated groups, such as via a sulfur, nitrogen, or oxygen atom or a carbonyl group, does not negatively affect the conjugation. In the case of the fluorene system, the two aromatic rings are directly bonded, with sp at position 9... 3 Hybridized carbon atoms do prevent the fusion of these rings, but conjugation is feasible because of the sp at position 9. 3 The hybrid carbon atom is not necessarily located between the atoms through which the electron-transporting Q group and the (QL) group bond with other structural elements of the compound of the present invention. In contrast, in the case of the second spirodifluorene structure, if the Q group and the L of (QL) 1Complete conjugation can be achieved when the bonds between the aromatic or heteroaromatic groups bonded by the group are via the same phenyl group in the spirodifluorene structure or via phenyl groups in the spirodifluorene structure that are directly bonded to each other and are in the same plane. If the Q group and the L group of formula (QL) 1 The bonds between the aromatic or heteroaromatic groups bonded by the group are transmitted via sp at the 9th position. 3 In the second spirodifluorene structure with hybrid carbon atom bonding, different phenyl bonds are bonded, thus interrupting conjugation.

[0068] In another preferred embodiment of the invention, L 1 It is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably having 6 to 12 carbon atoms and being soluble in one or more R atoms. 1 Aromatic ring systems with substituted but preferably unsubstituted groups, wherein R 1 It can have the definitions given above, especially for equations (Ia) and / or (Ib). More preferably, L 1 These are aromatic ring systems having 6 to 10 aromatic ring atoms or heteroaromatic ring systems having 6 to 13 heteroaromatic ring atoms, each of which can be generated by one or more R... 2 Group substitution, but preferably unsubstituted, wherein R 2 It can have the definitions given above, especially for equations (Ia) and / or (Ib).

[0069] More preferably, especially the symbol L shown in formula (QL) 1 In each case, the same or different, and is a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaryl group of the aromatic or heteroaryl ring system is directly (i.e., via the atoms of the aromatic or heteroaryl group) bonded to the corresponding atoms of another group.

[0070] In addition, the case where L is shown in equation (QL) is also possible. 1 The group comprises an aromatic ring system having no more than two fused aromatic and / or heteroaromatic 6-membered rings, and preferably does not contain any fused aromatic or heteroaromatic ring systems. Therefore, the naphthyl structure is preferred over the anthracene structure. Furthermore, fluorenyl, spirodifluorenyl, dibenzofuranyl, and / or dibenzothiopheneyl structures are preferred over the naphthyl structure.

[0071] A particularly preferred structure is one that does not contain fusion, such as phenyl, biphenyl, terphenyl, and / or tetraphenyl structures.

[0072] Suitable aromatic or heteroaromatic ring systems L 1Examples are selected from o-phenylene, m-phenylene or p-phenylene, o-biphenylene, m-biphenylene or p-biphenylene, terphenylene (especially branched terphenylene), tetraphenylene (especially branched tetraphenylene), fluorene, spirodifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which can be generated by one or more R 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0073] Furthermore, the case where L is shown in particular formula (QL) is also possible. 1 The group has no more than one nitrogen atom, preferably no more than two heteroatoms, especially preferably no more than one heteroatom, and more preferably no heteroatoms.

[0074] Preferably, the Q group or electron transport group shown in formula (QL) can be selected from the structures of formulas (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10):

[0075]

[0076]

[0077] The dashed key marks the connection position.

[0078] Q' is the same or different in every case and is CR 1 Or N;

[0079] Q" is NR 1 , O or S;

[0080] At least one of Q' is N;

[0081] R 1 As defined above, especially in equations (Ia) or (Ib).

[0082] Furthermore, the Q group or electron transport group shown in formula (QL) is preferably selected from the structures of formulas (Q-11), (Q-12), (Q-13), (Q-14) and / or (Q-15):

[0083]

[0084]

[0085] Where the symbol R 1 With the definitions given above, especially for equations (Ia) and / or (Ib), X 1 For N or CR 1 The dashed key marks the connection position, where X 1Nitrogen atoms are preferred.

[0086] In another embodiment, in particular, the Q group or electron transport group shown in formula (QL) may be selected from the structures of formulas (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and / or (Q-22):

[0087]

[0088]

[0089] Where the symbol R 1 With the definitions detailed above, especially for formulas (Ia) and / or (Ib), the dashed key marks the connection position, m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0, 1 or 2, and o is 0, 1 or 2, preferably 1 or 2. Here, the structures of formulas (Q-16), (Q-17), (Q-18) and (Q-19) are preferred.

[0090] In another embodiment, in particular, the Q group or electron transport group shown in formula (QL) may be selected from the structures of formula (Q-23), (Q-24) and / or (Q-25):

[0091]

[0092] Where the symbol R 1 With the definitions described above, especially for formulas (Ia) and / or (Ib), dashed keys mark the connection positions.

[0093] In another embodiment, in particular, the Q group or electron transport group shown in formula (QL) may be selected from the structures of formulas (Q-26), (Q-27), (Q-28), (Q-29) and / or (Q-30):

[0094]

[0095] The symbol Ar 1 and R 1 With the definitions given above, especially for equations (Ia) and / or (Ib), X 1 For N or CR 1 The dashed key marks the connection position. Preferably, in the structures of formulas (Q-26), (Q-27), and (Q-28), exactly one X 1 It is a nitrogen atom.

[0096] Preferably, the Q group or electron transport group shown in formula (QL) can be selected from the structures of formulas (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and / or (Q-44):

[0097]

[0098]

[0099] The symbol Ar 1 and R 1 With the definitions described above, especially for formulas (Ia) and / or (Ib), the dashed key marks the connection position, m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0 or 1, l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0100] In another preferred embodiment of the invention, Ar 1 In each case, the same or different, and being an aromatic or heteroaromatic ring system (preferably aryl or heteroaryl group) having 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably an aromatic ring system (preferably aryl group) having 6 to 12 aromatic ring atoms or a heteroaromatic ring system (preferably heteroaryl group) having 5 to 13 aromatic ring atoms, each of which may be derived from one or more R 2 Group substitution, but preferably unsubstituted, wherein R 2 It may have the definitions detailed above, especially in equations (Ia) and / or (Ib).

[0101] Preferably, the symbol Ar 1 It is an aryl or heteroaryl group that causes the aromatic or heteroaryl group of the aromatic or heteroaryl ring system to be directly (i.e., via the atom of the aromatic or heteroaryl group) bonded to the corresponding atom of another group, such as the carbon or nitrogen atom of the (H-1) to (H-26) or (Q-26) to (Q-44) groups shown above.

[0102] Advantageously, Ar in formulas (H-1) to (H-26) or (Q-26) to (Q-44) 1 It has 6 to 12 aromatic ring atoms and can be converted by one or more R 2 Aromatic ring systems with substituted but preferably unsubstituted groups, wherein R 2 It may have the definitions detailed above, especially for formulas (Ia) and / or (Ib).

[0103] Preferably, R in formulas (H-1) to (H-26) or (Q-1) to (Q-44) 1 or R 2 The group does not interact with aryl groups or heteroaryl groups. 1 Ar 2 Ar 3 and / or Ar 4 In and R 1 or R 2 Group-bonded ring atoms form fused ring systems. This includes those that can bond with R. 1 or R 2 Possible substituents R for group bonding 2 R 3 A fused ring system is formed.

[0104] These electron transport groups can achieve unexpected results.

[0105] The other possibilities are Ar, Ar 1 Ar 2 Ar 3 and / or Ar 4 The group is selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiopheneyl, 2-dibenzothiopheneyl, 3-dibenzothiopheneyl or 4-dibenzothiopheneyl, pyrene, triazinyl, imidazolyl, benzimidazolyl, benzo[] Azolyl, benzothiazolyl, 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, indenzocarbazole, 1-naphthyl or 2-naphthyl, anthracene (preferably 9-anthrayl), phenanthryl and / or biphenylidene, each of which can be substituted with one or more R 1 and / or R 2 The group may be substituted, but preferably unsubstituted, with phenyl, spirofluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, and biphenylidene groups being particularly preferred.

[0106] Furthermore, it is permissible for the substituent R in the heteroaromatic ring systems of formulas (Ia), (Ib), (II-1) to (II-16) and / or (III-1) to (III-16) not to form a fused aromatic ring system or a fused heteroaromatic ring system with the ring atoms of the heteroaromatic ring system, preferably any fused ring system. This includes possible R groups that can bond to the R group. 1 R 2 R 3The substituents form a fused ring system. Preferably, the substituent R in formulas (Ia), (Ib), (II-1) to (II-16) and / or (III-1) to (III-16) does not form any ring system with the ring atoms of an aromatic or heteroaromatic ring system. This includes possible R groups that can bond to the R group. 1 R 2 R 3 Substituents form ring systems.

[0107] Especially when it can be selected from R, R 1 R 2 , R and / or R 3 When two groups form a ring system with each other, the ring system can be monocyclic or polycyclic aliphatic, heterocyclic, aromatic, or heteroaromatic. In this case, the groups forming the ring system together can be adjacent, meaning that these groups are bonded to the same carbon atom or to carbon atoms directly bonded to each other, or they can be further separated from each other.

[0108] In a preferred embodiment, the compounds of the present invention are defined by the structures of formulas (Ia), (Ib), (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15), (II-16), (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), or (III-16), or by preferred embodiments of these structures, which will be described later. Therefore, compounds having the structures of formulas (Ia), (Ib), (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15), (II-16), (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), or (III-16) are preferred, or compounds of one of the preferred embodiments of these structures, which will be described later. Preferably, it includes formulas (Ia), (Ib), (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11 ), (II-12), (II-13), (II-14), (II-15), (II-16), (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III- Compounds with structures of (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), or (III-16), or compounds of preferred embodiments including these structures, have a molecular weight of not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, especially preferably not more than 2000 g / mol, and most preferably not more than 1200 g / mol.

[0109] Furthermore, the preferred compounds of the present invention are characterized in that they are sublimable. The molar mass of these compounds is typically less than about 1200 g / mol.

[0110] In another preferred embodiment, the R group in the structure shown above may be selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiopheneyl, 2-dibenzothiopheneyl, 3-dibenzothiopheneyl or 4-dibenzothiopheneyl, pyrene, triazine, imidazolyl, benzimidazolyl, benzo[a] Azolyl, benzothiazolyl, 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, 1-naphthyl or 2-naphthyl, anthracene (preferably 9-anthrayl), phenanthryl and / or biphenylidene, except for fluorenyl and carbazole, each of which may be atomized by one or more R or R 1 The groups are substituted, but preferably unsubstituted, with spirodifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, and biphenylide groups being particularly preferred.

