Cyclic compounds for organic electroluminescent devices

Abstract

The present invention relates to a cyclic compound suitable for use in an electronic device, and to an electronic device containing said compound, in particular an organic electroluminescent device.

Description

Technology Field

[0001] The present invention relates to cyclic compounds for use in electronic devices, particularly organic electroluminescent devices, and electronic devices, particularly organic electroluminescent devices, comprising these heterocyclic compounds. Background Technology

[0002] The emission materials used in organic electroluminescent devices are commonly phosphorescent organometallic complexes or fluorescent compounds. Generally, improvements are still needed in electroluminescent devices.

[0003] WO 2010 / 104047 A1 and WO 2019 / 132506 A1 disclose polycyclic compounds that can be used in organic electroluminescent devices. There is no disclosure regarding compounds according to the present invention. Additionally, the anti-aromatic properties of compounds were investigated by Wang et al. in Nature Communications | 8: 1948. However, there is no description by Wang et al. regarding the use of such compounds in organic electroluminescent devices.

[0004] In general, improvements are still needed for these heterocyclic compounds intended for use, for example as emitters, particularly fluorescent emitters, especially in relation to efficiency and operating voltage as well as device lifespan and color purity. The problem to be solved

[0005] Accordingly, the object of the present invention is to provide a compound suitable for use in organic electronic devices, particularly organic electroluminescent devices, and to provide a corresponding electronic device that achieves good device characteristics when used in such devices.

[0006] More specifically, the problem addressed by the present invention is to provide a compound with a high lifespan, good efficiency, and low operating voltage.

[0007] In addition, the compound must have excellent processability, and in particular, it must exhibit excellent solubility.

[0008] An additional problem addressed by the present invention may be considered to be providing a compound suitable for use in phosphorescent or fluorescent electroluminescent devices, particularly as an emitter. More specifically, the problem addressed by the present invention is to provide an emitter suitable for red, green, or blue electroluminescent devices.

[0009] In addition, the compounds must lead to devices with excellent color purity, particularly when they are used as emitters in organic electroluminescent devices.

[0010] An additional problem addressed by the present invention may be considered to be providing a compound suitable for use in phosphorescent or fluorescent electroluminescent devices, particularly as a matrix material. More specifically, the problem addressed by the present invention is to provide a matrix material suitable for red, yellow, and blue phosphorescent electroluminescent devices.

[0011] Furthermore, the compounds must lead to devices with excellent color purity, particularly when they are used as matrix materials, hole transport materials, or electron transport materials in organic electroluminescent devices.

[0012] An additional challenge can be considered to be providing electronic devices with excellent performance at very low prices and with consistent quality.

[0013] In addition, electronic devices must be usable or adaptable for many purposes. More specifically, the performance of electronic devices must be maintained over a wide temperature range. means of solving the problem

[0014] Surprisingly, it was found that this objective is achieved by specific compounds described in detail below, which lead to organic electroluminescent devices that are preferably very well suited for use in electroluminescent devices and exhibit very good characteristics, particularly with respect to lifetime, color purity, efficiency, and operating voltage. Accordingly, the present invention provides these compounds, and electronic devices comprising these compounds, in particular organic electroluminescent devices.

[0015] The present invention provides a compound comprising at least one structure of the following formula (I), preferably a compound of the following formula (I):

[0016]

[0017] The symbols and indices used in the food are as follows:

[0018] Z 1 , Z 2 In each case, is the same or different, and is N or B;

[0019] W 1 , W 2 , W 3 , W 4 is the same or different in each case, and is CAr, X, or 2 adjacent W 1 , W 2 , W 3 , W 4 Gi is Ar;

[0020] Y 1...is the same or different in each case and is N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr, C=C(R)2, O, S, Se, S=O, or SO2, preferably N(Ar), N(R), B(Ar), B(R), P(=O)R, P(=O)Ar, C=O, C(R)2, Si(R)2, O, S, Se, S=O, or SO2, more preferably C=O, N(Ar) or B(Ar);

[0021] Y 2 In each case, is the same or different, and is a bond, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr, C=C(R)2, O, S, Se, S=O, or SO2, preferably a bond, N(Ar), N(R), B(Ar), B(R), P(=O)R, P(=O)Ar, C=O, C(R)2, Si(R)2, O, S, Se, S=O, or SO2, more preferably C=O, N(Ar) or B(Ar);

[0022] Ar is an aromatic or heteroaromatic ring system that is the same or different in each case, has 5 to 60 aromatic ring atoms, and can be substituted with one or more R radicals; wherein the Ar group may form a ring system with at least one Ar group, R group, or additional group;

[0023] X is the same or different in each case, and is N or CR, preferably CR, provided that in one ring X, X 3 Two or fewer of the elements are N;

[0024] X1 is the same or different in each case, and N, CR a or CAr, preferably CR a and, provided that in one ring X 1 , X 2 , X 3 Two or fewer of the elements are N;

[0025] X 2 is the same or different in each case, and N, CR b or CAr, preferably CR b and, provided that in one ring X 1 , X 2 , X 3 Two or fewer of the elements are N;

[0026] X 3 are the same or different in each case, and when p is 1, N, CR c , CAr or C, preferably CR c and, provided that in a single ring X, X 1 , X 2 , X 3 Two or fewer of the elements are N;

[0027] p is the same or different and is 0 or 1, where W 3 , W 4 If is not Ar, p = 1;

[0028] R, R a , R b , R c are the same or different in each case, and H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)OAr', C(=O)OR 1 , C(=O)N(Ar')2, C(=O)N(R 1 )2, C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1, P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms (the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group having one or more R in each case 1 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 1 C=CR 1 , C≡C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), which can be replaced by -O-, -S-, SO or SO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 1 An aromatic or heteroaromatic ring system capable of being substituted by radicals, or having 5 to 60 aromatic ring atoms and one or more R 1 It is an aryloxy or heteroaryloxy group that can be substituted by a radical; simultaneously, two R, R a , R b , R c Radicals can also form ring systems together or with additional groups;

[0029] Ar' is the same or different in each case and has 5 to 60 aromatic ring atoms and one or more R 1It is an aromatic or heteroaromatic ring system that may be substituted by radicals; at the same time, two Ar' radicals bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are also a bridge formed by a single bond or B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 It is possible to connect together through a selected bridge;

[0030] R 1 are the same or different in each case, and H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)OAr'', C(=O)OR 2 , C(=O)Ar'', C(=O)R 2 , P(=O)(Ar'')2, P(Ar'')2, B(Ar'')2, B(R 2 )2, C(Ar'')3, C(R 2 )3, Si(Ar'')3, Si(R 2 )3, 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 group having 2 to 40 carbon atoms (each of these is one or more R 2 It can be substituted by radicals, where one or more non-adjacent CH2 groups are -R 2 C=CR 2 -, -C≡C-, Si(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), which may be replaced with -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced with D, F, Cl, Br, I, CN or NO2), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (each of these having one or more R 2 It may be substituted by radicals), or having 5 to 60 aromatic ring atoms and one or more R 2 An aryloxy or heteroaryloxy group that may be substituted by a radical, or one or more R having 5 to 60 aromatic ring atoms 2 An aralkyl or heteroaralkyl group that may be substituted by a radical, or a combination of these systems; and simultaneously, two or more preferably adjacent R 1 Radicals can form a ring system together; simultaneously, one or more R 1 Radicals may also form ring systems with additional parts of the compound;

[0031] Ar'' is the same or different in each case and has 5 to 30 aromatic ring atoms and one or more R 2 It is an aromatic or heteroaromatic ring system that may be substituted by radicals; at the same time, two Ar'' radicals bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are also a bridge formed by a single bond or B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 It is possible to connect together through a selected bridge;

[0032] R 2is the same or different in each case and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms (wherein one or more hydrogen atoms may be replaced with D, F, Cl, Br, I, or CN, or substituted by one or more alkyl groups each having 1 to 4 carbon atoms); and simultaneously, two or more, preferably adjacent, substituents R 2 They can form a ring system together.

[0033] In Equation (I), p may be the same or different, and may be 0 or 1, where W 3 , W 4 If is not Ar, p = 1. Therefore, W 3 , W 4 If this together forms an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R radicals, p may be only 0. W 3 , W 4 Aromatic or heteroaromatic ring systems formed by a group and which may be substituted by an R group are Z in Equation (I) when p = 0 2 It combines with the. Also, W 3 , W 4 When p = 1, the gas may be Ar. In this case, W 3 , W 4 The group together forms an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R radicals, wherein the aromatic or heteroaromatic ring system is formed through two adjacent and mutually bonded carbon atoms in formula (I) Z 2 and Y 2 Combined with the energy, the six rings are Z2 and Y 2 It is formed together with Qi. W 1 , W 2 In the case where the group is Ar, the aromatic or heteroaromatic ring system is Z through two adjacent and mutually bonded carbon atoms in formula (I). 1 and Y 1 Combined with the, the 6 rings are Z 1 and Y 1 It is formed together with the tile.

[0034] This is explained in detail below by Equations (Ia), (Ib), (Ic), and (Id). Here, Equations (Ia) and (Ib) exemplify the case where p = 1, which was explained in detail above, and Equation (Ic) exemplifies the case where p = 0. W 1 , W 2 When the group is Ar, the formula (Id) can be applied accordingly.

[0035] In Equation (I), p may be the same or different, and may be 0 or 1, where:

[0036] - When p = 1, Equation (I) follows Equation (Ia) or (Ib);

[0037] - When p = 0, Equation (I) follows Equation (Ic);

[0038]

[0039] W in Equation (I) 1 , W 2 Qi can also be Ar together. This gives rise to the expression (Id):

[0040]

[0041] In equations (Ia), (Ib), (Ic), and (Id), the symbol has the definition shown in detail above for equation (I).

[0042] In the context of the present invention, the aryl group contains 6 to 40 carbon atoms; in the context of the present invention, the heteroaryl group contains 2 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. The aryl group or heteroaryl group is understood here to mean a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, e.g., pyridine, pyrimidine, thiophene, etc., or a fused (annelated) aryl or heteroaryl group, e.g., naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics connected to each other by a single bond, e.g. biphenyl, are referred to as aromatic ring systems rather than aryl or heteroaryl groups.

[0043] In the context of the present invention, an electron-deficient heteroaryl group is a heteroaryl group having at least one heteroaromatic six-membered ring having at least one nitrogen atom. An additional aromatic or heteroaromatic five-membered or six-membered ring may be fused to this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazolin, or quinoxaline.

[0044] In the context of the present invention, an aromatic ring system contains 6 to 60 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, 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 the present invention, an aromatic or heteroaromatic ring system is understood to mean a system that does not necessarily contain only an aryl or heteroaryl group, but in which two or more aryl or heteroaryl groups may be connected by a non-aromatic unit, for example, a carbon, nitrogen, or oxygen atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also to be considered as aromatic ring systems in the context of the present invention, and systems in which two or more aryl groups are connected, for example, by a short alkyl group are also to be considered as such. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are connected to each other by a single bond.

