Materials for organic electroluminescent devices

Abstract

This invention relates to compounds suitable for use in electronic devices, and electronic devices containing said compounds, particularly organic electroluminescent devices.

Description

[0001] This invention relates to materials used in electronic devices, particularly organic electroluminescent devices, and electronic devices, particularly organic electroluminescent devices, that incorporate these materials.

[0002] The luminescent materials used in organic light-emitting devices (OLEDs) are typically phosphorescent organometallic complexes. Generally, improvements are still needed in OLEDs, especially in those exhibiting triplet emission (phosphorescence), for example, in terms of efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are not solely determined by the triplet emitter used. More specifically, other materials used, such as the matrix material, are also particularly important. Therefore, improvements to these materials can also lead to improvements in OLED properties. Suitable matrix materials for OLEDs include, for example, aromatic lactams disclosed in, for example, WO 2011 / 116865, WO 2011 / 137951, WO2013 / 064206, or KR 2015-037703.

[0003] One object of the present invention is to provide compounds suitable for use in OLEDs, particularly as a matrix material for phosphorescent emitters or as an electron transport material, resulting in improved properties therein.

[0004] Surprisingly, this objective has been achieved through specific compounds described in detail below, which are well-suited for use in OLEDs. These OLEDs, in particular, exhibit long lifetimes, high efficiency, and relatively low operating voltages. Therefore, the present invention provides these compounds, as well as electronic devices, especially organic electroluminescent devices, comprising these compounds.

[0005] This invention provides a compound of formula (1),

[0006]

[0007] The symbols and markings used are as follows:

[0008] X is the same or different in each case and is CR or N, provided that no more than two X groups in each ring are N, and further provided that two adjacent X groups that are part of the same six-membered ring are CR, wherein the adjacent R groups form an aromatic or heteroaromatic ring system having 4 to 8 ring atoms, the ring system being fused to the ring and being substituted by one or more R groups;

[0009] Y is BR, C(R)2, C=O, Si(R)2, NR, NAr 1 O, S, Se, SO, SO2, PR or P(=O)R, where, when m or n is 0, the carbon atoms bonded to Y are each X;

[0010] m and n are 0 or 1, where m+n is 1;

[0011] Ar 1 It has 6 to 40 aromatic ring atoms and can be converted into one or more R 1 Aromatic ring systems with substituted groups, or those having 5 to 40 aromatic ring atoms and capable of being substituted by one or more R groups. 1 Heteroaromatic ring systems with substituted groups;

[0012] R is the same or different in each case and is: H, D, F, Cl, Br, I, N(Ar')2, N(R) 1 )2,OAr',SAr',B(OR 1 )2, CHO, C(=O)R 1 CR 1 =C(R) 1 )2, CN, C(=O)OR 1 C(=O)NR 1 ,Si(R 1 )3,Ge(R) 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 OR 1 S(=O)R 1 S(=O)2R 1 SR 1 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 1 C = CR 1 -、-C≡C-、Si(R 1 2. NR 1 CONR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 The aromatic ring may be replaced by -O-, -S-, SO or SO2, or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be replaced by one or more R 1 A group-substituted aromatic or heteroaromatic ring system, wherein two or more R groups bonded to the same ring can together form an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system, wherein the aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system can be substituted by one or more R groups. 1Group substitution, wherein two R groups bonded to the same carbon or silicon atom can together form a monocyclic or polycyclic aliphatic, aromatic, or heteroaromatic ring system, said aliphatic, aromatic, or heteroaromatic ring system being substituted by one or more R groups. 1 Group substitution;

[0013] Ar' may be the same or different in each case and is a ring with 5 to 40 aromatic atoms and can be denoted by one or more R. 1 Aromatic or heteroaromatic ring systems with substituted groups;

[0014] R 1 In each case, they are the same or different and are: H, D, F, I, B (OR) 2 )2,N(R 2 )2, CHO, C(=O)R 2 CR 2 =C(R) 2 )2, CN, C(=O)OR 2 ,Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 SR 2 OR 2 S(=O)R 2 S(=O)2R 2 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 2 Group substitution, wherein one or more CH2 groups in the above groups can be -R 2 C = CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, NR 2 CONR 2 P(=O)(R) 2 The following groups may be replaced by -O-, -S-, SO, or SO2, and one or more hydrogen atoms in the above groups may be replaced by D, F, Cl, Br, I, CN, or NO2, or have 5 to 30 aromatic ring atoms and in each case may be replaced by one or more R... 2 Aromatic or heteroaromatic ring systems with substituted groups, wherein two or more R groups are present. 1 The groups can together form aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring systems;

[0015] R 2In each case, the same or different are: H, D, F, CN, or an aliphatic, aromatic, or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D or F; and simultaneously, two or more R 2 Substituents can connect with each other and form rings.

[0016] In the context of this invention, an aryl group contains 6 to 40 carbon atoms; in the context of this invention, a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. Here, aryl group or heteroaryl group should be understood to refer to: a simple aromatic ring, i.e., benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused (enhanced) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

[0017] In the context of this invention, an aromatic ring system contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms. In the context of this invention, a heteroaromatic ring system contains 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, an aromatic or heteroaromatic ring system should be understood to mean a system that does not necessarily contain only aryl or heteroaromatic groups, but in which two or more aryl or heteroaromatic groups can also be linked by non-aromatic units such as carbon, nitrogen, or oxygen atoms. These should also be understood to mean systems in which two or more aryl or heteroaromatic groups are directly linked to each other, such as biphenyl, terphenyl, bipyridine, or phenylpyridine. For example, in the context of this invention, systems such as fluorene, 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should also be considered aromatic ring systems, as should systems in which two or more aryl groups are linked by, for example, short alkyl groups. Preferred aromatic or heteroaromatic ring systems are: simple aryl or heteroaromatic groups, and groups in which two or more aryl or heteroaromatic groups are directly linked to each other, such as biphenyl or bipyridine, and fluorene or spirodifluorene.

[0018] Electron-rich heteroaryl ring systems are characterized by the absence of electron-deficient heteroaryl groups. Electron-deficient heteroaryl groups are: six-membered heteroaryl groups having at least one nitrogen atom, or five-membered heteroaryl groups having at least two heteroatoms, one of which is a nitrogen atom and the other nitrogen atom is an oxygen, sulfur, or substituted nitrogen atom, wherein other aryl or heteroaryl groups may also be fused to these groups in each case. In contrast, electron-rich heteroaryl groups are five-membered heteroaryl groups having exactly one heteroatom selected from oxygen, sulfur, and substituted nitrogen, to which other aryl groups and / or other electron-rich five-membered heteroaryl groups may be fused. Therefore, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, or indocarbazole. Electron-rich heteroaryl groups are also called electron-rich heteroaryl groups.

[0019] The electron-deficient heteroaryl ring system is characterized by containing at least one electron-deficient heteroaryl group, and is particularly preferred to contain no electron-rich heteroaryl group.