[0111] When X is CR, or when aromatic and / or heteroaromatic groups are substituted by substituents R, these substituents R are preferably selected from H, D, F, CN, N(Ar)2, C(=O)Ar, P(=O)(Ar)2, straight-chain alkyl or alkoxy groups having 1 to 10 carbon atoms, or branched or cyclic alkyl or alkoxy groups having 3 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, each of which can be replaced by one or more R. 1 Group substitution, wherein one or more non-adjacent CH2 groups may be replaced by O and one or more hydrogen atoms may be replaced by D or F, having 5 to 24 aromatic ring atoms and in each case being one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted but preferably unsubstituted groups, or having 5 to 25 aromatic ring atoms and being substituted by one or more R groups. 1 The alkyl or heteroaryl group is substituted with a substituent; simultaneously, two substituents R bonded to the same carbon atom or to adjacent carbon atoms may optionally form a group that can be substituted by one or more Rs. 1 Monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring systems with substituted groups; wherein the Ar group is the same or different in each case and represents having 5 to 40 aromatic ring atoms and can be replaced by one or more R groups in each case. 1Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 40 aromatic ring atoms and substituted with one or more R groups. 1 A group-substituted aryloxy group, or having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 1 A group-substituted aralkyl group, wherein two or more preferably adjacent substituents R 1 The ring system can optionally form a monocyclic or polycyclic aliphatic, heterocyclic, aromatic, or heteroaromatic ring system, preferably a monocyclic or polycyclic aliphatic ring system, which can be formed by one or more R... 2 Group substitution, where the symbol R 2 It can have the definitions given above, especially for formulas (Ia) and / or (Ib). Preferably, Ar is the same or different in each case, and is having 5 to 24, preferably 5 to 12, aromatic ring atoms, and in each case can be one or more R atoms. 1 The substituted group is preferably an unsubstituted aryl or heteroaryl group.

[0112] Suitable Ar groups are selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl or 4-dibenzothiophenyl, and 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, each of which can be substituted with one or more R groups. 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0113] More preferably, these substituents R are selected from H, D, F, CN, N(Ar)2, and are straight-chain alkyl groups having 1 to 8 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms; or branched or cyclic alkyl groups having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms; or alkenyl groups having 2 to 8 carbon atoms, preferably 2, 3, or 4 carbon atoms. Each of them can be replaced by one or more R. 1 The group is substituted but preferably unsubstituted, or has 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and in each case may be substituted by one or more non-aromatic R groups. 1 The group is substituted, but preferably unsubstituted, an aromatic or heteroaromatic ring system; meanwhile, the two substituents R bonded to the same carbon atom or to adjacent carbon atoms can optionally form a ring system that can be substituted by one or more Rs. 1The aliphatic ring system is a monocyclic or polycyclic ring system that is substituted, but preferably unsubstituted, wherein Ar can have the definition described above.

[0114] Most preferably, the substituent R is selected from H and aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which can be replaced by one or more non-aromatic Rs. 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0115] In a preferred configuration, the possible cases are R and / or R in equations (Ia), (Ib), (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7), (II-8), (II-9), (II-10), (II-11), (II-12), (II-13), (II-14), (II-15), (II-16), (III-1), (III-2), (III-3), (III-4), (III-5), (III-6), (III-7), (III-8), (III-9), (III-10), (III-11), (III-12), (III-13), (III-14), (III-15), or (III-16). a At least one of the groups can be derived from formula L 1 -Z represents a group, where L 1 It represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and can be expressed by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups, Z represents R 1 Ar or Z a or Z b The groups, wherein the symbols Ar and R 1 With the definitions given above, especially for equations (Ia) and / or (Ib), Z a or Z b for

[0116]

[0117] Where W is the same or different in each case and has 5 to 30 aromatic ring atoms and can be generated by one or more R. 1 Aromatic or heteroaromatic ring systems substituted with groups, nitrogen atoms, boron atoms, phosphorus atoms, or phosphine oxide groups, with dashed lines indicating the linkage positions, and the symbols Ar and R. 1 It has the definitions given above, especially for formulas (Ia) and / or (Ib).

[0118] In a preferred embodiment, the compounds of the present invention comprise at least one of the formulas (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-9), (IV-10), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21), (IV-22), (IV-23), and / or (IV-24). The structure, wherein the compound may preferably be represented by the structure of formula (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-9), (IV-10), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21), (IV-22), (IV-23) and / or (IV-24):

[0119]

[0120]

[0121]

[0122]

[0123] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols used are R, Y, p, and L. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0124] Furthermore, the structures of particularly preferred formulas (IV-9), (IV-13), (IV-17), and (IV-21) (preferred compounds) are as follows:

[0125]

[0126] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols used are R, Y, p, and L. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1-Z) gives the definition. For formulas (IV-9), (IV-13), (IV-17) and (IV-21), p = 0 is preferred, thus forming a structure with a bond between the two rings (preferred compounds).

[0127] In another embodiment, the compounds of the present invention may comprise at least one of the formulas (V-1), (V-2), (V-3), (V-4), (V-5), (V-6), (V-7), (V-8), (V-9), (V-10), (V-11), (V-12), (V-13), (V-14), (V-15), (V-16), (V-17), (V-18), (V-19), (V-20), (V-21), (V-22), (V-23), (V-24), (V-25), (V-26), (V-27), (V-28), (V-29), (V-30), (V-31) and / or (V- 32), wherein the compound may preferably be represented by the structure of formula (V-1), (V-2), (V-3), (V-4), (V-5), (V-6), (V-7), (V-8), (V-9), (V-10), (V-11), (V-12), (V-13), (V-14), (V-15), (V-16), (V-17), (V-18), (V-19), (V-20), (V-21), (V-22), (V-23), (V-24), (V-25), (V-26), (V-27), (V-28), (V-29), (V-30), (V-31) and / or (V-32):

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols used are R, Y, p, and L. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0134] Furthermore, the structures of particularly preferred formulas (V-17), (V-21), (V-25), and (V-29) (preferred compounds) are as follows:

[0135]

[0136] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols used are R, Y, p, and L. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 -Z) gives the definition. For formulas (V-17), (V-21), (V-25) and (V-29), p = 0 is preferred, thus forming a structure with a bond between the two rings (preferred compounds).

[0137] In a preferred embodiment, the compounds of the present invention may comprise at least one structure of formula (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-7), and / or (VI-8), wherein the compounds may preferably be represented by structures of formula (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-7), and / or (VI-8):

[0138]

[0139]

[0140] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols used are R, Y, p, and L. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 -Z) defines it as follows. Here, the structures (VI-1), (VI-2), (VI-4), (VI-5), (VI-6), and (VI-8) are preferred (preferred compounds), and the structures (VI-5), (VI-6), and (VI-8) are particularly preferred (preferred compounds). The structure (VI-5) is particularly preferred, preferably with p=0, thus forming a single bond between the two rings (preferred compound).

[0141] The Y group, especially in the structures of formulas (II-1) to (II-16), (III-1) to (III-16), (IV-1) to (IV-24), (V-1) to (V-32) and / or (VI-1) to (VI-8), is preferably O or NR.

[0142] More preferably, the compounds of the present invention may comprise at least one structure of formula (VII-1), (VII-2), (VII-3), (VII-4), (VII-5), (VII-6), (VII-7) and / or (VII-8), wherein the compounds may preferably be represented by structures of formula (VII-1), (VII-2), (VII-3), (VII-4), (VII-5), (VII-6), (VII-7) and / or (VII-8):

[0143]

[0144]

[0145] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols R and L are used. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0146] In another preferred embodiment, the compounds of the present invention may comprise at least one structure of formula (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII-5), (VIII-6), (VIII-7), (VIII-8), (VIII-9), and / or (VIII-10), wherein the compounds may preferably be represented by a structure of formula (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII-5), (VIII-6), (VIII-7), (VIII-8), (VIII-9), and / or (VIII-10).

[0147]

[0148]

[0149] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols R and L are used. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0150] Alternatively, in a preferred embodiment, the compounds of the present invention comprise at least one structure of formula (IX-1), (IX-2), (IX-3), (IX-4), (IX-5), (IX-6), (IX-7), and / or (IX-8), wherein the compounds may preferably be represented by structures of formula (IX-1), (IX-2), (IX-3), (IX-4), (IX-5), (IX-6), (IX-7), and / or (IX-8).

[0151]

[0152]

[0153] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols R and L are used. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0154] Alternatively, the compounds of the present invention may comprise at least one structure of formula (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7), and / or (X-8), wherein the compounds may preferably be represented by structures of formula (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7), and / or (X-8).

[0155]

[0156] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols R and L are used. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0157] Alternatively, in a preferred embodiment, the compounds of the present invention comprise at least one structure of formula (XI-1), (XI-2), (XI-3), (XI-4), (XI-5), (XI-6), (XI-7), (XI-8), (XI-9), and / or (XI-10), wherein the compounds may preferably be represented by a structure of formula (XI-1), (XI-2), (XI-3), (XI-4), (XI-5), (XI-6), (XI-7), (XI-8), (XI-9), and / or (XI-10).

[0158]

[0159]

[0160] Where the symbol X represents N, CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, and the symbols R and L are used. 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 The definition given by -Z).

[0161] In a preferred embodiment, in formulas (Ia), (Ib), (II-1) to (II-16), (III-1) to (III-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8) and / or (XI-1) to (XI-10), no more than two X groups in each ring are N; preferably at least one and more preferably at least two X groups in each ring are selected from CH and CD.

[0162] Preferably, in formulas (Ia), (Ib), (II-1) to (II-16), (III-1) to (III-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8) and / or (XI-1) to (XI-10), no more than four, and preferably no more than two, X groups are N; more preferably, all X groups are CR, wherein the CR groups represented by X preferably have no more than four, more preferably no more than three, and especially preferably no more than two that are not CH groups.

[0163] Alternatively, the compounds of the present invention may include at least one of the formulas (XII-1), (XII-2), (XII-3), (XII-4), (XII-5), (XII-6), (XII-7), (XII-8), (XII-9), (XII-10), (XII-11), (XII-12), (XII-13), (XII-14), (XII-15), (XII-16), (XII-17), (XII-18), (XII-19), (XII-20), (XII-21), (XII-22), (XII-23) and / or (XII-24). The structure, wherein the compound may preferably be represented by the structure of formula (XII-1), (XII-2), (XII-3), (XII-4), (XII-5), (XII-6), (XII-7), (XII-8), (XII-9), (XII-10), (XII-11), (XII-12), (XII-13), (XII-14), (XII-15), (XII-16), (XII-17), (XII-18), (XII-19), (XII-20), (XII-21), (XII-22), (XII-23) and / or (XII-24):

[0164]

[0165]

[0166]

[0167] The symbols R, Y, p, and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the designation l is 1, 2, 3, 4, or 5, preferably 0, 1, or 2; the designation m is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2; and the designation n is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1. Compounds having groups of formulas (XII-1) to (XII-9) and (XII-13) to (XII-21) are preferred here.

[0168] Furthermore, the structures of particularly preferred formulas (XII-13), (XII-17), and (XII-21) (preferred compounds) are as follows:

[0169]

[0170] The symbols R, Y, p, and L used in this context 1And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined in -Z), the notation l is 1, 2, 3, 4, or 5, preferably 0, 1, or 2; the notation m is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2; and the notation n is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1. With respect to formulas (XII-13), (XII-17), and (XII-21), p = 0 is preferred, thus forming a structure with a single bond between the two rings (preferred compounds).