[0045] In the context of the present invention, an aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group, which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be substituted by the aforementioned group, is preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, prophenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cycloheptenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethinyl, It is understood to mean propynyl, butynyl, pentynyl, hexinyl, heptynyl, or octynyl radicals. An alkoxy group having 1 to 40 carbon atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy.A thioalkyl group having 1 to 40 carbon atoms is particularly methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propphenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexeniltio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethinylthio, It is understood to mean propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio. Generally, the alkyl, alkoxy, or thioalkyl group according to the present invention may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the aforementioned groups; additionally, one or more hydrogen atoms may also be replaced by D, F, Cl, Br, I, CN, or NO2, preferably F, Cl, or CN, more preferably F or CN, particularly preferably CN.

[0046] An aromatic or heteroaromatic ring system having 5 to 60 or 5 to 40 aromatic ring atoms, which may also be substituted with the radicals mentioned above in each case and may be connected to an aromatic or heteroaromatic system through any desired position, in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxen, isotruxen, spirotruxen, spiroisotruxen, furan, benzofuran, isobenzofuran, dibenzofuran, Thiophene, benzothiophen, isobenzothiophen, dibenzothiophen, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazol, indazole, imidazole, benzimidazole, naftimidazole, phenanthrioimidazole, pyridimidazole, pyrazineimidazole, quinoxalinimidazole, oxazole, benzoxazole, naftoxazole, anthroxazole, phenanthrioxazole, isooxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, Pyrimidine, Benzopyrimidine, Quinoxaline, 1,5-Diazanthracen, 2,7-Diazapyrene, 2,3-Diazapyrene, 1,6-Diazapyrene, 1,8-Diazapyrene, 4,5-Diazapyrene, 4,5,9,10-Tetraazaperylene, Pyrazine, Phenazine, Phenoxazine, Phenothiazine, Fluorubin, Naftiridine, Azacarbazole, Benzocarbolin, Phenanthroline, 1,2,3-Triazole, 1,2,4-Triazole, Benzotriazole, 1,2,3-Oxadiazole, 1,2,4-Oxadiazole, 1,2,5-Oxadiazole, 1,3,4-Oxadiazole, 1,2,3-Thiadiazole, 1,2,4-Thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,It is understood to mean a group derived from 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or a group derived from a combination of these systems.

[0047] The phrase that two or more radicals may form a ring together should be understood, in the context of this detailed description specifically, to mean that two radicals are connected to each other by a chemical bond with the formal removal of two hydrogen atoms. This is illustrated by the following diagram:

[0048] .

[0049] However, additionally, the phrase mentioned above should also be understood to mean that when one of the two radicals is hydrogen, the second radical bonds to the position where the hydrogen atom was bonded, forming a ring. This will be illustrated by the following diagram:

[0050]

[0051] In a preferred configuration, the compound of the present invention may comprise the structures of formulas (IIa) to (IIk); more preferably, the compound of the present invention may be selected from the compounds of formulas (IIa) to (IIk):

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] W during the meal 1 , W 2 , Y 1 , Y 2 , Z 1, Z 2 , X 1 , X 2 and X 3 has the definition given above, specifically for Equation (I), and additional symbols and indices are as follows:

[0058] X is the same or different in each case, and when p is 1, it is N, CR, or C, preferably CR or C, provided that two or fewer X groups in one ring are N;

[0059] Y 3 In each case, is the same or different and is O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R), preferably C(R)2, O, S or N(Ar');

[0060] p is 0 or 1.

[0061] In a further preferred embodiment, the compound of the present invention comprises a structure of formulas (IIIa) to (IIIk), wherein the compound of the present invention may more preferably be selected from compounds of formulas (IIIa) to (IIIk):

[0062]

[0063]

[0064]

[0065]

[0066] Symbol Y in the formula 1 , Y 2 , Z 1 , Z 2 , X 1 , X 2 and X 3 has the definition given above, in particular for Equation (I), and symbols X, Y 3and index p has the definition given above, in particular for expressions (IIa) through (IIk).

[0067] Preferably, in formulas (I), (IIa) to (IIk) and / or (IIIa) to (IIIk), X, X 1 , X 2 and X 3 Four or fewer of the elements, preferably two or fewer, are N; more preferably all X, X 1 , X 2 and X 3 The CR, CR a , CR b , CR c or C is (X and X 3 This is the case when a ring system is formed through the combination of qi).

[0068] In a further preferred embodiment, the compound of the present invention comprises the structure of formulas (IV-1) to (IV-20), wherein the compound of the present invention may more preferably be selected from the compounds of formulas (IV-1) to (IV-20).

[0069]

[0070]

[0071]

[0072]

[0073] Symbol Y in the formula 1 , Y 2 , Z 1 , Z 2 , R, R a , R b and R c has the definition given above, in particular for Equation (I), and the symbol Y 3The above has the definition given in particular for formulas (IIa) to (IIk), wherein index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, index n is 0, 1, 2 or 3, preferably 0, 1 or 2, index j is 0, 1 or 2, preferably 0 or 1, and index k is 0 or 1.

[0074] Here, the structures / compounds of formulas (IV-1) to (IV-10) are preferred, and the structures of formulas (IV-1) to (IV-9) are particularly preferred.

[0075] The sum of indices j, l, m, and n in the structures / compounds of formulas (IV-1) to (IV-20) is preferably 8 or less, particularly preferably 6 or less, and more preferably 4 or less.

[0076] In addition, particularly in preferred embodiments of formulas (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or those formulas presented below, Z 1 and Z 2 At least one of the groups, preferably two, is N and Y 1 and Y 2 At least one, preferably two, of the groups may be B(Ar), B(R), P(=O)Ar, P(=O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O, or SO2, preferably C=O, B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O, or SO2, more preferably C=O, B(R), or B(Ar). Z 1 and Z 2 At least one of the groups is N and at least one, preferably two Y 1 , Y 2A composition in which the ion is B(Ar), B(R), P(=O)Ar, P(=O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O, or SO2 may be advantageously used as a emitting agent.

[0077] In addition, particularly in preferred embodiments of formulas (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or those formulas presented below, Z 1 and Z 2 At least one of the elements, preferably two, is N and Y 1 and Y 2 At least one, preferably two, of the group may be N(Ar), N(R), P(Ar), P(R), O, S, or Se, preferably N(Ar), N(R), O, or S, more preferably N(Ar).

[0078] Z 1 and Z 2 At least one of the elements, preferably two, is N and Y 1 , Y 2 An embodiment in which at least one, preferably two, of the group is N(Ar), N(R), P(Ar), P(R), O, S, or Se may be advantageously used as a hole conductor material.

[0079] In additional configurations, particularly in preferred embodiments of formulas (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or those formulas presented below, Z 1 and Z 2 At least one of the elements, preferably two, is B and Y 1 , Y 2 At least one, preferably two, of the groups may be N(Ar), N(R), P(Ar), P(R), O, S, or Se, preferably N(Ar), N(R), O, or S, and more preferably N(Ar). Z 1 and Z2 At least one of the groups is B and at least one, preferably two Ys 1 , Y 2 A composition in which the element is N(Ar), N(R), P(Ar), P(R), O, S, or Se may be advantageously used as a emitter.

[0080] In additional configurations, particularly in preferred embodiments of formulas (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or those formulas presented below, Z 1 and Z 2 At least one of the elements, preferably two, is B and Y 1 and Y 2 At least one, preferably two, of the group may be B(Ar), B(R), P(=O)Ar, P(=O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O or SO2, preferably C=O, B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO2, more preferably C=O, B(R) or B(Ar).

[0081] Z 1 and Z 2 At least one of the elements, preferably two, is B and Y 1 , Y 2 An embodiment in which at least one, preferably two, of the group is B(Ar), B(R), P(=O)Ar, P(=O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O, or SO2 may be particularly advantageously used as an electron transport material.

[0082] In addition, particularly in formulas (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or in preferred embodiments of these formulas described in detail below, two Y 3 It could be a case where the energy is the same.

[0083] In addition, particularly in formulas (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20) and / or in preferred embodiments of these formulas described in detail below, two Y 3 It could be a case where the energy is different.

[0084] More preferably, the compound comprises at least one structure of formulas (V-1) to (V-40); more preferably, the compound is selected from compounds of formulas (V-1) to (V-40):

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] Symbol Z in food 1 , Z 2 , X, X 1 and X 2 has the definition given above, in particular for Equation (I), and the symbol Y 3 has the definition given above, in particular for equations (IIa) through (IIk), and Z 3 , Z 4 In each case, is the same or different and is N, B, P(=O) or Si(R), preferably N, B or P(=O), more preferably N or B.

[0091] Here, the structures / compounds of formulas (V-1) to (V-30) are preferred, and the structures of formulas (V-2), (V-5) to (V-9), (V-12), (V-15) to (V-19), (V-22), (V-25) to (V-29) are particularly preferred.

[0092] In addition, in formulas (V-1) to (V-40), four or fewer, preferably two or fewer X, X1 and X 2 The is N; more preferably, all X, X 1 and X 2 The CR, CR a , CR b Or it may be the case of C (as is the case when the ring closure of the X tile is formed by the connection).

[0093] More preferably, the compound comprises at least one structure of formulas (VI-1) to (VI-40); more preferably, the compound is selected from compounds of formulas (VI-1) to (VI-40):

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100] Z in food 1 , Z 2 , R, R a and R b has the definition given above, in particular for Equation (I), and the symbol Y 3 has the definition given above, in particular for equations (IIa) through (IIk), and Z 3 , Z 4 In each case, is the same or different and is N, B, P(=O) or Si(R), preferably N, B or P(=O), more preferably N or B, index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and index j is 0, 1 or 2, preferably 0 or 1.

[0101] Here, structures / compounds of formulas (VI-1) to (VI-30) are preferred, and structures / compounds of formulas (VI-2), (VI-5) to (VI-9), (VI-12), (VI-15) to (VI-19), (VI-22), (VI-25) to (VI-29) are particularly preferred.

[0102] In addition, in formulas (V-1) to (V-20), (VI-1) to (VI-20) and / or particularly in preferred embodiments of these formulas detailed below, Z 1 and Z 2 At least one of the elements, preferably two, is N and Z 3 and Z 4 There may also be a case where at least one, preferably two, of the elements is B. Z 1 and Z 2 At least one of the elements, preferably two, is N and Z 3 and Z 4 A configuration in which at least one, preferably two, of the components is B may be advantageously used as a emitter.

[0103] In addition, in formulas (V-1) to (V-20), (VI-1) to (VI-20) and / or particularly in preferred embodiments of these formulas detailed below, Z 1 and Z 2 At least one of the elements, preferably two, is N and Z 3 and Z 4 There may be cases where at least one, preferably two, of the elements are N.

[0104] Z 1 , Z 2 , Z 3 , Z 4 An embodiment in which many, preferably all, of the components are N can be advantageously used as a hole conductor material.