[0020] In the context of this invention, the term "alkyl group" is used as a general term for straight-chain and branched alkyl groups as well as cyclic alkyl groups. Similarly, the terms "alkenyl group" and "alkynyl group" are used as a general term for straight-chain or branched alkenyl or alkynyl groups as well as cyclic alkenyl or alkynyl groups.

[0021] In the context of this invention, aliphatic hydrocarbon groups, alkyl groups, alkenyl groups, or alkynyl groups containing 1 to 40 carbon atoms, wherein some hydrogen atoms or CH2 groups may also be replaced by the aforementioned groups, are preferably understood to refer to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptenyl, or octenyl groups. Alkoxy groups having 1 to 40 carbon atoms OR 1 Preferably understood as methyl methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexyloxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy. A thioalkyl group SR having 1 to 40 carbon atoms. 1Specifically, it is understood to refer to thiols, ethylthiols, n-propylthiols, isopropylthiols, n-butylthiols, isobutylthiols, sec-butylthiols, tert-butylthiols, n-pentylthiols, sec-pentylthiols, n-hexylthiols, cyclohexylthiols, n-heptylthiols, cycloheptylthiols, n-octylthiols, cyclooctylthiols, 2-ethylhexylthiols, trifluoromethylthiols, pentafluoroethylthiols, 2,2,2-trifluoroethylthiols, ethylenethiols, propylenethiols, butenethiols, pentenethiols, cyclopentenethiols, hexenethiols, cyclohexenethiols, heptenthiols, cycloheptenethiols, octenenethiols, cyclooctenethiols, ethynthiols, propynthiols, butynthiols, pentynthiols, hexynthiols, heptenthiols, or octynthiols. Generally, the alkyl, alkoxy, or thioalkyl groups of the present invention can be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above groups; in addition, one or more hydrogen atoms can also be replaced by D, F, Cl, Br, I, CN, or NO2, preferably by F, Cl, or CN, more preferably by F or CN.

[0022] It has 5-60 aromatic ring atoms and can be converted to the above R in each case. 2 Aromatic or heteroaromatic ring systems in which a group or hydrocarbon group is substituted and can be attached to the aromatic or heteroaromatic system via any desired position are understood to particularly refer to groups derived from or combinations thereof of the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, pyrene, celestane, perylene, fluoranthene, tetraphenylbenzene, pentaphenylbenzene, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, terphenylidene, fluorene, spirofluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans Indofluorene, cis or trans indocarbazole, cis or trans indocarbazole, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthridine Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridiniumimidazoles, pyraziniumimidazoles, quinoxalineimidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylide, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazoles, benzo[a]triazoles, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0023] In the context of this specification, the phrase "two or more groups can form a ring system together" should be understood in particular to mean that two groups are linked together by chemical bonds under conditions that formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

[0024]

[0025] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, then the second group bonds to the site where the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following scheme:

[0026]

[0027] In a preferred embodiment, the compound comprises the structure of formula (1) above and formula (2) below.

[0028]

[0029] The symbols used have the definitions given above, and in addition:

[0030] X is the same or different in each case and is CR or N, provided that no more than two X groups in each ring are N, and further provided that two adjacent X groups that are part of the same ring are C, at which point the groups of formula (2) form an aromatic or heteroaromatic ring system fused to the ring by bonds indicated by *.

[0031] Q is the same or different in every case and is CR. 1 Or N, provided that at most two Q groups in each ring are N.

[0032] Equations (3) and (4) below show other preferred embodiments:

[0033]

[0034] The symbols and notations used have the definitions given above for equations (1) and (2).

[0035] In a preferred embodiment of the invention, Y in the preceding and subsequent embodiments is C(R)2, NAr. 1 O or S, preferably NAr 1 O or S, NAr is the preferred choice. 1 .

[0036] In a preferred embodiment, at least one R group among the symbols Y, X and / or Q in formulas (3) and (4) is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and more preferably 6 to 24 aromatic ring atoms, wherein the ring system may in each case be one or more R groups. 1 Group substitution, wherein R 1 The functional group is preferably non-aromatic.

[0037] In a preferred embodiment of the invention, each ring has no more than one symbol X that is N, and more preferably no symbol X that is N.

[0038] In a preferred embodiment of the present invention, X and Q are CR.

[0039] Equations (5) to (8) below show other preferred embodiments:

[0040]

[0041] The symbols used have the definitions given above for equation (2).

[0042] Therefore, the preferred embodiments of the compounds of formulas (5) to (8) are the compounds of formulas (5-1) to (8-1):

[0043]

[0044] If the symbol exists, it has the definition given above for equations (5) to (8).

[0045] In a preferred embodiment of the invention, in formulas (5) to (8), preferably in formulas (5-1) to (8-1), there are no more than 4 R groups, more preferably no more than 3 R groups, and most preferably no more than two R groups that are not H, CN, or D.

[0046] In a preferred embodiment of the invention, in formulas (5) to (8), preferably in formulas (5-1) to (8-1), there are no more than 4 R groups, preferably no more than 3 R groups, and most preferably no more than one R group is not H, CN, or D. In this case, R is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and more preferably 6 to 24 aromatic ring atoms, and the ring system may in each case be one or more R groups. 1 Group substitution.

[0047] If Y = NAr 1 Especially in formulas (5) to (8), preferably in formulas (5-1) to (8-1), in a preferred embodiment, no more than one R group and more preferably none of the Rs is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms; in particular, all Rs are H, D or CN, preferably H or D; more preferably Ar 1 It is an electron-deficient heteroaromatic ring system, especially electron-deficient heteroaromatic compounds.

[0048] In Y=NAr 1 Ar 1 In the case of an aromatic ring system or an electron-rich heteroaromatic ring system, in a preferred embodiment, no more than two R groups, preferably no more than one R group, are aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms, wherein the two R groups are not bonded to the same ring.

[0049] In the case of Y=O or S, in a preferred embodiment, no more than 3 R groups, preferably no more than 2 R groups, especially only one R group is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms, wherein all R groups are bonded to different rings.

[0050] The following equations (5-1-1) to (8-1-4) show other preferred embodiments of equations (5) to (8):

[0051]

[0052]

[0053]

[0054] If the aforementioned symbol exists, then it has the definitions given in equations (5) to (8), and additionally:

[0055] R' may be the same or different in each case, or it may be an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, wherein in each case the ring system may be one or more R's. 1 Group substitution.

[0056] In a preferred embodiment, only at most two other Rs in formulas (5-1-1) to (8-1-4) are the same or different in each case and are an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms, wherein the ring system may be composed of one or more Rs in each case. 1 Group substitution.