[0171] In a preferred embodiment, the compounds of the present invention comprise at least one of the formulas (XIII-1), (XIII-2), (XIII-3), (XIII-4), (XIII-5), (XIII-6), (XIII-7), (XIII-8), (XIII-9), (XIII-10), (XIII-11), (XIII-12), (XIII-13), (XIII-14), (XIII-15), (XIII-16), (XIII-17), (XIII-18), (XIII-19), (XIII-20), (XIII-21), (XIII-22), (XIII-23), (XIII-24), (XIII-25), (XIII-26), (XIII-27), (XIII-28), (XIII-29), (XIII-30), (XIII-31), and / or (XIII-32). The structure, wherein the compound may preferably be represented by the structure of formula (XIII-1), (XIII-2), (XIII-3), (XIII-4), (XIII-5), (XIII-6), (XIII-7), (XIII-8), (XIII-9), (XIII-10), (XIII-11), (XIII-12), (XIII-13), (XIII-14), (XIII-15), (XIII-16), (XIII-17), (XIII-18), (XIII-19), (XIII-20), (XIII-21), (XIII-22), (XIII-23), (XIII-24), (XIII-25), (XIII-26), (XIII-27), (XIII-28), (XIII-29), (XIII-30), (XIII-31) and / or (XIII-32):

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] The symbols R, Y, p, and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0178] Furthermore, the structures of particularly preferred formulas (XIII-13), (XIII-17), (XIII-21), (XIII-25), and (XIII-29) (preferred compounds) are as follows:

[0179]

[0180]

[0181] The symbols R, Y, p, and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined in -Z), the notation l is 1, 2, 3, 4, or 5, preferably 0, 1, or 2; the notation m is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2; and the notation n is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1. Regarding the structures of formulas (XIII-13), (XIII-17), (XIII-21), (XIII-25), and (XIII-29), p = 0 is preferred, thus forming a structure with one bond between the two rings (preferred compounds).

[0182] More preferably, the compounds of the present invention may comprise at least one structure of formula (XIV-1), (XIV-2), (XIV-3), (XIV-4), (XIV-5), (XIV-6), (XIV-7), and / or (XIV-8), wherein the compounds may preferably be represented by structures of formula (XIV-1), (XIV-2), (XIV-3), (XIV-4), (XIV-5), (XIV-6), (XIV-7), and / or (XIV-8):

[0183]

[0184]

[0185] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0186] Alternatively, in a preferred embodiment, the compounds of the present invention comprise at least one structure of formula (XV-1), (XV-2), (XV-3), (XV-4), (XV-5), (XV-6), (XV-7), (XV-8), (XV-9), and / or (XV-10), wherein the compounds may preferably be represented by a structure of formula (XV-1), (XV-2), (XV-3), (XV-4), (XV-5), (XV-6), (XV-7), (XV-8), (XV-9), and / or (XV-10).

[0187]

[0188]

[0189] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0190] In another preferred embodiment, the compounds of the present invention may comprise at least one structure of formula (XVI-1), (XVI-2), (XVI-3), (XVI-4), (XVI-5), (XVI-6), (XVI-7), and / or (XVI-8), wherein the compounds may preferably be represented by structures of formula (XVI-1), (XVI-2), (XVI-3), (XVI-4), (XVI-5), (XVI-6), (XVI-7), and / or (XVI-8).

[0191]

[0192]

[0193] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0194] Alternatively, the compounds of the present invention may comprise at least one structure of formula (XVII-1), (XVII-2), (XVII-3), (XVII-4), (XVII-5), (XVII-6), (XVII-7), and / or (XVII-8), wherein the compounds may preferably be represented by structures of formula (XVII-1), (XVII-2), (XVII-3), (XVII-4), (XVII-5), (XVII-6), (XVII-7), and / or (XVII-8).

[0195]

[0196] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0197] In a preferred embodiment, the compounds of the present invention comprise at least one structure of formula (XVIII-1), (XVIII-2), (XVIII-3), (XVIII-4), (XVIII-5), (XVIII-6), (XVIII-7), (XVIII-8), (XVIII-9), and / or (XVIII-10), wherein the compounds may preferably be represented by a structure of formula (XVIII-1), (XVIII-2), (XVIII-3), (XVIII-4), (XVIII-5), (XVIII-6), (XVIII-7), (XVIII-8), (XVIII-9), and / or (XVIII-10).

[0198]

[0199]

[0200] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0201] In another preferred embodiment, the compounds of the present invention may comprise at least one structure of formula (XIX-1), (XIX-2), (XIX-3), (XIX-4), (XIX-5), (XIX-6), (XIX-7), (XIX-8), (XIX-9), and / or (XIX-10), wherein the compounds may preferably be represented by a structure of formula (XIX-1), (XIX-2), (XIX-3), (XIX-4), (XIX-5), (XIX-6), (XIX-7), (XIX-8), (XIX-9), and / or (XIX-10).

[0202]

[0203]

[0204] The symbols R and L used in this context 1 And Z has the above, especially for formulas (Ia), (Ib), (II-1) to (II-16) and / or (L) 1 As defined by -Z), the numeral l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2; the numeral m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; and the numeral n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1.

[0205] Alternatively, in formulas (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10), the sum of the designations l, m, and n does not exceed 5, preferably not more than 3, and more preferably not more than 1.

[0206] Other possible cases are equations (Ia), (Ib), (II-1) to (II-16), (III-1) to (III-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), (XI-1) to (XI-10), ( At least one R group from (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10), preferably all R groups are derived from the formula R as described in the context. 1 The group represents the group, where R is a group. 1 It has the definitions given above, especially for formulas (Ia) or (Ib).

[0207] The hole-transporting groups and / or groups containing electron-transporting groups of formulas (H-1) to (H-26) detailed above, preferably groups containing electron-transporting groups of formula (QL), are preferred R groups. 1 In this case, the R groups in formulas (H-1) to (H-26), (QL) and / or (Q-1) to (Q-44) are... 1 The group will be R 2 Group substitution.

[0208] Another possible scenario is the L in the above formulas, especially in formulas (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), (XI-1) to (XI-10), (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10). 1 -Z groups include hole transport groups and / or electron transport groups or hole transport groups and / or electron transport groups.

[0209] Another possible scenario is equation L. 1-The symbol Z in Z or in the structures / compounds of formulas (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), (XI-1) to (XI-10), (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10) is a group selected from formulas (Z-1) to (Z-91):

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217] The symbols used are as follows:

[0218] k is 0 or 1 independently in each case;

[0219] i is 0, 1, or 2 independently in each case;

[0220] j is independently 0, 1, 2 or 3 in each case;

[0221] h is independently 0, 1, 2, 3 or 4 in each case;

[0222] Dashed lines mark connection points;

[0223] Ar 1 R 1 It has the definitions given above, especially for formulas (Ia) or (Ib).

[0224] Preferably, L 1 The group can react with Z and L groups 1 Group or according to formula (L 1The atoms bonded by -Z) form complete conjugation. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, complete conjugation of the aromatic or heteroaromatic system is achieved. Another bond between the aforementioned conjugated groups, such as via a sulfur, nitrogen, or oxygen atom or a carbonyl group, does not negatively affect the conjugation.

[0225] In another preferred embodiment of the invention, L 1 It is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably having 6 to 12 carbon atoms and being soluble in one or more R atoms. 1 Aromatic ring systems with substituted but preferably unsubstituted groups, wherein R 1 It can have the definitions given above, especially for equations (Ia) and / or (Ib). More preferably, L 1 These are aromatic ring systems having 6 to 10 aromatic ring atoms or heteroaromatic ring systems having 6 to 13 heteroaromatic ring atoms, each of which can be generated by one or more R... 1 Group substitution, but preferably unsubstituted, wherein R 1 It can have the definitions given above, especially for equations (Ia) and / or (Ib).

[0226] More preferably, especially formula (L) 1 The symbol L shown in -Z) 1 In each case, the same or different, and is a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaryl group of the aromatic or heteroaryl ring system is directly (i.e., via the atoms of the aromatic or heteroaryl group) bonded to the corresponding atoms of another group.

[0227] In addition, the possible case is equation (L) 1 L as shown in -Z) 1 The group comprises an aromatic ring system having no more than two fused aromatic and / or heteroaromatic 6-membered rings, preferably excluding any fused aromatic or heteroaromatic ring systems. Therefore, a naphthyl structure is preferred over anthracene structures. Furthermore, fluorenyl, spirodifluorenyl, dibenzofuranyl, and / or dibenzothiopheneyl structures are preferred over naphthyl structures.

[0228] A particularly preferred structure is one that does not contain fusion, such as phenyl, biphenyl, terphenyl, and / or tetraphenyl structures.

[0229] Suitable aromatic or heteroaromatic ring systems L 1Examples are selected from o-phenylene, m-phenylene or p-phenylene, o-biphenylene, m-biphenylene or p-biphenylene, terphenylene (especially branched terphenylene), tetraphenylene (especially branched tetraphenylene), fluorene, spirodifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which can be generated by one or more R 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0230] Another possible case is, especially, the formula (L) 1 L as shown in -Z) 1 The group has no more than one nitrogen atom, preferably no more than two heteroatoms, especially preferably no more than one heteroatom, and more preferably no heteroatoms.

[0231] Preferred possible configurations are structural units L of formulas (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), (XI-1) to (XI-10), (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10). 1 -Z and / or L in formula QL 1 Groups, L of formulas H-1 to H-44 1 Group or Ar 2 The group is a bond or selected from formula (L 1 -1) to (L 1 -167) group:

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242] The dashed key marks the connection position in each case: k is 0 or 1, l is 0, 1, or 2, j is independently 0, 1, 2, or 3 in each case; h is independently 0, 1, 2, 3, or 4 in each case; g is 0, 1, 2, 3, 4, or 5; the symbol Y 1 For O, S or NR 1 Preferably O or S; symbol R 1 It has the definitions given above, especially for formulas (Ia) or (Ib).

[0243] The preferred case is given by equation (L) 1 -1) to (L 1 The sum of the markers k, l, g, h and j in the structure of -167) is at most 3 in each case, preferably at most 2, and more preferably at most 1.

[0244] Having the formula (L) 1 -Z) and / or (QL) preferred compounds of the present invention contain L 1 Group, the group representing a bond or selected from formula (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 One of the following is the preferred formula (L) in -167). 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -167), especially the preferred formula (L) 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -167). Advantageously, formula (L) 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -167), preferred formula (L) 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -167), especially preferred formula (L) 1 -1) to (L 1 -29) and / or (L 1-92) to (L 1 In the structure of -167), the sum of the markers k, l, g, h and j can not exceed 3 in each case, preferably not more than 2, and more preferably not more than 1.

[0245] Preferably, formula (L) 1 -1) to (L 1 R in -167) 1 The group does not interact with R 1 The ring atoms of the aryl or heteroaryl groups bonded to the group form a fused aromatic ring system or a fused heteroaryl ring system, preferably without forming any fused ring system. This includes [the group that can bond with R]. 1 or R 2 Possible substituents R for group bonding 2 R 3 A fused ring system is formed.

[0246] Another possible scenario is Ar 1 and / or R 1 The group is selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiopheneyl, 2-dibenzothiopheneyl, 3-dibenzothiopheneyl or 4-dibenzothiopheneyl, pyrene, triazinyl, imidazolyl, benzimidazolyl, benzo[] Azolyl, benzothiazolyl, 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, 1-naphthyl or 2-naphthyl, anthracene (preferably 9-anthrayl), phenanthryl and / or biphenylidene, each of which can be substituted with one or more R 2 The group may be substituted, but preferably unsubstituted, with phenyl, spirofluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, and biphenylidene groups being particularly preferred.