[0105] In additional configurations, formulas (V-1) to (V-20), (VI-1) to (VI-20) and / or particularly in preferred embodiments of these formulas detailed below, Z1 and Z 2 At least one of the elements, preferably two, is B and Z 3 and Z 4 There may also be a case where at least one, preferably two, of the elements is N. Z 1 and Z 2 At least one of the elements, preferably two, is B and Z 3 and Z 4 A configuration in which at least one, preferably two, of the components is N may be advantageously used as a emitter.

[0106] In additional configurations, particularly in formulas (V-1) to (V-20), (VI-1) to (VI-20) and / or in preferred embodiments of these formulas detailed below, Z 1 and Z 2 At least one of the elements, preferably two, is B and Z 3 and Z 4 There may be cases where at least one, preferably two, of the elements is B.

[0107] Z 1 , Z 2 , Z 3 , Z 4 An embodiment in which many, preferably all, of the components are B can be advantageously used, particularly as an electronic transport material.

[0108] In additional configurations, particularly in formulas (V-1) to (V-20), (VI-1) to (VI-20) and / or in preferred embodiments of these formulas detailed below, Z 2 , Z 3 At least one of the elements, preferably two, is N and Z 4 , Z 5 There may be cases where at least one, preferably two, of the elements is B.

[0109] In the structures of formulas (VI-1) to (VI-40), the sum of indices j, l, and m may preferably be 8 or less, particularly preferably 6 or less, and more preferably 4 or less.

[0110] In a preferred embodiment of the present invention, at least two Rs, R a , R b , R c A radical consists of those two Rs, R a , R b , R c The radical forms a fused ring with additional groups to which it binds, where two R and R a , R b , R c The radical may form at least one structure of formulas (RA-1) to (RA-12):

[0111]

[0112]

[0113] R in food 1 has the definition presented above, and the dotted line combination consists of 2 Rs, R a , R b , R c It indicates the attachment site where a radical binds, and additional symbols have the following definitions:

[0114] Y 4 is the same or different in each case and C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 1 , NAr, O or S, preferably C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), is O or S;

[0115] R dis the same or different in each case, and F, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms (wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is one or more R in each case 2 It may be substituted by radicals, and one or more non-adjacent CH2 groups are R 2 C=CR 2 , C≡C, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 1 ), may be substituted with -O-, -S-, SO or SO2), or have 5 to 60 aromatic ring atoms and in each case one or more R 2 An aromatic or heteroaromatic ring system that may be substituted by a radical, or one or more R having 5 to 60 aromatic ring atoms 2 It is an aryloxy or heteroaryloxy group that may be substituted by a radical; at the same time, also two R d Radicals together or as a single R d Radicals R 1 It is possible to form a ring system with radicals or additional groups;

[0116] s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0117] t is 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2;

[0118] v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0119] In a preferred embodiment of the present invention, at least two Rs, R a , R b , R c A radical consists of those two Rs, R a , R b , R c The radical forms a fused ring with additional groups to which it binds, where two R and R a , R b , R c The radical preferably forms at least one of the structures of formulas (RA-1a) to (RA-4f):

[0120]

[0121]

[0122] The dotted line combination in the equation consists of 2 Rs, R a , R b , R c Indicates an attachment site where a radical binds, index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and symbol R 1 , R 2 , R d and indices s and t have the definitions given above, in particular for Equation (I) and / or Equations (RA-1) through (RA-12).

[0123] In addition, at least two Rs forming a fused ring and forming a structure of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f). a , R b , R c The radical is adjacent X, X 1 , X 2 , X 3 From R, R a , R b , Rc It may represent a radical or an R radical that bonds to adjacent carbon atoms, wherein these carbon atoms are preferably connected through bonding.

[0124] In a further preferred embodiment, at least two Rs, R a , R b , R c A radical consists of those two Rs, R a , R b , R c The radical forms a fused ring with additional groups to which it binds, where two R and R a , R b , R c Radicals form the structure of formula (RB):

[0125]

[0126] R in food 1 ...has the definition given above, specifically for Equation (I), and the dotted line combination is two Rs, R a , R b , R c Indicates a binding site where a radical binds, where index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and Y 5 is C(R 1 )2, NR 1 , NAr, BR 1 , BAr, O or S, preferably C(R 1 )2, NAr' or O is.

[0127] At least two Rs forming the structure of formula (RB) and forming a fused ring, R a , R b , R c The radical is adjacent X, X 1 , X 2 , X 3 From R, R a , R b , R cIt may represent a radical or an R radical that bonds to adjacent carbon atoms, wherein these carbon atoms are preferably connected to each other through bonding.

[0128] More preferably, the compound comprises at least one structure of formulas (VII-1) to (VII-50); more preferably, the compound is selected from compounds of formulas (VII-1) to (VII-50), wherein the compound has at least one fused ring:

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] Symbol Y in the formula 1 , Y 2 , Z 1 , Z 2 , R, R a , R b and R c has the definition given above, in particular for Equation (I), and the symbol Y 3 is given the definition above, in particular for formulas (IIa) through (IIk), the symbol o represents the attachment site of the fused ring, and additional symbols are defined as follows:

[0137] l is 0, 1, 2, 3, 4, or 5, preferably 0, 1, or 2;

[0138] m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2;

[0139] n is 0, 1, 2, or 3, preferably 0, 1, or 2;

[0140] j is 0, 1, or 2, preferably 0 or 1;

[0141] k is 0 or 1.

[0142] Preferably, particularly in formulas (VII-1) to (VII-50), the fusion ring comprises at least two R, R a , R b , R c Radical and its two Rs, R a , R b , R c It is formed by additional groups to which radicals combine, wherein at least two R, R a , R b , R c The radical forms the structure of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or formula (RB), preferably the structure of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0143] Preferably, the compounds have at least two fused rings, wherein at least one fused ring is formed by a structure of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and an additional ring is formed by a structure of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), wherein the compounds comprise at least one structure of formulas (VIII-1) to (VIII-50), and preferably, the compounds may be selected from compounds of formulas (VIII-1) to (VIII-50):

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] Symbol Y in the formula 1 , Y 2 , Z 1 , Z 2 , R, R a , R b and R c has the definition given above, in particular for Equation (I), and the symbol Y 3 has the definition given above, in particular for formulas (IIa) through (IIk), the symbol o indicates the attachment site, and additional symbols have the following definitions:

[0152] l is 0, 1, 2, 3, 4, or 5, preferably 0, 1, or 2;

[0153] m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2;

[0154] n is 0, 1, 2, or 3, preferably 0, 1, or 2;

[0155] j is 0, 1, or 2, preferably 0 or 1; and

[0156] k is 0 or 1.

[0157] In particular, in formulas (VII-1) to (VII-50) and / or (VIII-1) to (VIII-50), the sum of indices k, j, l, m and n is preferably 0, 1, 2 or 3, more preferably 1 or 2.

[0158] Here, formulas (VIII-1) through (VIII-50) have at least two fused rings, wherein the fused rings are identical and have two R, R a , R b , R cThe moiety formed by the radical may be one that can be represented by at least one structure of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0159] Additionally, formulas (VIII-1) to (VIII-50) have at least two fused rings, wherein the fused rings are different and have two R, R a , R b , R c The moiety formed by the radical may be one that can be represented by at least one structure of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) in each case.

[0160] Additionally, formulas (VIII-1) to (VIII-50) have at least two fused rings, wherein the fused rings are different and one of the two fused rings can be represented by at least one of the structures of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), with two R, R a , R b , R c Having a moiety formed by radicals, one of the two fused rings consists of two Rs that can be represented by one of the structures of formula (RB). a , R b , R c It may be a case where it has a moiety formed by radicals.

[0161] In addition, substituents R and R according to the above formula a , R b , R c and R d , R 1 and R 2 is substituent R, R a , R b , R c and R d , R 1 and R 2It may be a case where it does not form an aromatic or heteroaromatic ring system fused with the ring atoms of the ring system to which it bonds. This is R, R a , R b , R c , R d and R 1 Possible substituent R that may be bound to the radical 1 and R 2 It includes the formation of an aromatic or heteroaromatic ring system fused with.

[0162] Especially R, R a , R b , R c , R d , R 1 and / or R 2 When two radicals that may be selected from form a ring system together, this ring system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. In this case, the radicals forming the ring system together may be adjacent, which means that these radicals may be bonded to the same carbon atom, directly bonded to each other, or further apart from each other. Additionally, substituents R, R a , R b , R c , R d , R 1 and / or R 2 This provided ring system may also be interconnected through bonding, which can result in ring closure. In this case, each corresponding bonding site has a substituent R, R a , R b , R c , R d , R 1 and / or R 2 It is desirable that this be provided.

[0163] In a preferred configuration, the compound of the present invention may be represented by at least one of the structures of formula (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20), (V-1) to (V-40), (VI-1) to (VI-40), (VII-1) to (VII-50) and / or (VIII-1) to (VIII-50). Preferably, the compound of the present invention, which preferably comprises the structure of formula (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20), (V-1) to (V-40), (VI-1) to (VI-40), (VII-1) to (VII-50) and / or (VIII-1) to (VIII-50), has a molecular weight of 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, particularly preferably 2000 g / mol or less, and most preferably 1200 g / mol or less.

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

[0165] Desirable aromatic or heteroaromatic ring system R, R a , R b , R c , R d, Ar' and / or Ar is phenyl, biphenyl, particularly ortho-, meta- or para-biphenyl, terphenyl, particularly ortho-, meta- or para-terphenyl or branched terphenyl, quarterphenyl, particularly ortho-, meta- or para-quarterphenyl or branched quarterphenyl, fluorene that may be linked through the 1, 2, 3 or 4 position, spirobifluorene that may be linked through the 1, 2, 3 or 4 position, naphthalene, particularly 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole that may be linked through the 1, 2, 3, 4 or 9 position, dibenzofuran that may be linked through the 1, 2, 3 or 4 position, or dibenzothiophene that may be linked through the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, Selected from pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazolin, quinoxaline, phenanthrene, or triphenylene, each of which is one or more R 1 Alternatively, it may be substituted by an R radical.

[0166] Preferably, at least one substituent R, R a , R b , R c is selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75, wherein the substituents R, R a , R b , R c It preferably forms a ring according to the structure of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or a substituent R, R a , R b , R cis selected from the group consisting of aromatic or heteroaromatic ring systems selected from H, D, or the groups of the following formulas Ar-1 to Ar-75, which are identical or different in each case, and / or the Ar' group may be identical or different in each case and selected from the groups of the following formulas Ar-1 to Ar-75:

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173] During the meal, R 1 ...is as defined above, the dotted connection indicates the attachment site, and also:

[0174] Ar 1 is the same or different in each case, has 6 to 18 aromatic ring atoms, and in each case has one or more R 1 It is a divalent aromatic or heteroaromatic ring system that may be substituted with radicals;

[0175] A is the same or different in each case, and C(R 1 )2, NR 1 , O or S and;

[0176] p is 0 or 1, where p = 0 is Ar 1 It means the absence of a group and the direct bonding of a corresponding aromatic or heteroaromatic group to the corresponding radical;

[0177] q is 0 or 1, where q = 0 means that group A is not coupled at this position, and instead R 1 It means that the radical is bonded to the corresponding carbon atom.