[0057] In Y=NAr 1 Ar 1 When the compound is an aromatic ring system or an electron-rich heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and more preferably 6 to 24 aromatic ring atoms, the preferred compounds are those of formulas (5-1-1), (5-1-2), (5-1-3), (6-1-1), (6-1-2), (6-1-3), (7-1-1), (7-1-2), (7-1-3), (7-1-4), (8-1-1), (8-1-2), and (8-1-3), wherein preferably only one R group is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, and more preferably 6 to 24 aromatic ring atoms, wherein the R is not bonded to the same ring as R'.

[0058] When Y = O or S, preferably O, the preferred compounds are those of formulas (5-1-1), (5-1-2), (5-1-4), (5-1-5), (6-1-1), (6-1-2), (6-1-4), (7-1-1), (7-1-2), (7-1-3), (8-1-1), (8-1-2), and (8-1-4), wherein preferably only one R group is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 6 to 40 aromatic ring atoms, more preferably having 6 to 24 aromatic ring atoms, wherein the R is not bonded to the same ring as R'.

[0059] The following is a list of preferred substituents R and Ar. 1 Ar', R 1 and R 2 The description. In a particularly preferred embodiment of the invention, the following refers to R, Ar 1 Ar', R 1 and R 2The specified preferred options occur simultaneously and apply to the structure of Equation (1) and all preferred embodiments detailed above.

[0060] In a preferred embodiment of the present invention, Ar 1 It is an aromatic ring system having 6 to 30 aromatic ring atoms that can be substituted by one or more R groups, or a heteroaromatic ring system having 6 to 30 aromatic ring atoms that can be substituted by one or more R groups. In a particularly preferred embodiment of the invention, Ar is an aromatic ring system having 6 to 24 aromatic ring atoms that can be substituted by one or more preferred non-aromatic R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups.

[0061] Suitable aromatic or hybrid aromatic ring systems Ar 1 In each case, the same or different and selected from: phenyl, biphenyl, especially o-biphenyl, m-biphenyl, or p-biphenyl, terphenyl, especially o-terphenyl, m-terphenyl, or p-terphenyl or branched terphenyl, tetraphenyl, especially o-tetraphenyl, m-tetraphenyl, or p-tetraphenyl or branched tetraphenyl, fluorene linked at positions 1, 2, 3, or 4, spirodifluorene linked at positions 1, 2, 3, or 4, naphthalene linked at positions 1 or 2, indole, benzofuran, benzothiophene, dibenzofuran, carbazole linked at positions 1, 2, 3, or 4, dibenzofuran linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, phenanthrene, biphenylide, or combinations of two or three of these groups; each of the groups can be generated by one or more R 1 Groups, preferably non-aromatic R 1 Group substitution.

[0062] Ar 1 Other preferred embodiments, when they represent heteroaromatic ring systems, Ar 1 The group is selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, quinoxaline, and benzimidazole, or a combination of these groups with one of the aforementioned groups, each of which can be oxidized by one or more R groups. 1 Group substitution. When Ar 1 When the group is a heteroaryl group, especially a triazine, pyrimidine, quinazoline, or quinoxaline, the aromatic or heteroaryl R on that heteroaryl group... 1 The radical group may also be selected from its preferred options.

[0063] In a preferred embodiment of the invention, R may be the same or different in each case and is selected from: H, D, F, CN, OR 1A straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein each of the alkyl or alkenyl groups may be coupled with one or more R... 1 The groups are substituted, but preferably unsubstituted, and one or more non-adjacent CH2 groups may be replaced by O, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, the two R groups may also form an aliphatic, aromatic, or heteroaromatic ring system together. More preferably, R may be the same or different in each case and is selected from: H, a straight-chain alkyl group having 1 to 6 carbon atoms, especially having 1, 2, 3, or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R groups in each case. 1 The group is substituted, but preferably unsubstituted, or has 6 to 24 aromatic ring atoms and in each case can be substituted by one or more R groups. 1 Groups, preferably non-aromatic R 1 Aromatic or heteroaromatic ring systems with substituted groups. Most preferably, R is the same or different in each case and is selected from: H, or having 6 to 24 aromatic ring atoms and in each case can be one or more R. 2 Groups, preferably non-aromatic R 1 Aromatic or heteroaromatic ring systems with substituted groups.

[0064] Suitable aromatic or heteroaromatic ring systems R are selected from: phenyl, biphenyl, especially ortho-biphenyl, meta-biphenyl or para-biphenyl, terphenyl, especially ortho-terphenyl, meta-terphenyl or para-terphenyl or branched terphenyl, tetraphenyl, especially ortho-tetraphenyl, meta-tetraphenyl or para-tetraphenyl or branched tetraphenyl, fluorene that can be linked at positions 1, 2, 3 or 4, spirobifluorene that can be linked at positions 1, 2, 3 or 4, and spirobifluorene that can be linked at positions 1 or 2. Naphthalene, indole, benzofuran, benzothiophene linked at positions 1, 2, 3, or 4, dibenzofuran, carbazole linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene, biphenylene oxide, or combinations of two or three of these groups; each of these groups may be linked by one or more R 1 Group substitution. When R is a heteroaryl group, especially triazine, pyrimidine, or quinazoline, the aromatic or heteroaryl R on that heteroaryl group... 1 The radical group may also be selected from its preferred options.

[0065] The R group or Ar here 1When they are aromatic or heteroaromatic ring systems, groups preferably selected from the following formulas R-1 to R-82:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] Where R 1 As defined above, a dashed bond represents a bond connected to a carbon atom of the basic skeleton in formula (1) or the preferred embodiment, or a bond connected to a heteroatom in the N(Ar')2 or NR2 group; additionally:

[0073] Ar 3 In each case, they may be the same or different, and they have 6 to 18 aromatic ring atoms and in each case can be one or more R 1 Divalent aromatic or heteroaromatic ring systems with substituted groups;

[0074] A 1 The same or different in each case and is C(R) 1 2. NR 1 O or S, preferably O or S;

[0075] p is 0 or 1, where m = 0 means Ar 3 The functional group is absent and the corresponding aromatic or heteroaromatic group is directly bonded to the carbon atom of the basic skeleton in formula (1) or in the preferred embodiment, or to N (Ar) 1 )2. The nitrogen atom in the group; the condition is that for the structures R-12, R-17, R-21, R-25, R-26, R-30, R-34, R-38, R-39, and R-67, when these groups are Ar 1 In the implementation method, m = 1;

[0076] r can be 0 or 1, where r = 0 means that no A group is bonded at that position, and R is used instead. 1 The functional group is bonded to the corresponding carbon atom.

[0077] In a preferred embodiment, Ar 3 Containing divalent aromatic or heteroaromatic ring systems based on R-1 to R-82 groups, where m = 0 and the dashed bond and R 1This indicates a bond attached to an aromatic or heteroaromatic group according to R-1 to R-82.

[0078] When referring to R, the above R-1 to R-82, or Ar 1 Having two or more A's 1 When the group is A 1 Possible options for the functional group include those from A 1 All combinations defined. In this case, the preferred implementation is one of A. 1 The group is O or S and another A 1 The group is C(R) 1 )2 or two of them A 1 All groups are S or O or two of them are A. 1 Implementations where all radicals are O or S.