[0247] Other possibilities include equations (Ia), (Ib), (II-1) to (II-16), (III-1) to (III-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), (XI-1) In the structures (XII-1) to (XII-24), (XIII-1) to (XIII-32), (XIV-1) to (XIV-8), (XV-1) to (XV-10), (XVI-1) to (XVI-8), (XVII-1) to (XVII-8), (XVIII-1) to (XVIII-10) and / or (XIX-1) to (XIX-10), at least one R 1 Or Ar 1 The group is selected from formula (R) 1 -1) to (R) 1 -179) groups, or those in formulas (H-1) to (H-26), (Q-1) to (Q-44), (Z-1) to (Z-91), (L 1 -1) to (L 1 In the structure of -167), at least one Ar 1 or R 1 The group is selected from formula (R) 1 -1) to (R) 1 -179) group:

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261] The symbols used are as follows:

[0262] Y 1 For O, S or NR 2 O or S is preferred;

[0263] k is 0 or 1 independently in each case;

[0264] i is 0, 1, or 2 independently in each case;

[0265] j is independently 0, 1, 2 or 3 in each case;

[0266] h is independently 0, 1, 2, 3 or 4 in each case;

[0267] g is independently 0, 1, 2, 3, 4 or 5 in each case;

[0268] R 2 With the definitions given above, especially for equations (Ia) and / or (Ib),

[0269] The dashed key marks the connection position.

[0270] In the above formula (R) 1 -1) to (R) 1 In the structure of -179), the preferred formula (R) 1 -1) to (R) 1 The group of -177) is particularly preferred (R) 1 -1) to (R) 1 -64) and (R 1 -94) to (R 1 The group (-177) is particularly preferred (R) 1 -1) to (R) 1 -64) and (R 1 -115) to (R) 1 -177) group.

[0271] The preferred case is given by equation (R). 1 -1) to (R) 1 In the structure of -179), the sum of the markers k, i, j, h and g does not exceed 3 in each case, preferably not more than 2, and more preferably not more than 1.

[0272] Preferably, formula (R) 1 -1) to (R) 1 R in -179)2 The group does not interact with R 2 The ring atoms of the aryl or heteroaryl groups bonded to the group form a fused aromatic ring system or a fused heteroaryl ring system, preferably without forming any fused ring system. This includes [the group that can bond with R]. 2 Possible substituents R for group bonding 3 A fused ring system is formed.

[0273] When the compounds of this invention are reacted with aromatic or heteroaromatic compounds R 1 or R 2 When substituents are used, especially when configured as host materials, electron transport materials, or hole transport materials, it is preferable that they do not have any aryl or heteroaryl groups consisting of more than two directly fused aromatic six-membered rings. More preferably, the substituents do not have any aryl or heteroaryl groups consisting of six-membered rings directly fused to each other. The reason for this preferred option is the low triplet energy of such structures. While more than two directly fused aromatic six-membered rings are possible, fused aryl groups according to the invention are also suitable as phenanthrene and biphenylide, because these compounds also have high triplet energy levels.

[0274] In another preferred embodiment of the invention, for example, the structures of formulas (Ia) and / or (Ib) and the R in the preferred embodiments referencing these formulas or one or more of these structures 2 In each case, the same or different, and selected from H, D, having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, aliphatic hydrocarbon groups, or having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, and being substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but preferably unsubstituted, aromatic or heteroaromatic ring systems.

[0275] In another preferred embodiment of the invention, for example, the structures of formulas (Ia) and / or (Ib) and the R in the preferred embodiments referencing these formulas or one or more of these structures 3 In each case, the same or different, and selected from H, D, F, CN, having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, and being substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but preferably unsubstituted, aromatic or heteroaromatic ring systems.

[0276] The compounds of the present invention having the structures of formulas (Ia), (Ib), (II-1) to (II-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), and (XI-1) to (XI-10) are particularly preferred, wherein a total of no more than four, preferably no more than two, groups of formula X are not CH or CD, and at least one R group comprises an electron transport group, preferably a triazine group, more preferably of formula (L 1 The group (-Z), wherein Z represents a group of formula (Z-48), (Z-49), (Z-50) or (Z-51), more preferably a group of formula (Z-48), has the following properties:

[0277]

[0278] Particularly preferred are compounds of the present invention having the structures of formulas (Ia), (Ib), (II-1) to (II-16), (IV-1) to (IV-24), (V-1) to (V-32), (VI-1) to (VI-8), (VII-1) to (VII-8), (VIII-1) to (VIII-10), (IX-1) to (IX-8), (X-1) to (X-8), and (XI-1) to (XI-10), wherein a total of no more than four, preferably no more than two, groups of formula X are not CH or CD, wherein at least one R group comprises a fused aromatic ring system, preferably anthracene, phenanthrene, or biphenylene group, more preferably of formula (L 1 The group (-Z), where Z represents the group of formula (Z-78), (Z-79), or (Z-80), has the following properties:

[0279]

[0280] Suitable examples of compounds of the present invention are structures of formulas 1 to 432, as shown below:

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310] The examples detail preferred embodiments of the compounds of the present invention, which may be used alone or in combination with other compounds for all purposes of the present invention.

[0311] The above-described preferred embodiments can be combined with each other as needed, provided that the conditions described in claim 1 are met. In a particularly preferred embodiment of the invention, the above-described preferred embodiments are applied simultaneously.

[0312] The compounds of this invention can be prepared in principle by various methods. However, the methods described below have been found to be particularly suitable.

[0313] Therefore, the present invention also provides a method for preparing compounds comprising structures of formula (Ia) and / or (Ib), wherein in the coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is linked to a compound comprising at least one aromatic or heteroaromatic group.

[0314] Suitable compounds containing at least one nitrogen-containing heterocyclic group are commercially available in most cases. The starting compounds detailed in the examples can be obtained by known methods, and therefore, known methods are referred to.

[0315] Compounds containing at least one nitrogen-containing heterocyclic group can be reacted with other aryl or heteroaryl compounds by known coupling reactions. The necessary conditions for this purpose are known to those skilled in the art, and the detailed descriptions in the examples will help those skilled in the art to perform these reactions.

[0316] All particularly suitable and preferred coupling reactions leading to the formation of C-C bonds and / or CN bonds are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are well known, and the examples will provide further guidance to those skilled in the art.

[0317] The principles of the preparation method detailed above can be obtained from literature on similar compounds, and those skilled in the art can easily modify it to prepare the compounds of the present invention. Further information can be found in the examples.

[0318] These methods, followed by purification if necessary, such as recrystallization or sublimation, can yield high purity, preferably exceeding 99% (through...). 1 The compounds of the present invention containing the structures of formula (Ia) and / or (Ib) as determined by 1H NMR and / or HPLC.

[0319] The compounds of the present invention may also have suitable substituents, such as being substituted with relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesitylene, or branched terphenyl or tetraphenyl groups, thereby having solubility in standard organic solvents such that the compounds are soluble in toluene or xylene at room temperature, for example at a concentration sufficient to treat the compounds from solution. These soluble compounds are particularly well-suited for treatment from solution, for example by printing methods. Furthermore, it should be emphasized that the solubility of the compounds of the present invention comprising at least one structure of formula (Ia) and / or (Ib) in these solvents has been enhanced.

[0320] The compounds of this invention can also be mixed with polymers. These compounds can also be covalently incorporated into polymers. Compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid, or borate esters, or with reactive polymerizable groups such as olefins or oxetanes, are particularly feasible. These can be used as monomers for the manufacture of the corresponding oligomers, dendritic macromolecules, or polymers. Oligopolymerization or polymerization is preferably achieved via halogen or boric acid functionality or via polymerizable groups. Furthermore, it is feasible to crosslink the polymer via such groups. The compounds and polymers of this invention can be used in the form of crosslinked or uncrosslinked layers.

[0321] Therefore, the present invention also provides oligomers, polymers, or dendritic macromolecules containing one or more of the structures of formula (Ia) and / or (Ib) detailed above or compounds of the present invention, wherein bonds are present in one or more of the compounds of the present invention or in the structure of formula (Ia) and / or (Ib) linked to the polymer, oligomer, or dendritic macromolecule. According to the structure or linkage of the compounds of formula (Ia) and / or (Ib), these thus form side chains of the oligomer or polymer or are bonded within the main chain. The polymer, oligomer, or dendritic macromolecule may be conjugated, partially conjugated, or non-conjugated. The oligomer or polymer may be linear, branched, or dendritic. With respect to the repeating units of the compounds of the present invention in the oligomer, dendritic macromolecule, and polymer, the same preferred features as described above apply.

[0322] To prepare the oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers. Copolymers are preferred, wherein the units of formula (Ia) and / or (Ib) or the preferred embodiments described in the context are present in the range of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, more preferably 20 to 80 mol%. Suitable and preferred comonomers forming the basic polymer backbone are selected from fluorene (e.g., according to EP 842208 or WO 2000 / 022026), spirodifluorene (e.g., according to EP 707020, EP894107 or WO 2006 / 061181), p-phenylene (e.g., according to WO 92 / 18552), carbazole (e.g., according to WO2004 / 070772 or WO 2004 / 113468), thiophene (e.g., according to EP 1028136), dihydrophenanthrene (e.g., according to WO2005 / 014689), cis and trans-indenofluorene (e.g., according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g., according to WO 2005 / 040302), and phenanthrene (e.g., according to WO 92 / 18552). (2005 / 104264 or WO 2007 / 017066) or more of these units. The polymers, oligomers and dendritic macromolecules may contain other units, such as hole transport units, especially those based on triarylamines, and / or electron transport units.

[0323] Furthermore, particular interest is focused on the compounds of the present invention characterized by high glass transition temperatures. In this regard, compounds of the present invention comprising the structures of general formulas (Ia) and / or (Ib) or the preferred embodiments described in the context are especially preferred, having a glass transition temperature of at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, and particularly preferably at least 150°C, as measured according to DIN 51005 (2005-08 edition).

[0324] To process the compounds of the present invention from the liquid phase, such as by spin coating or printing, formulations of the compounds of the present invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthylene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, etc. Alkane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fonone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecyl Alkylbenzene, ethyl benzoate, indene, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindene, or mixtures of these solvents.

[0325] Therefore, the present invention also provides a formulation comprising the compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, particularly one of the solvents described above or a mixture of these solvents. The other compound may alternatively be at least one other organic or inorganic compound also used in electronic devices, such as a luminescent compound, particularly a phosphorescent dopant, and / or other matrix material. Such other compound may also be a polymer.

[0326] Therefore, the present invention also provides a composition comprising the compound of the present invention and at least one other organic functional material. The functional material is typically an organic or inorganic material introduced between the anode and cathode. Preferably, the organic functional material is selected from: phosphorescent emitters, phosphorescent emitters, multipodial emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide bandgap materials, and n-type dopants.

[0327] In one particular aspect of the invention, the compounds of the invention can be used as matrix materials, particularly as matrix materials for phosphorescent emitters, and the matrix materials are used in combination with other matrix materials in most cases.

[0328] Therefore, the present invention also relates to a composition comprising at least one compound comprising a structure or preferred embodiment of the formula (Ia) and / or (Ib) described in the context, and at least one other matrix material.

[0329] The present invention also provides a composition comprising at least one compound having a structure or preferred embodiment of at least one formula (Ia) and / or (Ib) as described in the context, and at least one wide-bandgap material, which is understood to mean a material in the sense disclosed in US 7,294,849. These systems have exhibited exceptionally favorable performance data in electroluminescent devices.