[0178] Where the above-mentioned group for Ar has two or more A groups, possible choices for these include all combinations from the definition of A. In that case, a preferred embodiment is one A group NR 1 and another A giga C(R 1 )2 or both A units are NR 1 These are either or both A groups are O.

[0179] A is NR 1 In this case, substituent R bonded to the nitrogen atom 1 Preferably, it has 5 to 24 aromatic ring atoms and also one or more R 2 It is an aromatic or heteroaromatic ring system that may be substituted by radicals. In a particularly preferred embodiment, this R 1 The substituents are, in each case, identical or different and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which does not have a fused aryl group and does not have a fused heteroaryl group in which two or more aromatic or heteroaromatic six-membered ring groups are directly fused to each other, and also, in each case, one or more R 2 It may also be substituted by radicals. Phenyl, biphenyl, terphenyl, and quadrphenyl having the bonding patterns listed above for Ar-1 to Ar-11 are preferred, wherein these structures are, R 1 Rather than by, one or more R 2 It may be substituted by radicals, but preferably not substituted. For Ar-47 to Ar-50, Ar-57 and Ar-58, the triazines, pyrimidines, and quinazolins listed above are also preferred, wherein these structures are, R 1 Rather than by, one or more R 2 It may also be substituted by radicals.

[0180] Desirable substituents R, R a , R b , R c , and R d An explanation of follows.

[0181] In a preferred embodiment of the present invention, R, R a , R b , R c ...are the same or different in each case, and H, D, F, CN, NO2, Si(R 1 )3, B(OR 1 )2, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms (the alkyl group has one or more R in each case) 1 (may be substituted by radicals), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case, one or more R 1 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals.

[0182] In a further preferred embodiment of the present invention, substituent R, R a , R b , R c ...is the same or different in each case, and H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms (the alkyl group has one or more R in each case). 1 (may be substituted by radicals), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case, one or more R 1 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals.

[0183] Also, at least one substituent R, Ra , R b , R c In each case, they are the same or different, having H, D, 6 to 30 aromatic ring atoms, and one or more R 1 It may be selected from the group consisting of an aromatic or heteroaromatic ring system that may be substituted with a radical, or an N(Ar')2 group. In a further preferred embodiment of the present invention, substituents R, R a , R b , R c ...forms a ring according to the structures of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or R, R a , R b , R c In each case, is the same or different, having H, D, 6 to 30 aromatic ring atoms, and one or more R 1 It is selected from the group consisting of an aromatic or heteroaromatic ring system that may be substituted with a radical, or an N(Ar')2 group. More preferably, substituent R, R a , R b , R c Each of these is the same or different and has H, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms (each of these having one or more R 1 It is selected from the group consisting of (which may be substituted by radicals).

[0184] In a preferred embodiment of the present invention, R d is the same or different in each case, and is a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms (the alkyl group has one or more R in each case). 1(may be substituted by radicals), or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case, one or more R 1 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals.

[0185] In a further preferred embodiment of the present invention, R d is the same or different in each case, and is a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms (the alkyl group has one or more R in each case). 1 (may be substituted by radicals), having 6 to 30 aromatic ring atoms and one or more R 1 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals. More preferably, R a is the same or different in each case, and is a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 5 carbon atoms (the alkyl group has one or more R in each case). 1 (may be substituted by radicals), or having 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, one or more R 1 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals.

[0186] In a preferred embodiment of the present invention, R d is, in each case, the same or different, a straight-chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms (the alkyl group has one or more R in each case). 1(may be substituted with radicals), or having 6 to 24 aromatic ring atoms and in each case one or more R 1 Selected from the group consisting of aromatic or heteroaromatic ring systems that may be substituted with radicals; simultaneously, two R d Radicals may also form a ring system together. More preferably, R d is, in each case, the same or different, a straight-chain alkyl group having 1, 2, 3, or 4 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms (the alkyl group has one or more Rs in each case). 1 It may be substituted with radicals, but preferably not substituted), or having 6 to 12 aromatic ring atoms, particularly 6 aromatic ring atoms, and in each case, one or more preferably non-aromatic R 1 Selected from the group consisting of aromatic ring systems that may be substituted with radicals but preferably are not; at the same time, two R d Radicals can also form a ring system together. Most preferably, R d is selected from the group consisting of straight-chain alkyl groups having 1, 2, 3, or 4 carbon atoms, or branched alkyl groups having 3 to 6 carbon atoms, which are the same or different in each case. Most preferably, R d is a methyl group or a phenyl group, where two phenyl groups can form a ring system together, and a methyl group is preferred over a phenyl group.

[0187] Desirable aromatic or heteroaromatic ring system substituents R, R a , R b , R c , R dor Ar or Ar' is phenyl, biphenyl, particularly ortho-, meta- or para-biphenyl, terphenyl, particularly ortho-, meta- or para-terphenyl or branched terphenyl, quarterphenyl, particularly ortho-, meta- or para-quarterphenyl or branched quarterphenyl, fluorene that may be linked through the 1, 2, 3 or 4 position, spirobifluorene that may be linked through the 1, 2, 3 or 4 position, naphthalene, particularly 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole that may be linked through the 1, 2, 3 or 4 position, dibenzofuran that may be linked through the 1, 2, 3 or 4 position, or dibenzothiophene that may be linked through the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, Selected from pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazolin, quinoxaline, phenanthrene, or triphenylene, each of which is one or more R, R 1 or R 2 It may also be substituted by radicals. The structures Ar-1 to Ar-75 listed above are particularly preferred, and the structures of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75) are preferred, and the structures of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred. With respect to structures Ar-1 to Ar-75, these have substituent R 1 It should be mentioned that it is indicated as having. In the case of the cyclic system Ar, these substituents R 1 must be replaced with R, and R d In the case of these substituents R 1 is R 2 It should be replaced with.

[0188] Additional suitable R, R a , R b , R c Gi is the formula -Ar 4 -N(Ar 2 )(Ar 3 ) investing in and here Ar 2 , Ar 3 and Ar 4 In each case, it is the same or different and has 5 to 24 aromatic ring atoms, and in each case, one or more R 1 It is an aromatic or heteroaromatic ring system that may be substituted by radicals. Here, Ar 2 , Ar 3 and Ar 4 The total number of aromatic ring atoms in is 60 or less, and preferably 40 or less.

[0189] In this case, Ar 4 and Ar 2 may also be combined with each other or and / or Ar 2 and Ar 3 is C(R 1 )2, NR 1 They may also be bonded to each other by groups selected from , O and S. Preferably, Ar 4 and Ar 2 Giga mutually and Ar 2 and Ar 3 They are connected at their respective ortho positions to the bond to the nitrogen atom. In a further embodiment of the present invention, Ar 2 , Ar 3 and Ar 4 None of the gis combine with each other.

[0190] Preferably, Ar 4 It has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in each case, one or more R 1 It is an aromatic or heteroaromatic ring system that may be substituted by radicals. More preferably, Ar 4is selected from the group consisting of ortho-, meta-, or para-phenylene or ortho-, meta-, or para-biphenyl, and each of these is one or more R 1 It may be substituted by radicals, but preferably not. Most preferably, Ar 4 is an unsubstituted phenylene group.

[0191] Preferably, Ar 2 and Ar 3 is the same or different in each case, has 6 to 24 aromatic ring atoms, and in each case has one or more R 1 It is an aromatic or heteroaromatic ring system that may be substituted with radicals. Particularly desirable Ar 2 and Ar 3 The group is the same or different in each case and is benzene, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl or branched terphenyl, ortho-, meta- or para-quaternphenyl or branched quaternphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophen, 1-, 2-, 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophen, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, Pyridazine, triazine, phenanthrene, or triphenylene (each of which has one or more R 1 It is selected from the group consisting of (which may be substituted by radicals). Most preferably, Ar 2 and Ar 3In each case, it is the same or different and is selected from the group consisting of benzene, biphenyl, particularly ortho-, meta- or para-biphenyl, terphenyl, particularly ortho-, meta- or para-terphenyl or branched terphenyl, quarterphenyl, particularly ortho-, meta- or para-quarterphenyl or branched quarterphenyl, fluorene, particularly 1-, 2-, 3- or 4-fluorene, or spirobifluorene, particularly 1-, 2-, 3- or 4-spirobifluorene.

[0192] In a further preferred embodiment of the present invention, R 1 ...is the same or different in each case, and is a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms (wherein the alkyl group is one or more R in each case). 2 (may be substituted by radicals), or having 6 to 24 aromatic ring atoms and in each case one or more R 2 It is selected from the group consisting of aromatic or heteroaromatic ring systems that can be substituted by radicals. In a particularly preferred embodiment of the present invention, R 1 is the same or different in each case, and is a straight-chain alkyl group having 1 to 6 carbon atoms, particularly having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms (the alkyl group has one or more R 5 It may be substituted by radicals, but preferably not substituted), or having 6 to 13 aromatic ring atoms and in each case one or more R 5 It is selected from the group consisting of aromatic or heteroaromatic ring systems that may be substituted with radicals, but preferably are not substituted.

[0193] In a further preferred embodiment of the present invention, R 2In each case, it is the same or different and is H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms (which may be substituted with an alkyl group having 1 to 4 carbon atoms, but preferably not substituted).

[0194] At the same time, in the compounds of the present invention treated by vacuum evaporation, the alkyl group preferably has five or fewer carbon atoms, more preferably four or fewer carbon atoms, and most preferably one or fewer carbon atoms. For the compounds treated from solution, suitable compounds are also those substituted by alkyl groups having 10 or fewer carbon atoms, in particular, branched alkyl groups, or oligoarylene groups, for example, ortho-, meta-, para-terphenyl or branched terphenyl or quarterphenyl groups.

[0195] Additionally, the compound comprises exactly two or exactly three structures of formula (I), (IIa) to (IIk), (IIIa) to (IIIk), (IV-1) to (IV-20), (V-1) to (V-40), (VI-1) to (VI-40), (VII-1) to (VII-50) and / or (VIII-1) to (VIII-50), wherein Y 1 , X 1 , X 2 , X 3 Preferably, one of the aromatic or heteroaromatic ring systems to which at least one of the groups is bonded may be shared by two structures.

[0196] In a preferred configuration, the compound is selected from the compounds of formula (D-1), (D-2), (D3) or (D-4):

[0197]

[0198]

[0199] During the meal, L 1The group is an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, aromatic ring atoms and capable of being substituted by one or more R radicals, and additional symbols and indices used have the definitions given above, particularly for formulas (V-1) to (V-40).

[0200] In a further preferred embodiment of the present invention, L 1 It is a silver 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 one or more R 1 It is an aromatic ring system that may be substituted with a radical, but preferably is not substituted, where R 1 may have the given definition above, particularly with respect to Equation (I). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which has one or more R 2 It may be substituted with a radical, but preferably not substituted, where R 2 It may have the definition given above, especially for Equation (I).

[0201] Additionally, preferably, the symbol L, particularly as indicated in Equation (D4). 1 In each case, it is the same or different, and is an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, and as a result, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly to each atom of the additional group, that is, through the atom of the aromatic or heteroaromatic group.