[0079] When A 1 It is NR 1 At that time, the substituent R bonded to the nitrogen atom 1 Preferably, it has 5 to 24 aromatic ring atoms and may also be composed of one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, the R... 1 The substituents may be the same or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and the ring system does not have any fused aryl groups or fused heteroaromatic groups in which two or more of the aromatic or heteroaromatic 6-membered ring groups are directly fused together, and in each case may also be subjected to one or more R 2 Group substitution. Particularly preferred are phenyl, biphenyl, terphenyl, and tetraphenyl groups having the bonding patterns listed above for R-1 to R-11, wherein these structures can be substituted by one or more R groups. 1 Group substitution is permitted, but unsubstituted groups are preferred.

[0080] When A 1 It is C(R) 1 At 2, the substituent R bonded to the carbon atom 1 Preferably, in each case, the same or different, 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, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms; it may also be one or more R 2 Group substitution. Most preferably, R 1 It is a methyl group or a phenyl group. In this case, R 1 Groups can also form ring systems together, resulting in spiro systems.

[0081] When Y is CR2, the substituent R bonded to the carbon atom is preferably 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, or an aromatic or electron-deficient heteroaromatic ring system having 5 to 24 aromatic ring atoms. It can also be one or more Rs. 1 Group substitution. Most preferably, these substituents R are methyl groups or phenyl groups. In this case, the R groups together can also form a cyclic system, resulting in a spirosystem.

[0082] In one embodiment of the invention, at least one R or Ar 1 The group is an electron-rich heteroaromatic ring system. This electron-rich heteroaromatic ring system is preferably selected from the R-13 to R-42 groups shown above, wherein, among the R-13 to R-16, R-18 to R-20, R-22 to R-24, R-27 to R-29, R-31 to R-33, and R-35 to R-37 groups, at least one A 1 The group is NR 1 , where R 1 The preferred type is the aromatic or hybrid aromatic ring system, especially the aromatic ring system.

[0083] In another particularly preferred embodiment of the invention, at least one R group, or Ar 1 The group is an electron-deficient heteroaromatic ring system. The electron-deficient heteroaromatic ring system is preferably selected from the R-47 to R-50, R-57, R-58, R-76, R-79, R-80, R-81 and R-82 groups shown above.

[0084] In another preferred embodiment of the invention, R 1 In each case, they may be the same or different and are selected from: H, D, F, CN, OR 2 A straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 2 The group is substituted, and one or more non-adjacent CH2 groups can be replaced by O, or it has 6 to 30 aromatic ring atoms and in each case can be replaced by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 1 The groups can together form an aliphatic ring system. In a particularly preferred embodiment of the invention, R 1 In each case, the same or different and selected from: H, a straight-chain alkyl group having 1 to 6 carbon atoms, especially having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be one or more R2 The group is substituted, but preferably unsubstituted, or has 6 to 24 aromatic ring atoms and in each case can be substituted by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups, but preferably unsubstituted.

[0085] In another preferred embodiment of the invention, R 2 In each case, the same or different are: H, F, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, said group may be substituted with an alkyl group having 1 to 4 carbon atoms, but preferably unsubstituted.

[0086] In another preferred embodiment of the invention, all R 1 Groups, if they are aromatic or heteroaromatic ring systems, or R 2 The groups, if they are aromatic or heteroaromatic groups, are selected from R-1 to R-82 groups; however, in this case, they are correspondingly replaced by R. 2 Instead of being R 1 Replace or be targeted at R 2 The mentioned group substitution.

[0087] In a preferred embodiment, the R groups other than those in formula (2) do not form any other aromatic or heteroaromatic groups that are fused with the basic skeleton of formula (1).

[0088] Furthermore, the alkyl groups in the compounds of the present invention processed by vacuum evaporation preferably have no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, suitable compounds also include those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or those substituted with oligomeric aromatic subunits such as o-terphenyl, m-terphenyl, or p-terphenyl, or branched terphenyl or tetraphenyl groups.

[0089] When the compound of formula (1) or the preferred embodiment is used as a matrix material for a phosphorescent emitter or in a layer directly adjacent to a phosphorescent layer, it is also preferred that the compound does not contain any fused aryl or fused heteroaryl groups in which more than two six-membered rings are directly fused together. Ar, R, and R are particularly preferred. 1 and R 2 The group does not contain any fused aryl or fused heteroaryl groups in which two or more six-membered rings are directly fused to each other. Annularity, biphenylene, quinazoline, and quinoxaline constitute exceptions to this case because their triplet energy is high, so they may be preferred despite the presence of fused aromatic six-membered rings.

[0090] The preferred embodiments described above can be combined with each other as needed within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above preferred options occur simultaneously.

[0091] Examples of preferred compounds according to the embodiments described above are detailed in the table below:

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] The basic structures of the compounds of the present invention can be prepared via the routes outlined in schemes 1, 2, and 3. Schemes 1 and 2 show the route where Y is NAr. 1 The synthesis of the compound, where Y is O in scheme 3.

[0119] Option 1:

[0120]

[0121] Option 2:

[0122]

[0123] Option 3:

[0124]

[0125] Indicates the fused phenyl ring at each position: d = 0 or 1, e = 0 or 1; d + e = 1

[0126] a, b, c = 0 or 1

[0127] The compounds of this invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. In schemes 1, 2, and 3, L represents a divalent aromatic or heteroaromatic ring system, and Ar represents an aromatic or heteroaromatic ring system.

[0128] To process the compounds of the present invention from the liquid phase, for example by spin coating or printing, formulations of the compounds of the present invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fonone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indene, NMP, p-methylisopropyl Benzene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or mixtures of these solvents.

[0129] Therefore, the present invention also provides a formulation comprising at least one compound of the present invention and at least one additional compound. The additional compound may be, for example, a solvent, particularly one of the solvents described above or a mixture of these solvents. The additional compound may alternatively be at least one other organic or inorganic compound also used in electronic devices, such as a luminescent compound and / or other matrix material. Suitable luminescent compounds and other matrix materials are listed later in connection with organic electroluminescent devices. The other compound may also be polymerized.

[0130] The compounds of the present invention are suitable for use in electronic devices, especially organic electroluminescent devices.

[0131] Therefore, the present invention also provides the use of the compounds of the present invention in electronic devices, particularly in organic electroluminescent devices.

[0132] The present invention also provides electronic devices comprising at least one compound of the present invention.

[0133] In the context of this invention, an electronic device is a device comprising at least one layer containing at least one organic compound. The component may also comprise other layers of inorganic materials or materials entirely composed of inorganic materials.

[0134] The electronic device is preferably selected from: organic light-emitting devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasma light-emitting devices, but organic light-emitting devices (OLEDs) are preferred, and phosphorescent OLEDs are even more preferred.