[0330] Preferably, the band gap of the other compounds can be 2.5 eV or higher, more preferably 3.0 eV or higher, and very preferably 3.5 eV or higher. One method for calculating the band gap is via the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0331] The molecular orbitals of the material, particularly the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels, and the energies of the lowest triplet state T1 and the lowest excited singlet state S1, were determined via quantum chemical calculations. For organic materials, the geometry was first optimized using the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet state" method. Subsequently, energy calculations were performed based on the optimized geometry. This was done using the "TD-SCF / DFT / default spin / B3PW91" method and with the "6-31G(d)" basis set (charge 0, spin singlet state). The HOMO level HEh or LUMO level LEh in Hartley was obtained from the energy calculations. This was used to determine the HOMO and LUMO levels in electron volts, calibrated by cyclic voltammetry measurements, as follows:

[0332] HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206

[0333] LUMO(eV)=((LEh*27.212)-2.0041) / 1.385

[0334] In the context of this application, these values ​​are considered as the HOMO and LUMO energy levels of the material.

[0335] The lowest triplet state T1 is defined as the triplet energy with the lowest energy, which is obviously generated by the quantum chemical calculations.

[0336] The lowest excited singlet state S1 is defined as the energy of the excited singlet state with the lowest energy, which is obviously generated by the quantum chemical calculations.

[0337] The methods described in this article are independent of the software package used and always produce the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Corporation) and Q-Chem4.1 (Q-Chem Corporation).

[0338] The present invention also relates to a composition comprising at least one compound comprising a structure or preferred embodiment of the formula (Ia) and / or (Ib) described in the context, and at least one phosphorescent emitter, the term "phosphorescent emitter" also being understood to mean a phosphorescent dopant.

[0339] In a system comprising a matrix material and a dopant, the dopant is understood to refer to a component that constitutes a small proportion of the mixture. Conversely, in a system comprising a matrix material and a dopant, the matrix material is understood to refer to a component that constitutes a large proportion of the mixture.

[0340] Preferred phosphorescent dopants used in matrix systems, preferably hybrid matrix systems, are the preferred phosphorescent dopants specified below.

[0341] The term "phosphorescent dopant" generally encompasses compounds that emit light through spin-forbidden transitions, such as from an excited triplet state or a state with a higher spin quantum number (e.g., a quintet state).

[0342] Suitable phosphorescent compounds (= triplet luminescent materials) are especially compounds that emit light when properly excited, 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, more preferably greater than 56 and less than 80, especially compounds of metals having that atomic number. Preferred phosphorescent materials are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum. In the context of this invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent compounds.

[0343] Examples of the aforementioned luminescent materials can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO 2016 / 000803、WO 2016 / 124304、WO 2016 / 015815、WO 2017 / 032439、WO 2018 / 019687、WO 2018 / 019688、WO WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197 and WO 2018 / 069273. Generally speaking, all phosphorescent complexes for phosphorescent OLEDs that are known to those skilled in the art, based on the prior art, are suitable, and those skilled in the art will be able to use other phosphorescent complexes without inventive effort.

[0344] The table below provides clear examples of phosphorescent dopants:

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353] In one specific aspect of the invention, the compound of the invention can be used as a hole-blocking material, preferably as a hole-blocking layer, wherein the compound of the invention used as a hole-blocking material comprises at least one electron transport group. In a preferred embodiment, the compound of the invention used as a hole-blocking material comprises fewer hole transport groups than electron transport groups, and more preferably contains no hole transport groups.

[0354] The compounds comprising the structures of formula (Ia) and / or (Ib) or the preferred embodiments detailed above can preferably be used as active components in electronic devices. Electronic devices are understood to mean any device comprising an anode, a cathode, and at least one layer between the anode and cathode, said layer comprising at least one organic compound or organometallic compound. Therefore, the electronic device of the present invention comprises an anode, a cathode, and at least one intermediate layer containing at least one compound comprising the structure of formula (Ia) and / or (Ib). Preferred electronic devices are selected from: organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), organic electrosensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon light-emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), with organic electroluminescent devices (OLEDs, PLEDs) being particularly preferred, especially phosphorescent OLEDs. The electronic device comprises at least one compound containing at least one structure of formula (Ia) and / or (Ib) in at least one layer. Organic electroluminescent devices are especially preferred. The active component is generally an organic or inorganic material introduced between the anode and cathode, such as a charge-injecting material, a charge-transporting material, or a charge-blocking material, but particularly a luminescent material and a matrix material.

[0355] A preferred embodiment of the present invention is an organic electroluminescent device. The organic electroluminescent device includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also include other layers, such as, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions. Simultaneously, the one or more hole transport layers may be p-type doped, for example, doped with metal oxides such as MoO3 or WO3 or doped with (per)fluorinated electron-deficient aromatic systems, and / or the one or more electron transport layers may be n-type doped. Similarly, intermediate layers may be introduced between the two light-emitting layers, these intermediate layers having, for example, exciton blocking functions and / or controlling the charge balance of the electroluminescent device. However, it should be noted that not every one of these layers is required.

[0356] In this context, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, these emitting layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in white emission; in other words, multiple luminescent compounds that can fluoresce or phosphore are used in the emitting layers. Particularly preferred are three-layer systems, in which the three layers exhibit blue, green, and orange or red emission (see, for example, WO 2005 / 011013 for basic construction), or systems with more than three emitting layers. The system may also be a mixture, in which one or more layers fluoresce and one or more other layers phosphore.

[0357] In a preferred embodiment of the present invention, the organic electroluminescent device comprises a structure containing formula (Ia) and / or (Ib) or a compound of the present invention according to the preferred embodiments described above, in one or more light-emitting layers as a matrix material, preferably as an electron-conducting matrix material, preferably in combination with other matrix materials, preferably a hole-conducting matrix material. In another preferred embodiment of the present invention, the other matrix material is a hole-transporting compound. In another preferred embodiment of the present invention, the other matrix material is an electron-conducting compound. In yet another preferred embodiment, the other matrix material is a compound with a large band gap, which, even if it participates in hole and electron transport in the layer, will not reach a significant level. The light-emitting layer comprises at least one light-emitting compound.

[0358] Suitable matrix materials that can be used in combination with compounds of formula (Ia) and / or (Ib) or according to preferred embodiments are aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones, such as those according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines, especially monoamines, such as those according to WO 2014 / 015935; carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl) or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851; indolecarbazole derivatives, such as those according to WO 2007 / 063754 or WO 2008 / 056746; indobenzocarbazole derivatives, such as those according to WO 2010 / 136109 and WO 2011 / 000455; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP1731584, JP 2005 / 347160; bipolar matrix materials, such as those according to WO 2007 / 137725; silanes, such as those according to WO 2005 / 111172; borazine 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 2008 / 056746; zinc complexes, such as those according to EP652273 or WO WO 2009 / 062578; silylated diazacyclopentane or silylated tetrazacyclopentane derivatives, such as those according to WO 2010 / 054729; phosphorus diazacyclopentane derivatives, such as those according to WO 2010 / 054730; bridged carbazole derivatives, such as those according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 and WO 2012 / 143080; triphenylide derivatives, such as those according to WO 2012 / 048781; lactams, such as those according to WO 2011 / 116865, WO 2011 / 137951 or WO 2013 / 064206; or 4-spirocarbazole derivatives, such as those according to WO Application EP 14002104.9, which has not yet been published, or 2014 / 094963. Other phosphorescent luminescent organisms that emit light at shorter wavelengths than the actual luminescent organisms can also exist as co-substrate in the mixture.

[0359] Preferred co-host materials are triarylamine derivatives, especially monoamines, indocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0360] Preferred triarylamine derivatives used together with the compounds of the present invention as co-host materials are selected from compounds of the following formula (TA-1):

[0361]

[0362] Among them, Ar 1 In each case, they may be the same or different, and they have 6 to 40 carbon atoms and in each case can be one or more R... 2 Aromatic or heteroaromatic ring systems with substituted groups, having 5 to 60 aromatic ring atoms and capable of being substituted by one or more R groups. 2 A group-substituted aryloxy group, or having 5 to 60 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Group-substituted aralkyl groups, wherein two or more adjacent R groups 2 The substituents may optionally form monocyclic or polycyclic aliphatic, heterocyclic, aromatic, or heteroaromatic ring systems, preferably monocyclic or polycyclic aliphatic ring systems, said ring system being denoted by one or more R groups. 3 Group substitution, where the symbol R 2 It has the definitions given above, especially for equations (Ia) and / or (Ib). Preferably, Ar 1 The same or different in each case, and having 5 to 24, preferably 5 to 12, aromatic ring atoms, and in each case can be one or more R 2 The substituted group is preferably an unsubstituted aryl or heteroaryl group.

[0363] Suitable Ar 1 Examples of the group are selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiopheneyl, 2-dibenzothiopheneyl, 3-dibenzothiopheneyl or 4-dibenzothiopheneyl, and 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, each of which can be substituted by one or more R 2 Group substitution is preferred, but unsubstituted groups are preferred.

[0364] Preferably, Ar 1 The functional groups may be the same or different in each case, and are selected from the R groups mentioned above. 1 -1 to R 1 -177 group, more preferably R 1 -1 to R 1 -64.

[0365] In a preferred embodiment of the compound of formula (TA-1), at least one Ar 1 The group is selected from biphenyl groups, which may be ortho-biphenyl, meta-biphenyl, or para-biphenyl. In another preferred embodiment of the compound of formula (TA-1), at least one Ar 1 The functional group is selected from fluorene or spirodifluorene groups, wherein these groups may be bonded to a nitrogen atom at positions 1, 2, 3, or 4. In another preferred embodiment of the compound of formula (TA-1), at least one Ar 1 The group is selected from phenylene group or biphenyl group, wherein the group is an ortho, meta or para bonded group, which is substituted by a dibenzofuran group, a dibenzothiophene group or a carbazole group, especially a dibenzofuran group, wherein the dibenzofuran or dibenzothiophene group is bonded to the phenylene group or biphenyl group via the 1, 2, 3 or 4 position, wherein the carbazole group is bonded to the phenylene group or biphenyl group via the 1, 2, 3 or 4 position or via a nitrogen atom.

[0366] In a particularly preferred embodiment of the compound of formula (TA-1), an Ar 1 The group is selected from fluorene or spirodifluorene groups, especially 4-fluorene or 4-spirodifluorene groups, one Ar 1 The group is selected from biphenyl groups (especially p-biphenyl groups) or fluorene groups (especially 2-fluorene groups), the third Ar 1 The group is selected from p-phenylene group or p-biphenyl group, which is replaced by dibenzofuran group (especially 4-dibenzofuran group) or carbazole group (especially N-carbazole group or 3-carbazole group).

[0367] Preferred indobenzocarbazole derivatives used together with the compounds of the present invention as co-host materials are selected from compounds of the following formula (TA-2):

[0368]

[0369] Among them, Ar 1 and R 1 It has the definitions listed above, especially for formulas (Ia), (Ib), and / or (TA-1). 1 The preferred embodiment of the group is the structure R listed above. 1 -1 to R 1 -177, more preferably R 1 -1 to R 1 -64.