[0202] Additionally, L shown in Equation (D4) 1 The group comprises an aromatic ring system having two or fewer fused aromatic and / or heteroaromatic six-membered rings, and preferably, may not comprise any fused aromatic or heteroaromatic ring system. Thus, a naphthyl structure is preferred over an anthracene structure. Additionally, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over a naphthyl structure.

[0203] Structures that do not have fusion, for example, phenyl, biphenyl, terphenyl and / or quadrphenyl structures are particularly preferred.

[0204] Suitable aromatic or heteroaromatic ring system L 1 Examples of are ortho-, meta-, or para-phenylene, ortho-, meta-, or para-biphenylene, terphenylene, particularly branched terphenylene, quadrphenylene, particularly branched quadrphenylene, fluorenylene, spirobifluorenylene, dibenzofuranilene, dibenzothienylene, and carbazolylene (each of these having one or more R 1 It is selected from the group consisting of (which may be substituted with radicals, but preferably not substituted).

[0205] The preferred embodiments mentioned above may be combined with one another as desired within the limitations defined in Claim 1. In a particularly preferred embodiment of the present invention, the preferred embodiments mentioned above occur simultaneously.

[0206] Examples of preferred compounds according to the embodiments described in detail above are the compounds shown in the table below:

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228] Preferred embodiments of the compounds of the present invention are described in more detail in the examples, and these compounds may be used in combination with additional compounds or alone for all purposes of the present invention.

[0229] As long as the conditions specified in Claim 1 are satisfied, the preferred embodiments mentioned above may be combined with one another as desired. In a particularly preferred embodiment of the present invention, the preferred embodiments mentioned above are applied simultaneously.

[0230] The compounds of the present invention can, in principle, be prepared by various methods. However, it has been found that the method described below is particularly suitable.

[0231] Accordingly, the present invention also provides a method for preparing the compound of the present invention, wherein Z 1 Gi or Z 2 Gi or Z 1 , Z 2 A base framework having one of the precursors is synthesized, and Y 1 , Y 2 A method for manufacturing is provided in which at least one of the groups is introduced by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0232] Z 1 Gi or Z 2 Suitable compounds comprising a base backbone having a group are commercially available in many cases, and the starting compounds described in detail in the examples can be obtained by known methods, so reference is made thereto.

[0233] These compounds may be reacted with additional compounds by known coupling reactions, and the necessary conditions for this purpose are known to those skilled in the art, and the detailed specifications in the examples provide support to those skilled in the art in carrying out these reactions.

[0234] Particularly suitable and desirable coupling reactions leading to the formation of CC bonds and / or CN bonds are the reactions according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are widely known, and the examples will provide further guidance to those skilled in the art.

[0235] The principle of the manufacturing method described above is, in principle, known from the literature on similar compounds and can be easily adapted by those skilled in the art for the manufacture of the compounds of the present invention. Further information can be found in the examples.

[0236] Following this method, if necessary, the compound of the present invention is purified, for example by recrystallization or sublimation, to a high purity, preferably exceeding 99% ( 1 It can be obtained by determining using 1H NMR and / or HPLC.

[0237] The compounds of the present invention may also be mixed with polymers. Likewise, these compounds can be incorporated into polymers by covalent bonding. This is particularly possible with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic esters, or by reactive polymerizable groups such as olefins or oxetanes. These can be used as monomers for the preparation of corresponding oligomers, dendrimers, or polymers. Oligomerization or polymerization is preferably carried out through halogen functional groups or boronic acid functional groups, or through polymerizable groups. Additionally, polymers can be crosslinked through these types of groups. The compounds and polymers of the present invention may be used in the form of crosslinked or non-crosslinked layers.

[0238] Accordingly, the present invention also provides an oligomer, polymer, or dendrimer containing one or more of the structures of Formula (I) and preferred embodiments of the formula described in detail above, or a compound of the present invention, wherein one or more bonds of the structure of Formula (I) and preferred embodiments of the formula are present with respect to the polymer, oligomer, or dendrimer. Accordingly, depending on the connection of the structure of Formula (I) and preferred embodiments of the formula, they form side chains of the oligomer or polymer or are bonded within the main chain. The polymer, oligomer, or dendrimer may be conjugated, partially conjugated, or non-conjugated. The oligomer or polymer may be linear, branched, or dendritic. With respect to the repeating unit of the compound of the present invention among the oligomer, dendrimer, and polymer, the same preferred features as described above apply.

[0239] For the preparation of an oligomer or polymer, the monomer of the present invention is homopolymerized or copolymerized with an additional monomer. The units of Formula (I) or the preferred embodiments mentioned above and below are preferably a copolymer present in an amount of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, more preferably 20 to 80 mol%. Suitable and preferred comonomers forming the polymer base backbone are fluorene (e.g., according to EP 842208 or WO 2000 / 022026), spirobifluorene (e.g., according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylene (e.g., according to WO 92 / 18552), carbazole (e.g., according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (e.g., according to EP 1028136), dihydrophenanthrene (e.g., according to WO 2005 / 014689), and cis- and trans-indenofluorene (e.g., WO 2004 / 041901 or WO 2004 / 113412). (according to), ketone (e.g., according to WO 2005 / 040302), phenanthrene (e.g., according to WO 2005 / 104264 or WO 2007 / 017066), or otherwise selected from a plurality of these units. Polymers, oligomers, and dendrimers may still contain other units, e.g., hole transport units, particularly those based on triarylamines, and / or electron transport units.

[0240] In addition, compounds of the present invention characterized by a high glass transition temperature are particularly interesting. In this regard, compounds of the present invention comprising the structure of formula (I) or preferred embodiments mentioned above and below, wherein the glass transition temperature is determined according to DIN 51005 (version 2005-08), at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, and particularly preferably at least 150°C.

[0241] For example, to process the compounds of the present invention from a liquid phase by a spin-coating or printing method, a formulation of the compounds of the present invention is required. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, particularly 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, Dodecylbenzene, Ethyl Benzoate, Indane, NMP, p-Cymene, Penethol, 1,4-Diisopropylbenzene, Dibenzyl Ether, Diethylene Glycol Butyl Methyl Ether, Triethylene Glycol Butyl Methyl Ether, Diethylene Glycol Dibutyl Ether, Triethylene Glycol Dimethyl Ether, Diethylene Glycol Monobutyl Ether, Tripropylene Glycol Dimethyl Ether, Tetraethylene Glycol Dimethyl Ether, 2-Isopropylnaphthalene, Pentylbenzene, Hexylbenzene, Heptylbenzene, Octylbenzene, 1,1-Bis(3,4-Dimethylphenyl)ethane, 2-Methylbiphenyl, 3-Methylbiphenyl, 1-Methylnaphthalene, 1-Ethylnaphthalene, Ethyl Octanoate, Diethyl Sebacate, Octyl Octanoate, Heptylbenzene, Menthyl It is isovalerate, cyclohexyl hexanoate, or a mixture of these solvents.

[0242] Accordingly, the present invention also provides a formulation or composition comprising at least one compound of the present invention and at least one additional compound. The additional compound may be, for example, a solvent, in particular one of the solvents mentioned above or a mixture of these solvents. If the additional compound comprises a solvent, this mixture is referred to herein as a formulation. Alternatively, the additional compound may be at least one additional organic or inorganic compound likewise used in electronic devices, for example, an emitter and / or matrix material, wherein these compounds differ from the compound of the present invention. Suitable emitter and matrix materials are listed below in relation to organic electroluminescent devices. The additional compound may also be polymeric.

[0243] Accordingly, the present invention also provides a composition comprising the compound of the present invention and at least one additional organic functional material. The functional material is generally an organic or inorganic material introduced between an anode and a cathode. Preferably, the organic functional material is selected from the group consisting of a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF (thermally activated delayed fluorescence), a host material, an electron transport material, an electron injection material, a hole conductor material, a hole injection material, an electron blocking material, a hole blocking material, a wide bandgap material, and an n-dopant.

[0244] The present invention also provides for the use of the compounds of the present invention in electronic devices, particularly in organic electroluminescent devices, preferably as emitters, more preferably as green, red, or blue emitters. In this case, the compounds of the present invention preferably exhibit fluorescent properties and thus preferentially provide fluorescent emitters. Additionally, the compounds of the present invention may be used as host materials, electron transport materials, and / or hole conductor materials. Here, Z 1 , Z 2, Z 3 , Z 4 It is particularly possible to advantageously use the compounds of the present invention, in which many, preferably all, of the group are N, as hole conductor materials. In addition, Z 1 , Z 2 , Z 3 , Z 4 It is particularly possible to use the compounds of the present invention, in which many, preferably all, of the group are B, as advantageous electron transport materials.

[0245] The present invention also provides an electronic device comprising at least one compound of the present invention. In the context of the present invention, the electronic device is a device comprising at least one layer comprising at least one organic compound. This component may also comprise a layer formed entirely from an inorganic material or otherwise from an inorganic material.

[0246] The electronic device is preferably selected from the group consisting of the following, and more preferably the electronic device is an organic electroluminescent device (OLED, sOLED, PLED, LEC, etc.), preferably an organic light-emitting diode (OLED), a small molecule-based organic light-emitting diode (sOLED), a polymer-based organic light-emitting diode (PLED), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser), an organic plasmon-emitting device (DM Koller et al. , Nature Photonics 2008, 1-4), selected from the group consisting of organic integrated circuits (O-IC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic light-emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photosensitive materials, organic field quench devices (O-FQD) and organic electric sensors, preferably organic field-emitting devices (OLED, sOLED, PLED, LEC, etc.), more preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), in particular phosphorescent OLEDs.

[0247] An organic electroluminescent device comprises a cathode, an anode, and at least one emission layer. In addition to these layers, it may also include additional layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers in each case. Similarly, an intermediate layer having an exciton blocking function may be introduced, for example, between two emission layers. However, it should be noted that not all of these layers necessarily need to be present. In this case, the organic electroluminescent device may comprise a single emission layer or multiple emission layers. If multiple emission layers are present, they are preferably to have multiple emission maxima between 380 nm and 750 nm in total so that the overall result is white emission; in other words, various emission compounds that may exhibit fluorescence or phosphorescence are used in the emission layers. A system having three emission layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, particularly for white-emitting OLEDs.

[0248] The compounds of the present invention may be used in different layers depending on the exact structure. An organic electroluminescent device comprising a compound of formula (I) or a preferred embodiment detailed above in an emission layer as an emitter, preferably a red, green, or blue emitter is preferred.

[0249] When the compound of the present invention is used as a emitter in an emission layer, it is preferable to use a suitable matrix material known as itself.

[0250] A preferred mixture of the compound and matrix material of the present invention contains the matrix material in an amount of 99 volume% to 1 volume%, preferably 98 volume% to 10 volume%, more preferably 97 volume% to 60 volume%, and particularly 95 volume% to 80 volume%, based on the total mixture of the emitter and matrix material. Correspondingly, the mixture contains the emitter in an amount of 1 volume% to 99 volume%, preferably 2 volume% to 90 volume%, more preferably 3 volume% to 40 volume%, and particularly 5 volume% to 20 volume%, based on the total mixture of the emitter and matrix material.