[0135] The organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may also include other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers in each case. Similarly, an intermediate layer having, for example, exciton blocking functionality can be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily required. In this case, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, these layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in an overall white light emission; in other words, various luminescent compounds capable of fluorescence or phosphorescence are used in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device of the present invention can also be a tandem OLED, especially a white-light-emitting OLED.

[0136] Depending on the exact structure, the compounds of the present invention according to the embodiments detailed above can be used in different layers. Preferably, organic electroluminescent devices contain compounds of formula (1) or those of the preferred embodiments described above as matrix materials for phosphorescent emitters or emitters exhibiting TADF (thermally excited delayed fluorescence), especially phosphorescent emitters, in the light-emitting layer. In this case, the organic electroluminescent device may contain one light-emitting layer, or it may contain multiple light-emitting layers, wherein at least one light-emitting layer contains at least one compound of the present invention as a matrix material. In addition, the compounds of the present invention can also be used in electron transport layers and / or hole blocking layers and / or hole transport layers and / or exciton blocking layers.

[0137] When the compounds of the present invention are used as matrix materials for phosphorescent compounds in the luminescent layer, they are preferably used in combination with one or more phosphorescent materials (triple-state emitters). In the context of this invention, phosphorescence is understood to refer to emission from excited states with higher spin multiplicity, i.e., spin > 1, particularly from excited triplet states. In the context of this application, all luminescent complexes containing transition metals or lanthanides, particularly all iridium, platinum, and copper complexes, should be considered phosphorescent compounds.

[0138] Based on the total mixture of the luminescent material and the matrix material, the mixture of the compound of the present invention and the luminescent compound contains between 99 vol% and 1 vol%, preferably between 98 vol% and 10 vol%, more preferably between 97 vol% and 60 vol%, and especially between 95 vol% and 80 vol%. Accordingly, based on the total mixture of the luminescent material and the matrix material, the mixture contains between 1 vol% and 99 vol%, preferably between 2 vol% and 90 vol%, more preferably between 3 vol% and 40 vol%, and especially between 5 vol% and 20 vol%.

[0139] Another preferred embodiment of the present invention is that the compounds of the present invention are used in combination with other matrix materials as a matrix material for phosphorescent emitters. Suitable matrix materials that can be used in combination with the compounds of the present invention are: aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones, such as those according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines, carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl) or carbazole derivatives disclosed in WO2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO2013 / 041176; indolecarbazole derivatives, such as those according to WO 2007 / 063754 or WO WO 2008 / 056746; indocarbazole derivatives, such as those according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160; bipolar matrix materials, such as those according to WO 2007 / 137725; silanes, such as those according to WO 2005 / 111172; borazine or borate esters, such as those according to WO 2006 / 117052; triazine derivatives, such as those according to WO 2007 / 063754, WO 2008 / 056746, WO WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO2011 / 060877; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; silylated diazacyclopentane or silylated tetrazacyclopentane derivatives, for example according to WO 2010 / 054729; phosphorus diazacyclopentane derivatives, for example according to WO2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; biphenylide derivatives, for example according to WO 2012 / 048781; or dibenzofuran derivatives, such as those according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565.Other phosphorescent emitters with shorter emission wavelengths than the actual emitter can also exist as co-substrate in the mixture, or compounds that participate in charge transport but not to a significant extent, such as those described in, for example, WO2010 / 108579.

[0140] In a preferred embodiment of the invention, the material is used in combination with other matrix materials. Preferred co-matrix materials, especially when the compounds of the invention are substituted with electron-deficient heteroaromatic rings, are selected from bicarbazole, bridged carbazole, triarylamine, dibenzofuranyl-carbazole derivatives or dibenzofuranyl-amine derivatives, and carbazoleamine.

[0141] The preferred bicarbazole has the structures of formulas (9) and (10):

[0142]

[0143] Among them, Ar, R and A 1 as follows:

[0144] A 1 The same or different in each case and is NAr 2 O, S or C(R)2;

[0145] Ar may be the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and being substituted by one or more R groups in each case;

[0146] R is the same or different in each case and is: H, D, F, Cl, Br, I, B (OR) 1 )2, CHO, C(=O)R 1 CR 1 =C(R) 1 )2, CN, C(=O)OR 1 C(=O)N(R) 1 )2,Si(R 1 )3, N(R 1 )2, NO2, P(=O)(R 1 )2, OSO2R 1 OR 1 S(=O)R 1 S(=O)2R 1 SR 1 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R1 C = CR 1 -、-C≡C-、Si(R 1 2. C=O, C=S, C=NR 1 -C(=O)O-, -C(=O)NR 1 -、NR 1 P(=O)(R) 1 The aromatic ring may be replaced by -O-, -S-, SO or SO2, or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be replaced by one or more R 1 A group-substituted aromatic or heteroaromatic ring system in which two or more R groups can be linked together and form a ring.

[0147] In a preferred embodiment of the present invention, A 1 It is CR2.

[0148] In the cases of formulas (9) and (10), Ar is preferably an aromatic or heteroaromatic ring system, preferably the same or different in each case, and selected from the following formulas Ar-1 to Ar-82:

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] The dashed lines represent the keys connecting to the basic skeleton. Additionally:

[0156] Ar 3 In each case they may be the same or different and are divalent aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms and in each case they may be substituted by one or more R groups;

[0157] Ar 2 It is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms that can be substituted by one or more R groups;

[0158] A 1 The same or different in each case and is NAr 2 O, S or C(R)2;

[0159] n is either 0 or 1, where n = 0 means there is no A. 1The group is bonded at this position, but instead, the R group is bonded to the corresponding carbon atom;

[0160] m can be 0 or 1, where m = 0 means Ar 3 The functional group is absent and the corresponding aromatic or heteroaromatic functional group is directly bonded to the nitrogen atom.

[0161] Preferred embodiments of the compounds of formulas (9) and (10) are the compounds of formulas (9a) and (10a):

[0162]

[0163] The symbols used have the definitions specified above according to equations (9) and (10).

[0164] Examples of suitable compounds of formulas (9) and (10) are the compounds shown below:

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] The preferred bridged carbazole has the structure of formula (11):

[0171]

[0172] Where A 1 And R has the definitions specified above according to equations (9) and (10), and A 1 Preferably, the same or different in each case and selected from NAr and CR2.

[0173] Preferred dibenzofuran derivatives are compounds of formula (12):

[0174]

[0175] Oxygen can also be replaced by sulfur to form dibenzothiophene, where L is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms that can also be substituted by one or more R groups, and R and Ar have the definitions given above. It is also possible for two Ar groups bonded to the same nitrogen atom, or an Ar group bonded to the same nitrogen atom and an L group, to bond together to, for example, produce carbazole.

[0176] Examples of suitable dibenzofuran derivatives are the compounds shown below.