[0370] A preferred embodiment of the compound of formula (TA-2) is the compound of formula (TA-2a):

[0371]

[0372] Among them, Ar 1 and R 1 It possesses the definitions listed above, especially for formulas (Ia), (Ib), and / or (TA-1). The two R atoms bonded to the indene carbon atom... 1 The groups are preferably the same or different, and are alkyl groups having 1 to 4 carbon atoms, especially methyl groups, or aromatic ring systems having 6 to 12 carbon atoms, especially phenyl groups. More preferably, the two R groups bonded to the indene carbon atom are... 1 The group is a methyl group. More preferably, the substituent R bonded to the indocarbazole basic skeleton in formula (TA-2a) is... 1 It is an H or carbazole group, which can be bonded to the indocarbazole basic skeleton via the 1, 2, 3 or 4 position or via a nitrogen atom, especially via the 3 position.

[0373] Preferred 4-spirocarbazole derivatives used together with the compounds of the present invention as co-host materials are selected from compounds of the following formula (TA-3):

[0374]

[0375] Among them, Ar 1 and R 1 It has the definitions listed above, especially for equations (Ia), (Ib), and / or (Q-1). 1 The preferred embodiment of the group is the structure R listed above. 1 -1 to R 1 -177, more preferably R 1 -1 to R 1 -64.

[0376] A preferred embodiment of the compound of formula (TA-3) is the compound of formula (TA-3a):

[0377]

[0378] Among them, Ar 1 and R 1 It has the definitions listed above, especially for equations (Ia), (Ib), and / or (Q-1). 1 The preferred embodiment of the group is the structure R listed above. 1 -1 to R 1 -177, more preferably R 1 -1 to R 1 -64.

[0379] Preferred lactams used together with the compounds of the present invention as co-host materials are selected from compounds of the following formula (LAC-1):

[0380]

[0381] Where R 1 It has the definitions listed above, especially for formulas (Ia) and / or (Ib).

[0382] A preferred embodiment of the compound of formula (LAC-1) is a compound of formula (LAC-1a):

[0383]

[0384] Where R 1 It has the definitions given above, especially for equations (Ia) and / or (Ib). Here R 1 Preferably, they are the same or different in each case, and are H or have 5 to 40 aromatic ring atoms and can be converted by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 2 It can have the definitions given above, especially for formulas (Ia) and / or (Ib). Most preferably, the substituent R 1 Selected from H or aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, and in each case can be substituted by one or more non-aromatic R 2 The substituent group is substituted, but preferably unsubstituted. Suitable substituent R 1 Examples are selected from phenyl, o-phenyl, meta-phenyl or para-phenyl, terphenyl (especially branched terphenyl), tetraphenyl (especially branched tetraphenyl), 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl or 4-spirodifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothiopheneyl, 2-dibenzothiopheneyl, 3-dibenzothiopheneyl or 4-dibenzothiopheneyl, and 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole, each of which can be substituted by one or more R 2 Group substitution is preferred, but unsubstituted groups are preferred. Here, suitable R... 1 The structure is the same as that described above for R-1 to R-177, with R being more preferred. 1 -1 to R 1 -64 describes the same structure.

[0385] The preferred co-host material is biscarbazole.

[0386] It is also preferable to use a variety of different matrix materials as a mixture, especially at least one electron-conducting matrix material and at least one hole-conducting matrix material. A mixture of charge-transporting matrix material and electrically inert matrix material is also preferred, wherein the electrically inert matrix material participates in charge transport only in a minor manner, as described, for example, in WO 2010 / 108579.

[0387] More preferably, a mixture of two or more triplet emitters and a matrix is ​​used. In this case, a triplet emitter with a shorter wavelength emission spectrum is used as a co-matrix for a triplet emitter with a longer wavelength emission spectrum.

[0388] More preferably, in a preferred embodiment, the compounds of the present invention comprising the structures of formula (Ia) and / or (Ib) can be matrix materials in organic electronic devices, particularly in the light-emitting layers of organic electroluminescent devices such as OLEDs or OLECs. In this case, the matrix material comprising the compounds containing the structures of formula (Ia) and / or (Ib) or the preferred embodiments described in the context is present in the electronic device with one or more dopants, preferably a combination of phosphorescent dopants.

[0389] In this case, the proportion of matrix material in the luminescent layer is 50.0 vol% to 99.9 vol% for the fluorescent luminescent layer, preferably 80.0 vol% to 99.5 vol%, more preferably 92.0 vol% to 99.5 vol%, and for the phosphorescent luminescent layer it is 85.0 vol% to 97.0 vol%.

[0390] Accordingly, the proportion of dopant is 0.1 vol% to 50.0 vol% for the fluorescent emissive layer, preferably 0.5 vol% to 20.0 vol%, more preferably 0.5 vol% to 8.0 vol%, and for the phosphorescent emissive layer it is 3.0 vol% to 15.0 vol%.

[0391] The light-emitting layer of an organic electroluminescent device can also comprise a system containing multiple matrix materials (a mixed matrix system) and / or multiple dopants. In this case, the dopants are typically those materials present in a smaller proportion of the system, while the matrix materials are those materials present in a larger proportion. However, in some cases, the proportion of a single matrix material in the system may be less than the proportion of a single dopant.

[0392] In another preferred embodiment of the invention, a compound comprising the structure or preferred embodiment of formula (Ia) and / or (Ib) described in the context is used as a component of the mixed matrix system. 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 with hole transport properties, and the other is a material with electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components can also be primarily or completely incorporated into a single mixed matrix component, in which case other mixed matrix components fulfill other functions. The two different matrix materials can 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. The mixed matrix system is preferably used in phosphorescent organic light-emitting devices. A source of more detailed information about the mixed matrix system is application WO 2010 / 108579.

[0393] The present invention also provides an electronic device, preferably an organic electroluminescent device, wherein the electronic device comprises one or more compounds of the present invention and / or at least one oligomer, polymer or dendritic macromolecule of the present invention as a hole-conducting compound in one or more hole-conducting layers.

[0394] In a preferred embodiment of the present invention, the organic electroluminescent device comprises an inventive compound containing a structure of formula (Ia) and / or (Ib) or a preferred embodiment of the present invention detailed above, and / or at least one oligomer, polymer or dendritic macromolecule of the present invention as an electron-conducting compound in an electron-conducting layer.

[0395] The present invention also provides an electronic device, preferably an organic electroluminescent device, wherein the electronic device comprises one or more compounds of the present invention and / or at least one oligomer, polymer, or dendritic macromolecule of the present invention in one or more electron transport layers, preferably in combination with materials having a high dielectric constant, such as alkali metal or alkaline earth metal fluorides and corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.), lanthanide compounds (e.g., Yb₂O₃), or organoalkali metal complexes, such as Liq (lithium hydroxyquinoline), particularly preferably organoalkali metal complexes, preferably Liq, in combination with compounds of the present invention and / or oligomers, polymers, or dendritic macromolecules of the present invention. The two different materials in the electron transport layer may be present in a ratio of 1:50 to 50:1, preferably 1:10 to 10:1, more preferably 1:4 to 4:1, and most preferably 1:2 to 2:1.

[0396] The present invention also provides an electronic device, preferably an organic electroluminescent device, wherein the electronic device comprises one or more compounds of the present invention and / or at least one oligomer, polymer or dendritic macromolecule of the present invention as a matrix material in the light-emitting layer, preferably in combination with a phosphorescent emitter.

[0397] Preferred cathodes are metals, metal alloys, or multilayer structures with low work function, comprising a variety of metals such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys comprising alkali metals or alkaline earth metals and silver are also suitable, for example, alloys comprising magnesium and silver. In the case of multilayer structures, other metals with relatively high work function, such as Ag, can be used in addition to the metals mentioned above. In this case, combinations of metals such as Mg / Ag, Ca / Ag, or Ba / Ag are generally used. It is also preferable to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides, and their corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Organoalkali metal complexes, such as Liq (lithium hydroxyquinoline), are also useful for this purpose. The thickness of this layer is preferably between 0.5 nm and 5 nm.

[0398] The preferred anode is a material with a high work function. Preferably, the work function of the anode is greater than 4.5 eV relative to vacuum. First, metals with high redox potentials are suitable for this purpose, such as Ag, Pt, or Au. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are preferred. x Al / PtO x Alternatively, a conductive mixed metal oxide may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to allow irradiation of organic materials (O-SC) or light-emitting materials (OLED / PLED, O-laser). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers such as PEDOT, PANI, or derivatives of these polymers, are also preferred. More preferably, a p-type doped hole transport material is applied to the anode as a hole injection layer. In this case, suitable p-type dopants are metal oxides, such as MoO3 or WO3, or (per)fluorinated electron-deficient aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexaazatriphenylide) or NPD9 from Novaled. Such a layer simplifies hole injection in materials with low HOMO (i.e., high HOMO in terms of magnitude).

[0399] In other layers, any material used for said layers according to the prior art can typically be used, and those skilled in the art can combine any of these materials with the materials of the present invention in electronic devices without inventive effort.

[0400] Because the lifespan of such devices is significantly shortened in the presence of water and / or air, the devices are structured accordingly (depending on the application), provided with contact, and ultimately hermetically sealed.

[0401] Furthermore, an electronic device, particularly an organic electroluminescent device, is preferred, characterized by coating one or more layers via a sublimation process. In this case, in a vacuum sublimation system, typically below 10... -5 millibars, preferably below 10 -6 The material is applied via vapor deposition at an initial pressure of millibars. The initial pressure can also be even lower or higher, for example, below 10. -7 millibar.

[0402] Similarly, an electronic device, particularly an organic electroluminescent device, is preferred, characterized by coating one or more layers using an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, at 10 -5 The material is coated under pressures between millibar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thus structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0403] Furthermore, an electronic device, particularly an organic electroluminescent device, is preferred, characterized by the fabrication of one or more layers from a solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, or nozzle printing, but more preferably by LITI (photoinitiated thermal imaging, thermal transfer) or inkjet printing. For this purpose, a soluble compound is required, for example, through suitable substitution.

[0404] The electronic devices, particularly organic electroluminescent devices, can also be fabricated as hybrid systems by applying one or more layers from a solution and by applying one or more other layers by vapor deposition. For example, a light-emitting layer comprising the compound of the present invention containing a structure of formula (Ia) and / or (Ib) and a matrix material can be applied from a solution, and a hole-blocking layer and / or an electron transport layer can be applied thereto by vapor deposition under reduced pressure.

[0405] These methods are generally known to those skilled in the art and can be applied without difficulty by those skilled in the art to electronic devices, especially organic electroluminescent devices, that contain the compounds of the present invention with structures or preferred embodiments of formulas (Ia) and / or (Ib) detailed above.

[0406] Compared with the prior art, the electronic devices of the present invention, especially organic electroluminescent devices, are known for one or more of the following surprising advantages:

[0407] 1. Compounds, oligomers, polymers, or dendritic macromolecules comprising structures or preferred embodiments of formulas (Ia) and / or (Ib) as described in the context, particularly for electronic devices, especially organic electroluminescent devices, exhibiting very good lifetimes as host materials or as electron-conducting and / or hole-conducting materials. In this case, these compounds particularly contribute to low roll-off, i.e., the power efficiency of the device decreases only slightly at high brightness.