[0251] Suitable matrix materials that can be used in combination with the compounds of the present invention are, for example, aromatic ketones, aromatic phosphine oxides, aromatic sulfoxides, or sulfones, triarylamines, carbazole derivatives according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680, for example, CBP (N,N-biscarbazolylbiphenyl), or carbazole derivatives described in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851, or WO 2013 / 041176, for example, according to WO 2007 / 063754 or WO 2008 / 056746. Indolocarbazole derivatives, e.g., indenocarbazole derivatives according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, e.g., EP 1617710, EP 1617711, EP 1731584, azacarbazole derivatives according to JP 2005 / 347160, e.g., bipolar matrix materials according to WO 2007 / 137725, e.g., silanes according to WO 2005 / 111172, e.g., azaborol according to WO 2006 / 117052, or boronic esters, e.g., WO 2007 / 063754, WO 2008 / 056746, WO Triazine derivatives according to 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, e.g., zinc complexes according to EP 652273 or WO 2009 / 062578, e.g., diazacilol or tetraazcilol derivatives according to WO 2010 / 054729, e.g., diazaphosphol derivatives according to WO 2010 / 054730, e.g., WO 2011 / 042107, WO 2011 / 060867,Bridging carbazole derivatives according to WO 2011 / 088877 and WO 2012 / 143080, e.g., triphenylene derivatives according to WO 2012 / 048781, e.g., dibenzofuran derivatives according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565, or e.g., biscarbazole according to JP 3139321 B2.

[0252] In addition, the co-host used may be a compound that, even if present, does not participate in charge transport, as described, for example, in WO 2010 / 108579. A compound having a large band gap and, even if, itself does not participate in charge transport in the emission layer to at least a significant degree is particularly suitable to be combined with the compound of the present invention as a co-matrix material. Such a material is preferably a pure hydrocarbon. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0253] In a preferred configuration, the compound of the present invention used as an emitter is preferably used in combination with a compound that is one or more phosphorescent materials (triplet emitters) and / or TADF (thermally activated delayed fluorescence) host materials. Here, it is preferable to form a hyperfluorescence and / or hyperphosphorescence system.

[0254] WO 2015 / 091716 A1 and WO 2016 / 193243 A1 disclose an OLED containing both a phosphorescent compound and a fluorescent emitter in the emission layer, wherein energy is transferred from the phosphorescent compound to the fluorescent emitter (superphosphorescence). In this context, the phosphorescent compound accordingly behaves as a host material. As is known to those skilled in the art, the host material has higher singlet and triplet energies compared to the emitter so that energy from the host material can also be transferred to the emitter with maximum efficiency. Systems disclosed in the prior art have exactly such energy relationships.

[0255] Phosphorescence is understood in the context of the present invention to mean luminescence from an excited state having a higher spin multiplicity, i.e., a spin state > 1, in particular an excited triplet state. In the context of the present application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum, and copper complexes, should be considered as phosphorescent compounds.

[0256] Suitable phosphorescent compounds (= triplet emitters) are compounds that, in particular, when suitably excited, preferably emit light in the visible region, and also contain at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, particularly a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, in particular compounds containing iridium or platinum.

[0257] Examples of the emitters described above are applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 001990, WO 2018 / 019687, WO It can be found in WO 2018 / 019688, WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197, WO 2018 / 069273, WO 2018 / 178001, WO 2018 / 177981, WO 2019 / 020538, WO 2019 / 115423, WO 2019 / 158453 and WO 2019 / 179909. In general, all phosphorescent complexes as used in phosphorescent electroluminescent devices according to the prior art and as known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art may use additional phosphorescent complexes without exercising progressive ability.

[0258] The compound of the present invention may preferably be used in combination with a TADF host material and / or a TADF emitter as described above.

[0259] A method referred to as thermally activated delayed fluorescence (TADF) is described, for example, by [BH Uoyama et al., Nature 2012, Vol. 492, 234]. To enable this method, for example, about 2000 cm⁻¹ -1 A relatively small singlet-triplet separation △E(S1-T1) of less than 1 is required in the emitter. In order to open the T1→S1 transition, which is, in principle, spin-forbidden, as well as in the emitter, additional compounds in the matrix with strong spin-orbit coupling can be provided, thus enabling cross-systems through possible intermolecular interactions and spatial proximity, or spin-orbit coupling is generated by metal atoms present in the emitter.

[0260] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the emission layer is immediately adjacent to the hole injection layer or the anode and / or the emission layer is immediately adjacent to the electron transport layer or the electron injection layer or the cathode (e.g., as described in WO 2005 / 053051). Additionally, as described in WO 2009 / 030981, a metal complex identical or similar to the metal complex in the emission layer may be used as a hole transport or hole injection material immediately adjacent to the emission layer.

[0261] In addition, an organic electroluminescent device comprising a hole conductive layer containing a compound of formula (I) or a preferred embodiment detailed above as a hole conductor material is preferred. Here, Z 1 and Z 2 At least one of the elements, preferably two, is N and Y 1 and Y 2A compound in which at least one, preferably two, of the groups is N(Ar), N(R), P(Ar), P(R), O, S, or Se, preferably N(Ar), N(R), O, or S, and more preferably N(Ar), is particularly preferred. In addition, Z 1 , Z 2 At least one or preferably two of the elements are N and Z 3 , Z 4 A compound in which at least one, preferably two, of the group is N is particularly preferred here.

[0262] In addition, an organic electroluminescent device comprising a compound of formula (I) or a preferred embodiment detailed above as an electron transport material in an electron conductive layer is preferred. Z 1 and Z 2 At least one or preferably two of the elements are B and Z 3 and Z 4 A compound in which at least one, preferably two, of the groups is B is preferred here. Also, Z 1 , Z 2 At least one or preferably two of the elements are B and Z 3 , Z 4 A compound in which at least one, preferably two, of the group is B is particularly preferred here.

[0263] In an additional layer of the organic electroluminescent device of the present invention, any material typically used according to the prior art may be used. Thus, those skilled in the art will be able to use any material known for organic electroluminescent devices in combination with the compounds of Formula (I) or the preferred embodiments of the present invention mentioned above without exercising inventive capability.

[0264] An organic electroluminescent device characterized by having one or more layers coated by a sublimation method is also preferred. In this case, the material is 10 -5 Less than mbar, preferably 10 -6It is applied by deposition in a vacuum sublimation system at an initial pressure of less than mbar. However, the initial pressure is also much lower, for example, 10 -7 It may be less than mbar.

[0265] Likewise, an organic electroluminescent device is preferred, characterized in that one or more layers are coated by an OVPD (organic vapor phase deposition) method or with the help of carrier gas sublimation. In this case, the materials are 10 -5 It is applied at pressures of mbar to 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which materials are applied directly by a nozzle and structured.

[0266] Additionally, an organic electroluminescent device is preferred, characterized in that one or more layers are prepared from a solution, for example by spin coating, or by any printing method, for example, screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging, thermal transfer printing), inkjet printing, or nozzle printing. For this purpose, a soluble compound obtained, for example, through suitable substitution is required.

[0267] The formulation for the application of the compound of Formula (I) or the preferred embodiment thereof described above is novel. Accordingly, the present invention further provides a formulation comprising at least one solvent and the compound according to Formula (I) or the preferred embodiment thereof described above.

[0268] In addition, a hybrid method is possible in which, for example, one or more layers are applied from a solution and one or more additional layers are applied by deposition.

[0269] Those skilled in the art generally know these methods and can apply them to organic electroluminescent devices containing the compounds of the present invention without exercising progressive capabilities.

[0270] The compounds of the present invention and the organic electroluminescent devices of the present invention have specific features of improved lifespan compared to the prior art. At the same time, additional electronic characteristics of the electroluminescent devices, such as efficiency or operating voltage, are maintained in at least equally good condition. In further variations, the compounds of the present invention and the organic electroluminescent devices of the present invention are particularly characterized by improved efficiency and / or operating voltage and a higher lifespan compared to the prior art.

[0271] The electronic device of the present invention, in particular the organic electroluminescent device, is notable for one or more of the following remarkable advantages over the prior art:

[0272] 1. An electronic device comprising a compound of formula (I) or a preferred embodiment as the emitter mentioned above and below, in particular an organic electroluminescent device, has a very low FWHM ( F ull W idth H alf M It has a very narrow emission band with an aximum value and reaches particularly pure color emission recognizable by a low CIE y value. What is particularly surprising here is that both a blue emitter with a low FWHM value and an emitter with a low FWHM emitting in the green, yellow, or red regions of the color spectrum are provided.

[0273] 2. An electronic device, particularly an organic electroluminescent device, comprising the compound of formula (I) or the preferred embodiment described above and below, particularly as an emitter, particularly as a hole conductor material and / or an electron transport material, has a very good lifetime. In this context, these compounds result in a low roll-off, that is, a small degradation of the device power efficiency at high brightness.

[0274] 3. An electronic device, particularly an organic electroluminescent device, comprising formula (I) or a compound of a preferred embodiment described above and below, has excellent efficiency as an emitter, particularly as a hole conductor material and / or as an electron transport material. In this context, a compound of the present invention having the structure of formula (I) or a preferred embodiment described above and below results in a low operating voltage when used in an electronic device.

[0275] 4. Formula (I) of the present invention or the compounds of the preferred embodiments described above and below exhibit very high stability and lifespan.

[0276] 5. By using the compound of formula (I) or the preferred embodiment mentioned above and below, the formation of light loss channels in electronic devices, particularly organic electroluminescent devices, can be avoided. As a result, these devices are characterized by high PL efficiency of the emitter and consequently high EL efficiency, and excellent energy transfer from the matrix to the dopant.

[0277] 6. Formula (I) or the compounds of the preferred embodiments mentioned above and below have excellent glass film formation.

[0278] 7. The compounds of formula (I) or the preferred embodiments mentioned above and below form a very good film from a solution and exhibit excellent solubility.

[0279] These aforementioned advantages do not entail excessive degradation of additional electronic characteristics.

[0280] It should be noted that variations of the embodiments described in the present invention are covered by the scope of the present invention. Any feature disclosed in the present invention may be exchanged for an alternative feature that provides the same purpose or an equivalent or similar purpose, unless explicitly excluded. Accordingly, any feature disclosed in the present invention should be considered as an example of a generic series or as an equivalent or similar feature, unless otherwise stated.

[0281] All features of the present invention may be combined with one another in any manner, provided that specific features and / or steps are not mutually exclusive. This applies particularly to the preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (rather than in combination).

[0282] Furthermore, it should be noted that many features of the present invention and features of particularly preferred embodiments should be regarded as inventions in themselves and not merely as part of embodiments of the present invention. With respect to these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.

[0283] The technical teachings disclosed in the present invention may be extracted or combined with other examples.