[0177]

[0178]

[0179] Preferred carbazoles have the structures of formulas (13), (14), and (15):

[0180]

[0181] Where L is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and being substituted by one or more R groups, and R and Ar have the definitions specified above according to formulas (9) and (10).

[0182] Examples of suitable carbazole derivatives are the compounds shown below.

[0183]

[0184]

[0185]

[0186] Other particularly preferred co-matrix materials, especially hole transport co-hosts, especially when the compounds of the present invention are substituted with electron-deficient heteroaromatic ring systems, are shown in the table below:

[0187]

[0188]

[0189]

[0190]

[0191] Preferred co-matrix materials, especially when the compounds of the present invention are substituted with electron-rich heterocyclic aromatic rings such as carbazole groups, are also selected from triazine derivatives, pyrimidine derivatives, and quinazoline derivatives. Preferred triazine, quinazoline, or pyrimidine derivatives that can be used in mixtures with the compounds of the present invention are compounds of formulas (16), (17), (18), and (19):

[0192]

[0193] Ar and R have the definitions specified above according to equations (9) and (10).

[0194] Triazine derivatives of formula (16) and quinoxaline derivatives of formula (19) are particularly preferred, especially triazine derivatives of formula (16).

[0195] In a preferred embodiment of the invention, the Ar in formulas (16), (17), (18), and (19) may be the same or different in each case and is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, especially 6 to 24 aromatic ring atoms, and which may be substituted by one or more R groups. The suitable aromatic or heteroaromatic ring system Ar here is the same as that described above for the embodiments of Ar, especially the structures Ar-1 to Ar-82.

[0196] Examples of suitable triazine and pyrimidine compounds that can be used together with the compounds of the present invention as matrix materials are shown in the table below:

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] Examples of suitable quinazoline and quinoxaline compounds are shown in the table below:

[0207]

[0208]

[0209] Suitable phosphorescent compounds (= triplet emitters) are especially compounds that emit light upon appropriate excitation, preferably in the visible light region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, particularly a metal having that atomic number. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum.

[0210] Examples of the aforementioned luminescent materials can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO 2016 / 015815、WO 2016 / 124304、WO 2017 / 032439、WO 2018 / 011186、WO 2018 / 041769、WO 2019 / 020538、WO 2018 / 178001, WO 2019 / 115423 and WO 2019 / 158453. Generally speaking, all phosphorescent complexes known to those skilled in the art in the field of organic electroluminescence are suitable for use in phosphorescent OLEDs, and those skilled in the art will be able to use other phosphorescent complexes without inventive effort.

[0211] Examples of phosphorescent dopants are listed below.

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] In the other layers of the organic electroluminescent device of the present invention, any material commonly used according to the prior art can be used. Therefore, those skilled in the art will be able to combine any material known for use in organic electroluminescent devices with the compounds of formula (1) of the present invention or the preferred embodiments described above without any inventive effort.

[0220] Another preferred embodiment is an organic electroluminescent device characterized by coating one or more layers via a sublimation method. In this case, the coating is carried out in a vacuum sublimation system at a temperature of less than 10... -5 millibars, preferably less than 10 -6 The material is applied via vapor deposition at an initial pressure of millibars. However, the initial pressure can also be even lower, for example, less than 10. -7 millibar.

[0221] Also preferred is an organic electroluminescent device, characterized by coating one or more layers by OVPD (organic vapor deposition) or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied at a pressure between millibar and 1 bar. A special case of this method is OVJP (Organic Vapor Jetting), in which the material is applied directly through a nozzle and thus structured.

[0222] Another preferred organic electroluminescent device is characterized by generating one or more layers from a solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (photoinduced thermal imaging, thermal transfer), inkjet printing, or nozzle printing. For this purpose, a soluble compound is required, which is obtained, for example, through appropriate substitution.

[0223] Alternatively, a hybrid approach is feasible, in which one or more layers are applied from a solution and one or more other layers are applied via vapor deposition.

[0224] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices containing the compounds of the present invention without any inventive effort.

[0225] The compounds of the present invention and the organic electroluminescent devices of the present invention are noteworthy due to one or more of the following surprising properties:

[0226] 1. The compounds of the present invention are used as matrix materials for phosphorescent emitters, resulting in a long lifespan.

[0227] 2. The compounds of the present invention result in high efficiency, especially high EQE. This is particularly true when said compounds are used as matrix materials for phosphorescent emitters.

[0228] 3. The compounds of the present invention result in low operating voltages. This is especially true when said compounds are used as matrix materials for phosphorescent emitters.

[0229] The invention is illustrated in more detail by way of the following examples, but is not intended to limit the invention. Those skilled in the art will be able to practice the invention throughout the scope of the disclosure using the information provided, and to prepare other compounds of the invention without inventive effort, and to use them in electronic devices or employ the methods of the invention. Example

[0230] Unless otherwise stated, the following synthesis was carried out under a protective gas atmosphere in a dry solvent. Solvents and reagents are commercially available from, for example, Sigma-Aldrich or ABCR. For individual compounds, the corresponding number in square brackets or the reference number corresponds to the CAS number of that compound as known from the literature.

[0231] Preparation of synthons:

[0232] S1a:

[0233]

[0234] Trifluoromethanesulfonic acid (73 g, 482 mmol) was added dropwise over 30 minutes at 0 °C to a solution of 2-iodo-1,1'-biphenyl (45 g, 160 mmol) and 3-chlorobenzoic acid (55.5 g, 241 mmol) in DCM (700 mL). The reaction mixture was then heated to room temperature and stirred for one hour, after which it was concentrated. MTBE (300 mL) was added to the residue, and the mixture was stirred at room temperature for one hour. The solid was filtered off, washed with MTBE (3 × 50 mL), and dried in a vacuum oven. Yield: 56.4 g (131 mmol, 82%), 96% as determined by NMR.

[0235] S2a:

[0236]

[0237] In a sealed 1L flask under an inert atmosphere, an initial feed consisting of 3-amino-1-chloro-2-naphthylcarboxylic acid (11.59 g, 52.3 mmol) [CAS-1823470-44-5], S1a (56.4 g, 131 mmol), K2CO3 (16.00 g, 115.9 mmol), and NMP (350 mL) was prepared. Subsequently, Pd(OAc)2 (350 mg, 1.66 mmol) was added, and the reaction mixture was stirred at 145 °C for 17 hours. After cooling, the reaction was treated by extraction with ethyl acetate and water. The combined organic phases were washed three times with water (200 mL each time) and twice with saturated NaCl solution (100 mL each time), dried over Na2SO4, and the solvent was removed by rotary evaporation on a rotary evaporator. The crude product was further purified by column chromatography. Yield: 3.8 g (13 mmol, 25%), obtained by column chromatography. 1 The purity was determined to be 95% by HNMR.