[0408] 2. Electronic devices, particularly organic electroluminescent devices, that incorporate compounds, oligomers, polymers, or dendritic macromolecules having the structures or preferred embodiments of formulas (Ia) and / or (Ib) described in the context as electron conducting materials, hole conducting materials, and / or host materials exhibit excellent efficiency. In this case, the compounds, oligomers, polymers, or dendritic macromolecules of the present invention having the structures or preferred embodiments of formulas (Ia) and / or (Ib) described in the context result in low operating voltages when used in electronic devices.

[0409] 3. Electronic devices comprising compounds, oligomers, polymers or dendritic macromolecules having structures or preferred embodiments of formulas (Ia) and / or (Ib) as described in the context, especially organic electroluminescent devices, exhibiting excellent color purity.

[0410] 4. The compounds, oligomers, polymers or dendritic macromolecules of the present invention having the structures of formulas (Ia) and / or (Ib) described in the context or preferred embodiments exhibit extremely high stability and lifetime.

[0411] 5. By utilizing compounds, oligomers, polymers, or dendritic macromolecules having the structures of formulas (Ia) and / or (Ib) described in the context, or preferred embodiments, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. Therefore, these devices are characterized by high PL efficiency of the light emitter and consequently high EL efficiency, as well as excellent energy transfer of the matrix to the dopant.

[0412] 6. The use of compounds, oligomers, polymers or dendritic macromolecules having structures of formulas (Ia) and / or (Ib) as described in the context, or preferred embodiments, in layers of electronic devices, particularly organic electroluminescent devices, results in high mobility of the electronic conductor structure.

[0413] 7. Compounds, oligomers, polymers or dendritic macromolecules having the structure or preferred embodiments of formula (Ia) and / or (Ib) as described in the context are characterized by excellent thermal stability and good sublimation properties in compounds with a molar mass of less than about 1200 g / mol.

[0414] 8. Compounds, oligomers, polymers or dendritic macromolecules having the structure or preferred embodiment of formula (Ia) and / or (Ib) as described in the context have excellent glass film formation.

[0415] 9. Compounds, oligomers, polymers, or dendritic macromolecules having the structure of formula (Ia) and / or (Ib) as described in the context, or preferred embodiments, form excellent films from solution.

[0416] 10. Compounds, oligomers, polymers, or dendritic macromolecules comprising the structures or preferred embodiments of formulas (Ia) and / or (Ib) described in the context have surprisingly high triplet state levels T1.

[0417] These advantages are not accompanied by a deterioration in other electronic properties.

[0418] The compounds and mixtures of the present invention are suitable for use in electronic devices. Here, "electronic device" should be understood to mean a device containing at least one layer comprising at least one organic compound. However, the components may also comprise inorganic materials or layers formed entirely of inorganic materials.

[0419] Therefore, the present invention also provides the use of the compounds or mixtures of the present invention in electronic devices, particularly in organic electroluminescent devices, preferably as hole transport materials, electron transport materials or host materials, and more preferably as host materials of red phosphorescent compounds.

[0420] The present invention also provides the use of the compounds of the present invention and / or the oligomers, polymers or dendritic macromolecules of the present invention as host materials for phosphorescent emitters, electron transport materials and / or hole transport materials in electronic devices, preferably as host materials for red or green phosphorescent compounds or as hole transport materials or electron transport materials in organic electroluminescent devices having fluorescent emitters.

[0421] The present invention also provides the use of the compounds of the present invention and / or the oligomers, polymers or dendritic macromolecules of the present invention as part of an electron transport layer in electronic devices, especially in combination with materials having a high dielectric constant.

[0422] The present invention also provides an electronic device comprising at least one of the compounds or mixtures of the present invention detailed above. In this case, the preferred options detailed above for the compounds also apply to the electronic device. More preferably, the electronic device is selected from organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon light-emitting devices (DMKoller et al., Nature Photonics 2008, 1-4), preferably organic electroluminescent devices (OLEDs, PLEDs), especially phosphorescent OLEDs.

[0423] In another embodiment of the invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, meaning that the light-emitting layer is directly adjacent to the hole injection layer or 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, metal complexes identical or similar to those in the light-emitting layer can be used as hole transport or hole injection materials directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0424] In the other layers of the organic electroluminescent device of the present invention, any material commonly used in the prior art can be used. Therefore, those skilled in the art can combine any material known for use in organic electroluminescent devices with the compounds of formula (Ia) and / or (Ib) or the present invention according to preferred embodiments without inventive effort.

[0425] The compounds of the present invention generally exhibit very good performance when used in organic electroluminescent devices. In particular, when used in organic electroluminescent devices, the lifetime is significantly better compared to similar compounds according to the prior art. Simultaneously, other properties of the organic electroluminescent devices, especially efficiency and voltage, are also better or at least comparable.

[0426] It should be noted that the scope of this invention covers variations of the embodiments described herein. Unless expressly excluded, any feature disclosed in this invention may be interchanged with optional features for the same or equivalent or similar purposes. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered as an instance of a general series or as an equivalent or similar feature.

[0427] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true for the preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (rather than in combination).

[0428] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered inventive in themselves, rather than merely as some embodiments of the invention. These features may be sought independently as supplements to or alternatives to any currently claimed invention.

[0429] The technical teachings disclosed in this invention can be extracted and combined with other embodiments.

[0430] The invention has been illustrated in detail by means of the following embodiments, but is not intended to limit the invention thereto.

[0431] Those skilled in the art will be able to use the details provided to manufacture other electronic devices of the present invention without inventive effort, and thus practice the invention throughout the scope of the claims.

[0432] Synthesis Examples

[0433] a) 2-(4-chlorophenyl)-3-phenylquinoline-4-carboxylic acid

[0434]

[0435] In a 1 L flask, 14.0 g (93.3 mmol; 1.00 equivalent; 98% pure) indigo [CAS 91-56-5], 24.2 g (103 mmol; 1.10 equivalent) 1-(4-chlorophenyl)-2-phenylethyl ketone [CAS 1889-71-0], and 15.7 g (280 mmol; 3.00 equivalent) potassium hydroxide powder [CAS 1310-58-3] were suspended in 630 mL of ethanol [CAS 64-17-5]. The reaction mixture was stirred at 100 °C for 48 hours. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in 200 mL of ethyl acetate [CAS 141-78-6] and 200 mL of water for phase separation. The organic phase was extracted with water (2 × 100 mL), and the combined aqueous phase was washed with ethyl acetate (3 × 100 mL). The aqueous phase was adjusted to pH 1 with 25 mL of fuming hydrochloric acid [CAS 7647-01-0], and the precipitated solid was filtered off. The product was then washed with ethanol to obtain 22.5 g (62.7 mmol; 67% of theoretical value) of the product as a white solid.

[0436] The following compounds can be obtained similarly:

[0437]

[0438]

[0439] b) 6-(4-chlorophenyl)indeno[1,2-c]quinolin-11-one

[0440]

[0441] In a 500 mL flask, 21.0 g (58.4 mmol; 1.00 equivalent) of 2-(4-chlorophenyl)-3-phenylquinoline-4-carboxylic acid and 32.1 mL (350 mmol; 6.00 equivalent) of phosphoryl chloride [CAS 10025-87-3] were dissolved in 183 mL of chlorobenzene [CAS 108-90-7] and heated to 150 °C for 24 hours. After checking the conversion, the reaction mixture was cooled to room temperature, and 8.17 g (61.3 mmol; 1.05 equivalent) of anhydrous aluminum chloride [CAS 7446-70-0] was added. The mixture was heated to reflux for 3 hours. After cooling, the reaction mixture was allowed to precipitate in ice water. The water was discarded, and ethanol was added to the crude product. The resulting solid was filtered off and dried. 15.53 g (44.9 mmol; 77% of the theoretical value) of the product was converted without further purification.

[0442] The following compounds can be obtained similarly:

[0443]

[0444]

[0445] c) 11-Biphenyl-2-yl-6-(4-chlorophenyl)-11H-indeno[1,2-c]quinoline-11-ol

[0446]

[0447] In a 500 mL flask, under a protective gas atmosphere, 13.0 g (53.3 mmol; 1.24 equivalents) of 2-bromobiphenyl [CAS2052-07-5] was dissolved in 80 mL of anhydrous THF [CAS 109-99-9] and cooled to -76 °C. Then, 20.7 mL (2.5 mol / L; 51.7 mmol; 1.20 equivalents) of n-butyllithium [CAS 109-72-8] was added dropwise, and the mixture was stirred for another hour. At -40 °C, a suspension of 14.8 g (43.1 mmol, 1.00 equivalents) of 6-(4-chlorophenyl)indo[1,2-c]quinoline-11-one in 370 mL of anhydrous THF [CAS 109-99-9] was added dropwise to the mixture. The resulting mixture was gradually heated to room temperature and stirred for another 72 hours. The reactants were quenched with 100 mL of water, and the resulting phases were separated. The aqueous phase was extracted with ethyl acetate (3 × 150 mL) [CAS 141-78-6], and the combined organic phases were washed with water (3 × 150 mL). The organic phase was concentrated under reduced pressure and precipitated in heptane [CAS 142-82-5]. The crude product was purified by column chromatography to give 7.65 g (15.4 mmol; 36% of theoretical value) of the product in solid form.

[0448] The following compounds can be obtained similarly:

[0449]

[0450]

[0451]

[0452] d) 6'-(4-chlorophenyl)spiro[fluorene-9,11'-indeno[1,2-c]quinoline]

[0453]

[0454] In a 500 mL flask, 7.50 g (15.1 mmol; 1.00 equivalent) of 11-biphenyl-2-yl-6-(4-chlorophenyl)-11H-indeno[1,2-c]quinoline-11-ol and 28.8 g (150 mmol; 10.0 equivalent) of toluenesulfonic acid monohydrate [CAS 6192-52-5] were suspended in 250 mL of toluene [CAS 108-88-3] and the mixture was stirred at 115 °C for 24 hours. After conversion, the mixture was cooled to room temperature, and the reaction solution was mixed with water. After phase separation, the aqueous phase was extracted with dichloromethane [CAS 75-09-2] (3 × 150 mL). The combined organic phases were washed with water (3 × 150 mL). The organic solvent was removed on a rotary evaporator, and the resulting solid was dried. 7.00 g of product (14.6 mmol; 97% of the theoretical value) was converted without further purification.

[0455] The following compounds can be obtained similarly:

[0456]

[0457]

[0458] e)6'-[4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]spiro[fluorene-9,11'-indeno[1,2-c]quinoline]

[0459]

[0460] In a 500 mL flask, under a protective gas atmosphere, 6.34 g (13.3 mmol; 1.00 equivalent) of 6'-(4-chlorophenyl)spiro[fluorene-9,11'-indeno[1,2-c]quinoline] and 4.30 g (16.9 mmol; 1.28 equivalent) of bis(pinacol)diborane [CAS73183-34-3] were dissolved in 200 mL of anhydrous dioxane. The mixture was degassed for 45 minutes in alkane [CAS 123-91-1]. Then, 3.20 g (32.6 mmol; 2.46 equivalents) of potassium acetate [CAS 127-08-2] and 510 mg (0.69 mmol; 0.05 equivalents) of bis(tricyclohexylphosphine)palladium dichloride [CAS 29934-17-6] were added, and the mixture was heated to 110 °C overnight. After conversion, the mixture was cooled to room temperature, and 300 mL of ethyl acetate [CAS 141-78-6] and 300 mL of water were added to the reaction mixture. The phases were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were concentrated and washed with water. After solvent removal, the desired product (7.60 g; 12.3 mmol; 93% of theoretical value) was obtained.