[0284] The present invention is illustrated in more detail by the following examples, but is not intended to limit the invention. Those skilled in the art will be able to use the given information to practice the present invention over the entire scope disclosed, and to manufacture additional compounds of the present invention without exercising inventive capability, and to use them in electronic devices or the methods of the present invention. Specific details for implementing the invention

[0285] Example:

[0286] The following syntheses are performed in dry solvents under a protective gas atmosphere unless otherwise noted. Metal complexes are additionally handled in the absence of light or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. Each number in brackets or the number cited for an individual compound refers to the CAS number of the compound known in the literature. For compounds that may have multiple enantiomers, diastereomers, or tautomeric forms, one form is shown in a representative manner.

[0287] Synthesis of Sinton S:

[0288] Yes S1:

[0289]

[0290] A procedure similar to that of Chung-Chieh Lee et al., Synthesis 2008, 9, 1359. A complete procedure including post-treatment in a shielding gas.

[0291] A mixture of 34.0 g (120 mmol) of 1-bromo-2-iodobenzene [583-55-1], 8.5 g (50 mmol) of 2,3-dihydro-1H-perimidine [69098-80-2], 20.7 g (150 mmol) of potassium carbonate, 1.9 g (10 mmol) of copper iodide [7681-65-4], 2.9 g (20 mmol) of 1R,2R-N,N-dimethylcyclohexane-1,2-diamine [67579-81-8], 50 g of glass beads, and 200 ml of o-xylene is stirred at 130°C for 24 hours. After cooling, 300 ml of ethyl acetate and 500 ml of water were added to the reaction mixture, the organic phase was removed, washed once with 500 ml of water and twice with 300 ml of saturated sodium chloride solution each time, and dried over magnesium sulfate. The mixture was filtered through a silica gel layer in the form of an ethyl acetate slurry, the filtrate was concentrated and dried, the residue was boiled with 150 ml of ethanol, the solid was suction-filtered, washed twice with 30 ml of ethanol, dried under reduced pressure, and recrystallized from acetonitrile / DCM (dichloromethane). Further purification can be performed by flash chromatography on an automated column system (Torrent from A. Semrau). Yield: 15.8 g (33 mmol) 65%; Purity: 1 Approximately 95% by 1H NMR.

[0292] The following compounds can be prepared similarly:

[0293]

[0294]

[0295]

[0296]

[0297]

[0298] Yes, Dopant D1:

[0299] Steps 1 through 3 of the following sequence are carried out as a three-stage one-pot reaction. Post-treatment in step 3 is carried out under a shielding gas.

[0300] Step 1: Lithium oxidation of S1:

[0301]

[0302] 1700 ml of baked-out, argon-inert 4-neck flask with magnetic stirrer rod, dropping funnel, water separator, reflux condenser and argon blanket tert- 24.0 g (50 mmol) of S1 in butylbenzene is charged. The reaction mixture is cooled to -40°C, and then, n- 1.9M of pentane, tert- Add 110.5 ml (210 mmol) of butyllithium dropwise. Stir the mixture at -40°C for an additional 30 minutes, allow it to warm to room temperature, then heat to 70°C, and during this process n- Pentane is distilled through a water separator over a period of about 1 hour.

[0303] Step 2: Transmetalation and Cyclation

[0304]

[0305] The reaction mixture is cooled again to -40°C. 10.4 ml (110 mmol) of boron tribromide is added dropwise over a period of approximately 10 minutes. Upon completion of the addition, the reaction mixture is stirred at room temperature for 1 hour. Subsequently, the reaction mixture is cooled to 0°C, and the -Iso 19.2 ml (110 mmol) of propylethylamine is added dropwise over a period of approximately 30 minutes. Then, the reaction mixture is stirred at 160°C for 16 hours. After cooling, D -Iso- Propylethylammonium hydrobromide is filtered using a double-ended frit, and the filtrate is cooled to -78°C.

[0306] Step 3: Arylization

[0307]

[0308] 27.8 g (150 mmol) of 2-bromo-1,3-dimethylbenzene [576-22-7] in 1000 ml of diethyl ether was charged into a second baked-out, argon-inert Schlenk flask equipped with a magnetic stirring bar and cooled to -78°C. Next, 60.0 ml (150 mmol) of 2.5 M n-butyllithium in n-hexane was added dropwise, and the mixture was stirred for an additional 30 minutes. The reaction mixture was heated to room temperature and stirred for an additional 1 hour, and the solvent was completely removed under reduced pressure. Lithium organyl was suspended in 300 ml of toluene and transferred to the cryogenic reaction mixture from Step 2. The mixture was stirred for an additional 1 hour, and the reaction mixture was heated overnight to reach room temperature. 15 ml of acetone was carefully added to the reaction mixture and concentrated and dried. The oily residue was isolated with DCM. ® It is absorbed into the phase and high-temperature filtered through a silica gel layer with a pentane-DCM mixture (10:1). The filtrate is concentrated and dried. Flash chromatography (silica gel, n - Perform the heptane / ethyl acetate, Torrent automated column system from A. Semrau twice.

[0309] Step 4: Oxidation to D1

[0310]

[0311] R. Doringer et al., Monatshefte f Procedure similar to r Chemie, 2006, 137, 185. Take up the product from Step 3 into 150 ml of chlorobenzene, add 20 g of activated 3A molecular sieve, and stir the mixture in a dark room under air at 60°C until oxidation is complete (approx. 5 hours). Filter the molecular sieve, rinse with a small amount of chlorobenzene, and concentrate and dry the mixture under reduced pressure. Flash chromatography (silica gel, n - Heptane / ethyl acetate (Torrent automated column system from A. Semrau) is performed twice. Further purification is achieved by repeated high-temperature extraction crystallization using DCM / acetonitrile and final fractional sublimation or heat treatment under reduced pressure. Yield: 12.43 g (22 mmol) 44%; Purity: 1 Approximately 99.9% by 1H NMR.

[0312] The following compounds can be prepared similarly:

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322] Yes, dopants D6PA, D6PB, and D6PC

[0323]

[0324] Preparation from D6 by flash vacuum pyrolysis, carrier gas: argon, reduced pressure approx. 10°C -2torr, pyrolysis zone temperature 550℃, catalyst: 1% PdO on alumina. Chromatographic separation, DCM / n-heptane, silica gel. Yield: D100A 9%; D100B 15%, D100C 8%.

[0325] Manufacturing of OLED components

[0326] 1) Vacuum-treated components:

[0327] The OLED of the present invention and the OLED according to the prior art are manufactured by a general method according to WO 2004 / 058911, which is adapted to the circumstances described herein (variation in layer thickness, materials used).

[0328] In the following examples, results for various OLEDs are presented. A cleaned glass plate coated with a 50 nm thick structured ITO (indium tin oxide) (Miele laboratory glass cleaner, cleaned in Merck Extran detergent) is pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator, UVP manufactured), and within 30 minutes, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-on from aqueous solution) for improved processing, and then fired at 180°C for 10 minutes. These coated glass plates form a substrate to which an OLED is applied.

[0329] The OLED basically has the following layer structure: a substrate / a hole injection layer 1 (HIL1) consisting of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm / a hole transport layer 1 (HTL1) consisting of 150 nm HTM1 for UV and blue OLEDs; 50 nm for green and yellow OLEDs; and 110 nm for red OLEDs / a hole transport layer 2 (HTL2) consisting of 10 nm for blue OLEDs; 20 nm for green and yellow OLEDs; and 10 nm for red OLEDs / an emission layer (HTL2): 25 nm for blue OLEDs; 40 nm for green and yellow OLEDs; and 35 nm for red OLEDs / a hole blocking layer (HBL) 10 nm / an electron transport layer (ETL) 30 nm / an electron injection layer (EIL) consisting of 1 nm ETM2 / and finally a cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm.

[0330] First, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal evaporation in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emission dopant (emitter) added to the matrix material(s) in specific volume ratios by co-evaporation. Details given in this form, such as SMB1:D1 (95:5%), mean that material SEB1 is present in the layer in a volume ratio of 95% and D1 in a ratio of 5%. Similarly, the electron transport layer may also consist of a mixture of the two materials. The exact structure of the OLED can be found in Table 1. The materials used for the fabrication of the OLED are shown in Table 3.

[0331] OLEDs are characterized using standard methods. For this purpose, the electroluminescence spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in %) are calculated from the current-voltage-luminance characteristic line (IUL characteristic line) as a function of luminance, assuming Lambertian radiation characteristics. The electroluminescence spectrum is recorded at a luminance of 1000 cd / m², which is used to infer the emission color and EL-FWHM values ​​( EL ectroluminescence - F ull W idth H alf M aximum - width of EL emission at half the peak height in eV units; for better comparability across the full spectral range).

[0332] Use of the compound of the present invention as a material in OLEDs:

[0333] One use of the compounds of the present invention may be as transport or blocking materials (HBL) in OLEDs and as dopants in the emission layer. Compound D-Ref.1 according to Table 3 is used as a comparison according to the prior art. Results for OLEDs are collected in Table 2.

[0334]

[0335]

[0336]

[0337]

[0338]

[0339] 2) Solution-treated components:

[0340] The fabrication of solution-based OLEDs is essentially described in the literature, for example, WO 2004 / 037887 and WO 2010 / 097155. The following examples combine two fabrication processes (application from vapor phase and solution processing) so that the emission layer and the layers including it are processed from solution, and subsequent layers (hole blocking layer / electron transport layer) are applied by vapor deposition under reduced pressure. For this purpose, the general method described above is matched to the situation described herein (layer thickness variation, material) and combined as follows.

[0341] The structure used is as follows:

[0342] - Substrate,

[0343] - ITO (50 nm),

[0344] - PEDOT (20 nm),

[0345] - Hole transport layer (HIL2) (20 nm),

[0346] - Emission layer (92% host, 8% dopant) (60nm),

[0347] - Electron transport layer (ETM1 50% + ETM2 50%) (20 nm),

[0348] - Cathode (Al).

[0349] The substrate used is a glass plate coated with structured ITO (Indium Tin Oxide) with a thickness of 50 nm. For better processing, they are coated with a buffer (PEDOT) Clevios P ​​VP AI 4083 (Heraeus Clevios GmbH, Leverkusen); the PEDOT is placed on top. Spin coating is performed under air rather than water. Subsequently, the layer is calcined at 180°C for 10 minutes. The hole transport layer and the emission layer are applied to the glass plate thus coated. The hole transport layer is a polymer of the structure shown in Table 3, synthesized according to WO 2010 / 097155. The polymer is dissolved in toluene such that the solution typically has a solid content of about 5 g / l, where, as in this case, a layer thickness of 20 nm, typical for the device, is to be achieved by spin coating. The layer is spun on in an inert gas atmosphere, in this case argon, and calcined at 180°C for 60 minutes.

[0350] The emission layer always consists of at least one matrix material (host material) and an emission dopant (emitter). Details given in the form H1 (92%):D (8%) indicate that material H1 is present in the emission layer at a weight ratio of 92% and dopant D at a weight ratio of 8%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solid content of such a solution is about 18 g / l when a layer thickness of 60 nm, typical for the device as shown here, is achieved by spin-coating. The layer is spin-on in an inert gas atmosphere, in this case argon, and calcined at 140 to 160 °C for 10 minutes. The materials used are shown in Table 3.