[0238] S2b:

[0239]

[0240] Compound S2b can be prepared from 1-amino-3-chloronaphthalene-2-carboxylic acid and S1a using a procedure similar to that described for synthon S2a. Yield: 21%

[0241] S3a:

[0242]

[0243] Under an inert atmosphere, an initial feed was prepared from 2-bromo-1-chloro-3-nitrobenzene (23.6 g, 100 mmol) [CAS-19128-48-4], β-[2-(1-naphthyl)phenyl]boronic acid (24.8 g, 100 mmol) [CAS-500904-93-8], and sodium carbonate (21.2 g, 200 mmol) in toluene (700 mL) and water (150 mL). Tetra(triphenylphosphine)palladium(0) (2.32 g, 2.00 mmol) was then added, and the reaction mixture was stirred under reflux for 16 hours. After cooling, the reaction mixture was filtered through a glass frit packed with toluene and diatomaceous earth, and then treated by extraction with toluene and water. The organic phase was washed with water (200 mL) and a saturated NaCl solution (100 mL) and dried over Na₂SO₄, with the solvent removed on a rotary evaporator. The crude product was recrystallized from ethanol. Yield: 21.6 g (60 mmol, 60%), via 1 The purity was determined to be 96% by ¹H NMR.

[0244] S3b:

[0245]

[0246] Compound S3b can be prepared using a procedure similar to that described for synthon S3a. β-[2-(2-naphthyl)phenyl]boronic acid is used instead of β-[2-(1-naphthyl)phenyl]boronic acid. Yield: 55%

[0247] S3c:

[0248]

[0249] Compound S3c can be prepared by a procedure similar to that described for synthesizing S3a, from 2-bromo-3-chloro-6-methoxynitrobenzene [1698810-56-8] and β-[2-(1-naphthyl]phenyl]boronic acid. Yield: 46%

[0250] S4a:

[0251]

[0252] Under an inert atmosphere, an initial feed was prepared from S3a (21.6 g, 60 mmol) and potassium carbonate (41.5 g, 300 mmol) in dimethylacetamide (400 mL). Subsequently, palladium acetate (674 mg, 3.00 mmol) and 1,3-bis(2,6-diisopropylphenyl)-3H-imidazolium-1-chloroacetate were added. (2.55 g, 6.00 mmol) [CAS-250285-32-6] and the reaction mixture was stirred at 145 °C for 24 hours. After cooling, DMAc was removed in large quantities by rotary evaporation, and the mixture was treated by extraction with toluene (600 mL) and water. The aqueous phase was extracted twice with toluene (250 mL each time). Subsequently, the combined organic phases were washed twice with water (300 mL each time) and twice with saturated NaCl solution (150 mL) and dried over Na2SO4. The filtrate was concentrated by rotary evaporation. 400 mL of n-heptane was added to the crude product, and the mixture was stirred at room temperature for 30 minutes. The solid was then filtered off, washed with n-heptane, and dried in a vacuum drying oven. Yield: 10.1 g (31.2 mmol, 52%), by 1 The purity was determined to be 95% by ¹H NMR.

[0253] S4b:

[0254]

[0255] Compound S4b can be prepared from S3b using a procedure similar to that described for synthon S4a. Yield: 32%

[0256] S4c:

[0257]

[0258] Compound S4c can be prepared from S3c using a procedure similar to that described for synthon S4a. Yield: 49%

[0259] S5a:

[0260]

[0261] S4a (14.4 g, 44.4 mmol) was hydrogenated in 150 mL of ethanol with 1 g of palladium / carbon at 3 bar hydrogen pressure for 36 h. The reaction mixture was filtered twice through a Celite bed. The filtrate was concentrated by rotary evaporation, and the resulting solid was recrystallized from toluene.

[0262] Yield: 10.7g (36.6mmol, 82%), via 1 The purity was determined to be 97% by ¹H NMR.

[0263] S5b:

[0264]

[0265] Compound S5b can be prepared from S4b using a procedure similar to that described for synthon S5a. Yield: 87%

[0266] S5c:

[0267]

[0268] Compound S5c can be prepared from S4c using a procedure similar to that described for synthon S5a. Yield: 62%

[0269] S6a:

[0270]

[0271] The initial feed consisted of S2a (3.8 g, 13.0 mmol), neopentanoic acid (2.66 g, 26.0 mmol), Cu(OAc)2 [CAS-142-71-2] (485 mg, 2.67 mmol), [Cp*IrCl2]2 [CAS-12354-84-6] (426 mg, 0.53 mmol), and NMP (100 mL) in a flask. Air was passed through the reaction mixture using a syringe, and the reaction was stirred at 120 °C for 50 min. After cooling, the NMP was distilled off, and the residue was further purified by column chromatography. Yield: 3.1 g (10.5 mmol, 81%), obtained by column chromatography. 1 The purity was determined to be 98% by ¹H NMR.

[0272] S6b:

[0273]

[0274] Similar to S6a, compound S6b can be prepared from S5a. Yield: 72%

[0275] S6c:

[0276]

[0277] Similar to S6a, compound S6c can be prepared from S5b. Yield: 76%

[0278] S6d:

[0279]

[0280] Similar to S6a, compound S6d can be prepared from S2b. Yield: 44%

[0281] S6e:

[0282]

[0283] Similar to S6a, compound S6e can be prepared from S5c. Yield: 36%

[0284] S7a:

[0285]

[0286] An initial feed was prepared under an inert atmosphere using DMSO (100 mL), K3PO4 (106.15 g, 500 mmol), pyridine-2-carboxylic acid (3.06 g, 24.87 mmol), and CuI (2.37 g, 12.44 mmol). Then, 3-chloro-5-methoxyphenol (45.57 g, 300 mmol) [65262-96-6] and 3-bromo-1-chloronaphthalene (60.38 g, 250 mmol) [325956-47-6] were added sequentially, and the reaction mixture was heated at 85 °C for 16 hours. After cooling, the reaction mixture was treated by extraction with ammonia solution and methyl tert-butyl ether. The organic phase was washed five times with water and twice with saturated NaCl solution. The combined phase was dried over Na2SO4, and the solvent was removed by rotary evaporator. The crude product was further purified by fractional distillation. Yield: 64.64 g (202 mmol), purity: 81%, obtained through... 1 The purity was determined to be 95% by ¹H NMR.