[0461] The following compounds can be obtained similarly:

[0462]

[0463]

[0464] f) 6'-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]spiro[fluorene-9,11'-indo[1,2-c]quinoline]

[0465]

[0466] 7.00 g (11.3 mmol; 1.05 equivalent) of 6'-[4-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)phenyl]spiro[fluorene-9,11'-indeno[1,2-c]quinoline], 2.89 g (10.8 mmol; 1.00 equivalent) of 2-chloro-4,6-diphenyl-[1,3,5]triazine [CAS 3842-55-5] and 8.04 g (32.4 mmol; 3.00 equivalent) of tripotassium phosphate [CAS 7778-53-2] were suspended in 75 mL of dioxane. Alkane [CAS 123-91-1], 75 mL toluene [CAS 108-88-3], and 75 mL water were added. 121 mg (0.54 mmol; 0.05 equivalent) palladium(II) acetate [CAS 3375-31-3] and 329 mg (1.08 mmol; 0.10 equivalent) tri-o-tolylphosphine [CAS 6163-58-2] were added to the suspension, and the reaction mixture was heated under reflux for 16 hours. After cooling, the solvent was removed, and the residue was dissolved in dichloromethane [CAS 75-09-2] and water for phase separation. The aqueous phase was extracted with dichloromethane (2 × 150 mL), the combined organic phases were washed with water (2 × 150 mL), and then concentrated to dryness. Purification was performed by Soxhlet extraction, followed by washing with ethyl acetate [CAS 141-78-6] and sublimation under vacuum to give the desired product (1.78 g; 2.64 mmol; 24% of theoretical value).

[0467] The following compounds can be obtained similarly:

[0468]

[0469]

[0470]

[0471]

[0472]

[0473] According to the above embodiments, isoquinoline derivatives of formula (Ia) can be obtained, some of which are commercially available, or these can be obtained by known reactions, such as the Bischler-Napieralski reaction, the Pictet-Gams reaction, or the Pictet-Spengler reaction.

[0474] OLED

[0475] The compounds of this invention can be used in organic electroluminescent devices, particularly OLEDs. These are manufactured and characterized using methods well known to those skilled in the art. OLEDs containing the compounds of this invention have the aforementioned advantages compared to known OLEDs. In particular, the use of the compounds of this invention can enhance OLED performance data such as voltage, lifetime, stability, and efficiency.

[0476] General manufacturing process and characterization of OLEDs: A 50nm thick glass plate coated with structured ITO (indium tin oxide) forms the substrate for applying OLEDs.

[0477] OLEDs essentially have 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 from a 100 nm thick aluminum layer. Table 1 shows typical materials that can be used to manufacture OLEDs.

[0478]

[0479]

[0480] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer consists of at least one matrix material (host material) and a luminescent dopant (emissive) added to the matrix material by co-evaporation in a specific volume ratio. Details given in the form of H:SEB (95%:5%) mean here that material H is present in the layer at a volume ratio of 95% and SEB at a ratio of 5%.

[0481] Similarly, the electron transport layer and hole injection layer are also composed of a mixture of two materials.

[0482] OLEDs were characterized using standard methods. For this purpose, the electroluminescence spectrum was measured, the external quantum efficiency (EQE, measured as a function of luminance, %) was calculated from the current-voltage-luminance characteristic line (IUL characteristic line) exhibiting Lambertian emission characteristics, and the lifetime was determined. Parameters were measured at 10 mA / cm². 2The EQE below refers to the value at 10 mA / cm. 2 The external quantum efficiency achieved is 10 mA / cm². 2 U below refers to 10 mA / cm 2 The operating voltage is specified. Lifetime LT is defined as the time it takes for the brightness to decrease to a certain percentage during operation at a constant current density. The LT80 value here means that the reported lifetime corresponds to the time after the brightness decreases to 80% of its initial value. At 60 or 40 mA / cm² 2 The values ​​below indicate that the lifetime is 60 or 40 mA / cm. 2 Take the measurement.

[0483] OLEDs containing the compounds of this invention have been found to have excellent performance data; in particular, they exhibit significantly improved lifetime compared to comparable OLEDs of the prior art. Furthermore, voltage and efficiency are both at extremely high levels.

[0484] Device Example: OLED Manufacturing

[0485] The OLEDs of the present invention and those of the prior art are manufactured by the general method according to WO 04 / 058911, which has been adapted for the situation described herein (by changing the layer thickness and materials).

[0486] The following examples (see Tables 2 through 4) present data for various OLEDs. The substrate used is a 50nm thick glass substrate coated with structured ITO (indium tin oxide). The OLED essentially has the following layer structure:

[0487] -Base,

[0488] -ITO (50nm),

[0489] - Buffer layer (20nm),

[0490] - Hole injection layer (HTL 95%, HIL 5%) (20nm)

[0491] -Hole transport layer (HTL) (195nm),

[0492] -Emitting layer (EML) (20nm),

[0493] - Electron transport layer (ETL 50%, EIL 50%) (30nm)

[0494] - Electron-injected layer (EIL) (1nm),

[0495] -cathode.

[0496] The cathode is formed from a 100 nm thick aluminum layer. The buffer layer, applied by spin coating, is a 20 nm thick Clevios P ​​VP AI4083 layer (from Heraeus Clevios GmbH, Leverkusen). All remaining materials are applied by thermal vapor deposition in a vacuum chamber. The OLED structure is shown in Table 2. The materials used are shown in Table 4.

[0497] The luminescent layer always consists of at least one matrix material (body = H) and a luminescent dopant ( = D) added to the matrix material by co-evaporation in a specific volume ratio. Details given in the form of H:D (97%:3%) mean that material H is present in the layer at a volume ratio of 97% and D at a volume ratio of 3%. Similarly, the electron transport layer can also be composed of a mixture of the two materials.

[0498] OLEDs were characterized using standard methods. For this purpose, electroluminescence spectra were recorded, and current efficiency (measured in cd / A) and external quantum efficiency (EQE, measured as a percentage) as a function of luminance were calculated from the current-voltage-luminance characteristic line (IUL characteristic line) exhibiting Lambertian emission characteristics. Finally, the module lifetime was determined. OLEDs were recorded at 1000 cd / m². 2 The electroluminescence spectrum at a given brightness was determined, and the CIE 1931 x and y color coordinates were calculated accordingly. Parameters were set at 1000 cd / m². 2 The EQE below refers to 1000 cd / m 2 External quantum efficiency at operating brightness. Lifetime is at initial brightness of 1000 cd / m². 2 The time elapsed before a 5% decrease, i.e., at 1000 cd / m 2 The LD95 value is shown below. Data obtained for various OLEDs are summarized in Table 3.

[0499] Using the compounds of this invention as electron transport materials for OLEDs

[0500] The material of the present invention is suitable for use as an electron transport material (ETL) for OLEDs and has yielded excellent performance data; see Examples E1 to E4.

[0501]

[0502]

[0503]

[0504]

[0505]

Claims

1. A compound that conforms to one of formulas (VII-1), (VII-2), (VII-3), (VII-4), (VII-5), (VII-6), (VII-7), or (VII-8): Where the symbol X represents CR, or if -L 1 When a -Z group is bonded to X, the symbol X represents C, where R may be the same or different in each case and is H, D, F, CN, N(Ar)2, a straight-chain alkyl group having 1 to 8 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be replaced by one or more R. 1 Group substitution; In L 1 In the group represented by -Z, L 1 This indicates a bond or a ring with 5 to 24 aromatic atoms that can be bonded by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; Z represents R 1 Ar or Z a or Z b The groups, wherein the symbols Ar and R 1 It has the definition given below, and Z a or Z b for in W may be the same or different in each case and is a ring with 5 to 30 aromatic atoms and can be generated by one or more R. 1 Aromatic or heteroaromatic ring systems with substituted groups; Ar may be the same or different in each case and is a ring with 5 to 30 aromatic atoms and can be replaced by one or more non-aromatic R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; R 1 In each case, they may be the same or different and are H, D, F, CN, N (Ar) 1 )2, a straight-chain alkyl group having 1 to 40 carbon atoms, said alkyl group being soluble in one or more R 2 Group substitution, wherein one or more hydrogen atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be replaced by one or more R groups. 2 Group substitution; Ar 1 In each case, they may be the same or different and are composed of 5 to 30 aromatic ring atoms and can be separated by one or more non-aromatic R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; R 2 In each case, the same or different alkyl group is H, D, F, CN, having a straight chain with 1 to 40 carbon atoms, said alkyl group may be one or more R 3 Group substitution, wherein one or more hydrogen atoms may be replaced by D, F, or CN, or having 5 to 30 aromatic ring atoms and in each case being replaced by one or more R groups. 3 Aromatic or heteroaromatic ring systems with substituted groups; R 3 In each case, the same or different and selected from H, D, F, CN, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein one or more hydrogen atoms may be replaced by D, F or CN and may be replaced by one or more alkyl groups, each of which has 1 to 4 carbon atoms.

2. A compound that conforms to one of formulas (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII-5), (VIII-6), (VIII-7), (VIII-8), (VIII-9), or (VIII-10): Where the symbol X represents CR, or if -L 1 When the -Z group is bonded to X, the symbol X represents C, and the symbol R and the -L group are bonded together. 1 The -Z group has the definition given in claim 1.

3. A compound that conforms to one of formulas (IX-1), (IX-2), (IX-3), (IX-4), (IX-5), (IX-6), (IX-7), or (IX-8): Where the symbol X represents CR, or if -L 1 When the -Z group is bonded to X, the symbol X represents C, and the symbol R and the -L group are bonded together. 1 -Z group has the definition given in claim 1.

4. An oligomer, polymer, or dendritic macromolecule containing one or more compounds according to any one of claims 1 to 3, wherein the compound has one or more bonds connected to the polymer, oligomer, or dendritic macromolecule in place of hydrogen atoms or substituents.

5. A composition comprising at least one compound according to any one of claims 1 to 3 or an oligomer, polymer or dendritic macromolecule according to claim 4, and at least one other compound selected from: phosphorescent emitters, phosphorescent emitters, host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials.

6. The composition according to claim 5, wherein the phosphor is a phosphor exhibiting TADF (thermally activated delayed fluorescence).

7. A formulation comprising at least one compound according to any one of claims 1 to 3, or an oligomer, polymer, or dendritic macromolecule according to claim 4, or a composition according to claim 5 or 6, and at least one solvent.

8. Use of a compound according to any one of claims 1 to 3, an oligomer, polymer or dendritic macromolecule according to claim 4, or a composition according to claim 5 or 6 as a host material, hole transport material or electron transport material in an electronic device.

9. The use according to claim 8, wherein the host material is the host material of a red phosphorescent compound.

10. A method for preparing the compound according to any one of claims 1 to 3 or the oligomer, polymer and / or dendritic macromolecule according to claim 4, characterized in that, In a coupling reaction, a compound containing at least one nitrogen-containing heterocyclic group is linked to a compound containing at least one aromatic or heteroaromatic group.

11. An electronic device comprising at least one compound according to any one of claims 1 to 3, an oligomer, polymer, or dendritic macromolecule according to claim 4, or a composition according to claim 5 or 6, wherein the electronic device is selected from organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, luminescent electrochemical cells, or organic laser diodes.

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