[0351] Materials for the electron transport layer and the cathode are applied by thermal evaporation in a vacuum chamber. For example, the electron transport layer may consist of more than one material, and the materials are added to each other by co-evaporating in specific volume ratios. Details given in the form ETM1:ETM2 (50%:50%) indicate that ETM1 and ETM2 materials are present in the layer at a volume ratio of 50% each. The materials used in this case are shown in Table 3.

[0352]

[0353]

[0354]

[0355] Compared to the reference example, some compounds of the present invention have smaller or equal EL-FWHM values ​​( EL ectroluminescence - F ull W idth H alf M It exhibits a narrower or similarly narrow electroluminescence spectrum recognizable as aximum (width of the emission spectrum in eV units at half the peak height). The narrower electroluminescence spectrum results in a distinct improvement in color purity (lower CIE y values). In addition, the EQE value ( E xternal Q uantum E The efficiency is significantly larger and the operating voltage is lower, so the power efficiency of the device is significantly improved and power consumption is reduced.

Claims

Claim 1 A compound comprising at least one structure of the following formula (I). The symbols and indices used in the food are as follows: Z 1 , Z 2 is N;W 1 , W 2 , W 3 , W 4 is the same or different in each case, and is CAr, X, or 2 adjacent W 1 , W 2 , W 3 , W 4 Gi is Ar; Y 1 are the same or different in each case, and are N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr, C=C(R)2, O, S, Se, S=O, or SO2;Y 2 is, in each case, the same or different and is bonded, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr, C=C(R)2, O, S, Se, S=O, or SO2; Ar is, in each case, the same or different and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and capable of being substituted with one or more R radicals; wherein the Ar group may form a ring system with at least one Ar group, R group, or additional group; X is, in each case, the same or different and is N or CR, provided that X and X in one ring 3 Two or fewer of the elements are N; X 1 is the same or different in each case, and N, CR a or CAr, provided that X in one ring 1 , X 2 , X 3 Two or fewer of the elements are N; X 2 is the same or different in each case, and N, CR b or CAr, provided that X in one ring 1 , X 2 , X 3 Two or fewer of the elements are N; X 3 are the same or different in each case, and when p is 1, N, CR c , CAr or C, provided that in one ring X, X 1 , X 2 , X 3 Two or fewer of the elements are N; p is the same or different and is 0 or 1, where W 3 , W 4 If is not Ar, p = 1; R, R a , R b , R c are the same or different in each case, and H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)OAr', C(=O)OR 1 , C(=O)N(Ar')2, C(=O)N(R 1 )2, C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms (the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group having one or more R in each case 1 It can be substituted by radicals, and one or more non-adjacent CH2 groups are R 1 C=CR 1 , C≡C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), which can be replaced by -O-, -S-, SO or SO2), or having 5 to 60 aromatic ring atoms and in each case one or more R 1 An aromatic or heteroaromatic ring system capable of being substituted by radicals, or having 5 to 60 aromatic ring atoms and one or more R 1 It is an aryloxy or heteroaryloxy group that can be substituted by a radical; simultaneously, two R, R a , R b , R c Radicals may also form ring systems together or with additional groups; Ar' is the same or different in each case and has 5 to 60 aromatic ring atoms and one or more R 1 It is an aromatic or heteroaromatic ring system that may be substituted by radicals; at the same time, two Ar' radicals bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are also a bridge formed by a single bond or B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 It is possible to connect together through a selected bridge from;R 1 are the same or different in each case, and H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2, C(=O)OAr'', C(=O)OR 2 , C(=O)Ar'', C(=O)R 2 , P(=O)(Ar'')2, P(Ar'')2, B(Ar'')2, B(R 2 )2, C(Ar'')3, C(R 2 )3, Si(Ar'')3, Si(R 2 )3, 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 group having 2 to 40 carbon atoms (each of these is one or more R 2 It can be substituted by radicals, where one or more non-adjacent CH2 groups are -R 2 C=CR 2 -, -C≡C-, Si(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 ), which may be replaced with -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced with D, F, Cl, Br, I, CN or NO2), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (each of these having one or more R 2 It may be substituted by radicals), or having 5 to 60 aromatic ring atoms and one or more R 2 An aryloxy or heteroaryloxy group that may be substituted by a radical, or one or more R having 5 to 60 aromatic ring atoms 2 An aralkyl or heteroaralkyl group that may be substituted by a radical, or a combination of these systems; and simultaneously, two or more R 1 Radicals can form a ring system together; simultaneously, one or more R 1 Radicals may also form ring systems with additional parts of the compound; Ar'' is the same or different in each case and has 5 to 30 aromatic ring atoms and one or more R 2 It is an aromatic or heteroaromatic ring system that may be substituted by radicals; at the same time, two Ar'' radicals bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom are also a bridge formed by a single bond or B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 It is possible to connect together through a selected bridge from;R 2 is the same or different in each case and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms (wherein one or more hydrogen atoms may be replaced with D, F, Cl, Br, I, or CN, or substituted by one or more alkyl groups having 1 to 4 carbon atoms, respectively); and simultaneously, two or more substituents R 2 It can also form a ring system together;Y 1 and Y 2 At least one of them is B(Ar), B(R), C=O, P(=O)Ar, S, SO2, N(Ar), Si(R)2 or Si(Ar)2. Claim 2 A compound according to claim 1, comprising at least one structure of the following formulas (IIa) to (IIk). W during the meal 1 , W 2 , Y 1 , Y 2 , Z 1 , Z 2 , X 1 , X 2 and X 3 has the definition given in Article 1, and additional symbols and indices are as follows: X is the same or different in each case, and is N, CR, or C when p is 1, provided that no more than two X elements in a single ring are N; Y 3 In each case, is the same or different and is O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R); p is 0 or 1. Claim 3 A compound according to claim 1, comprising at least one structure of the following formulas (IIIa) to (IIIk). Y in food 1 , Y 2 , Z 1 , Z 2 , X 1 , X 2 and X 3 has the definition given in Article 1, where X is the same or different in each case, and when p is 1, it is N, CR, or C, provided that in one ring, there are no more than two X groups, and Y 3 In each case, is the same or different and is O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R); p is 0 or 1. Claim 4 A compound according to claim 1, comprising at least one structure of the following formulas (IV-1) to (IV-20). Y in food 1 , Y 2 , Z 1 , Z 2 , R, R a , R b and R c has the definition given in Article 1, and Y 3 In each case, are the same or different and are O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R); index l is 0, 1, 2, 3, 4 or 5, index m is 0, 1, 2, 3 or 4, index n is 0, 1, 2 or 3, index j is 0, 1 or 2, and index k is 0 or 1. Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 A compound according to claim 1, comprising at least one structure of the following formulas (V-1) to (V-40). Z in food 1 , Z 2 , X, X 1 and X 2 has the definition given in Article 1, and Y 3 are the same or different in each case, and O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R), and;Z 3 , Z 4 In each case, it is the same or different and is N, B, P(=O) or Si(R). Claim 10 A compound according to claim 1, comprising at least one structure of the following formulas (VI-1) to (VI-40). Symbol Z in food 1 , Z 2 , R, R a and R b has the definition given in Article 1, and Y 3 are the same or different in each case, and O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R); and Z 3 , Z 4 In each case, they are the same or different and are N, B, P(=O) or Si(R), index l is 0, 1, 2, 3, 4 or 5, index m is 0, 1, 2, 3 or 4, and index j is 0, 1 or 2. Claim 11 In claim 1, at least two Rs, R a , R b , R c The radical is the above two R, R a , R b , R c The radical forms a fused ring with an additional group to which it binds, where the two R, R a , R b , R c A compound characterized in that the radical forms at least one structure of the following formulas (RA-1) to (RA-12). R in food 1 ... has the definition set forth in Claim 1, and the dotted line combination is the two Rs, R a , R b , R c It represents the attachment site on the atom of the group to which the radical binds, and additional symbols are defined as follows: Y 4 is the same or different in each case and C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 1 , NAr', O or S is; R d is the same or different in each case, and F, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms (the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group having one or more R in each case 2 It may be substituted by radicals, and one or more non-adjacent CH2 groups are R 2 C=CR 2 , C≡C, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 1 ), may be substituted with -O-, -S-, SO or SO2), or have 5 to 60 aromatic ring atoms and in each case one or more R 2 An aromatic or heteroaromatic ring system that may be substituted by a radical, or one or more R having 5 to 60 aromatic ring atoms 2 It is an aryloxy or heteroaryloxy group that may be substituted by a radical; at the same time, two R d Radicals together or as a single R d Radicals R 1 It may also form a ring system with radicals or additional groups;s is 0, 1, 2, 3, 4, 5 or 6;t is 0, 1, 2, 3, 4, 5, 6, 7 or 8;v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9. Claim 12 In claim 1, the at least two Rs, R a , R b , R c The radical is the above two R, R a , R b , R c A fused ring is formed with an additional group to which the radical binds, and the two R, R a , R b , R c Radicals are compounds that form the structure of the following formula (RB). R in food 1 ... has the definition set forth in Claim 1, and the dotted line combination is the two Rs, R a , R b , R c Indicates the attachment site where the radical binds, index m is 0, 1, 2, 3, or 4, and Y 5 is C(R 1 )2, NR 1 , NAr', BR 1 , BAr', O or S. Claim 13 A compound according to claim 1, comprising at least one structure of the following formulas (VII-1) to (VII-50), wherein the compound has at least one fused ring. Y in food 1 , Y 2 , Z 1 , Z 2 , R, R a , R b and R c has the definition given in Article 1, and Y 3 In each case, are the same or different and are O, S, N(Ar'), N(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, B(Ar') or B(R); the symbol o indicates the attachment site, and additional symbols are defined as follows: l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2; and k is 0 or 1. Claim 14 An oligomer, polymer, or dendrimer containing at least one compound described in any one of claims 1 to 4 and claims 9 to 13, wherein one or more bonds of said compound to said polymer, oligomer, or dendrimer are formed rather than hydrogen atoms or substituents. Claim 15 A formulation comprising at least one compound described in any one of claims 1 to 4 and claims 9 to 13, and at least one additional compound. Claim 16 A composition comprising at least one compound described in any one of claims 1 to 4 and claims 9 to 13, and at least one additional compound selected from the group consisting of a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF, a host material, an electron transport material, an electron injection material, a hole conductor material, a hole injection material, an electron blocking material, and a hole blocking material. Claim 17 A method for manufacturing a compound described in any one of claims 1 to 4 and claims 9 to 13, wherein Z 1 Gi or Z 2 Gi or the above Z 1 , Z 2 A base framework having one of the precursors is synthesized, and the Y 1 , Y 2 A manufacturing method characterized in that at least one of the groups is introduced by a nucleophilic aromatic substitution reaction or a coupling reaction. Claim 18 A compound used in an electronic device, in any one of claims 1 to 4 and claims 9 to 13. Claim 19 An electronic device comprising at least one compound described in any one of claims 1 to 4 and claims 9 to 13.

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