[0287] The following compounds can be prepared similarly: purification can be carried out not only by distillation but also by column chromatography, or recrystallization can be carried out using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0288]

[0289]

[0290] S8a:

[0291]

[0292] The initial feed of S7a (159.6 g, 500 mmol) in THF (750 mL) was cooled to -75 °C under an inert atmosphere. Then, n-butyllithium (2.5 mol / L in hexane, 400 mL, 1.00 mmol) was slowly added dropwise at an internal temperature not exceeding -65 °C. The mixture was stirred at -75 °C for another 4 hours, followed by the dropwise addition of bromine (28.0 mL, 546.5 mmol) at an internal temperature not exceeding -65 °C. After the addition was complete, the mixture was stirred at -75 °C for 1 hour, then gradually heated to 10 °C over 1 hour and stirred at 10 °C for 1 hour. The mixture was then cooled to 0 °C and carefully quenched with a saturated Na₂SO₃ solution (250 mL). The mixture was treated by extraction with toluene and water; the combined organic phases were washed three times with water, once with a saturated NaCl solution, dried over Na₂SO₄, and the solvent was removed using a rotary evaporator. The crude product was extracted by refluxing with 2-propanol three times with stirring. The product was further converted into a mixture of isomers. Yield: 133.8 g (370 mmol, 74%), obtained by... 1 The purity was determined to be 95% by ¹H NMR.

[0293] The following compounds can be prepared similarly: purification can be carried out not only by extraction with stirring but also by distillation, or by column chromatography or recrystallization using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-diethyl ether, etc. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0294]

[0295]

[0296] S9a:

[0297]

[0298] S8d (139.0 mmol), β-(6-methoxy-2-naphthyl)boronic acid (31.21 g, 154.5 mmol) [156641-984], and K2CO3 (38.84 g, 281.0 mmol) were inertized for 30 min in an initial feed of THF (720 mL) and water (180 mL). Subsequently, tetrakis(triphenylphosphine)palladium [14221-01-3] (1.78 mg, 1.54 mmol) was added, and the reaction mixture was refluxed and stirred for 16 h. The mixture was treated by extraction with toluene and water, the combined organic phases were washed with water and a saturated NaCl solution, dried over Na2SO4, and the solvent was removed on a rotary evaporator. The crude product was recrystallized from ethyl acetate. Yield: 35.8 g (100 mmol, 72%), obtained by… 1 The H NMR measurement was 97%.

[0299] The following compounds can be prepared similarly: purification can be carried out by column chromatography, or recrystallization can be carried out using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0300]

[0301]

[0302]

[0303] S10a:

[0304]

[0305] DMAc (500 mL) was added to the initial feed of S9b (35.08 g, 100 mmol) and K2CO3 (41.37 g, 299.3 mmol) under an inert atmosphere, and the mixture was inertized for 30 minutes. Subsequently, Pd(OAc)2 (447 mg, 1.99 mmol) and 1,3-bis(2,6-diisopropylphenyl)-3H-imidazolium-1-chlorodimethylamine were added. (1.69 g, 3.98 mmol), and the reaction mixture was stirred at 155 °C for 16 hours. After cooling, the mixture was poured into ethanol / water (1:1, 800 mL) and stirred for another 30 minutes. The precipitated solid was filtered off, washed 5 times with water and 3 times with ethanol. The crude product was extracted by reflux with 2-propanol. Yield: 26.4 g (82 mmol, 82%), obtained by... 1 The H NMR measurement was 97%.

[0306] The following compounds can be prepared similarly: purification can be carried out by column chromatography, or recrystallization can be carried out using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0307]

[0308]

[0309]

[0310] S11a:

[0311]

[0312] The initial feed of S10a (32.21 g, 100 mmol) in dichloromethane (650 mL) was cooled to 0 °C in an ice bath. Then, BBr3 (6.0 mL, 63.2 mmol) was carefully added dropwise. After the addition was complete, the mixture was warmed to room temperature. Upon completion of the conversion, the mixture was cooled back to 0 °C and carefully quenched with MeOH (200 mL). The solvent was removed on a rotary evaporator. Subsequently, 300 mL of MeOH was added to the mixture in three portions, followed by removal on a rotary evaporator. Another 200 mL of MeOH was added, and the solid was filtered off. The crude product was dried and used in the next stage. Yield: 19.4 g (63 mmol, 63%).

[0313] The following compounds can be prepared similarly: purification can be carried out by column chromatography, or recrystallization can be carried out using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0314]

[0315]

[0316]

[0317] S12a:

[0318]

[0319] The initial feed of S11a (13.95 g, 45.3 mmol) and triethylamine (18.8 mL, 135.9 mmol) in dichloromethane (650 mL) was cooled to 0 °C in an ice bath. Trifluoromethanesulfonic anhydride (9.9 mL, 58.9 mmol) was then slowly added dropwise. After the addition was complete, the mixture was warmed to room temperature. Upon completion of the conversion, the mixture was extracted with dichloromethane and water, the combined organic phases were dried over Na₂SO₄, and the solvent was removed using a rotary evaporator. The residue was added to 400 mL of cyclohexane, and the mixture was stirred at room temperature for 30 min. The solid was filtered off and dried in a vacuum drying oven. Yield: 14.95 g (34.0 mmol, 75%)

[0320] The following compounds can be prepared similarly: purification can be carried out by column chromatography, or recrystallization can be carried out using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0321]

[0322]

[0323]

[0324] S13a:

[0325]

[0326] S12b (13.28 g, 30.2 mmol), bis(pinacol)diboron (9.40 g, 36.3 mmol), and KOAc (8.90 g, 90.68 mmol) were prepared in a 1,4-dioxanone atmosphere. The initial feed in alkyl (250 ml) was inert for 30 minutes. Then Pd(dppf)Cl2 (740 mg, 0.91 mmol) was added, and the mixture was kept at 20 mL. Compounds can be prepared similarly as follows: Alternatively, the catalyst system used can be Pd(PCy3)2Cl2 or Pd2(dba)3 with S-Phos (1:3). Purification can be carried out not only by column chromatography, but also by thermal extraction, or by using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-di(2,3 ... The process can be carried out by recrystallization or thermal extraction of alkane, or by recrystallization using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0327]

[0328]

[0329]

[0330] S14:

[0331]

[0332] The initial feed consisted of S6e (32.1 g, 100 mmol), bromobenzene (17.3 g, 110 mmol), and sodium tert-butoxide (20.18 g, 210 mmol) in toluene (800 mL). XPhos Pd G3 [CAS-1445085-55-1] (3.40 g, 4.6 mmol) was then added, and the reaction solution was heated to boiling for 24 hours. The reaction solution was then cooled to room temperature. The reaction mixture was treated by extraction with toluene and water. The combined organic phases were dried over Na2SO4, and the solvent was removed on a rotary evaporator. The crude product was recrystallized from n-butyl acetate. Yield: 18.0 g (87 mmol, 87%), obtained by… 1 The purity was determined to be 98% by ¹H NMR.

[0333] Preparation of the compounds of the present invention

[0334] Synthesis of P1a:

[0335]

[0336] The initial feed consisted of S6a (8.30 g, 28.5 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.40 g, 31.3 mmol) [CAS-3842-55-5], and sodium tert-butoxide (3.00 g, 31.3 mmol) in toluene (250 mL). XPhos Pd G3 [CAS-1445085-55-1] (2.10 g, 2.8 mmol) was then added, and the reaction mixture was heated to boiling for 72 hours. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporator. The crude product was purified by column chromatography (n-heptane / ethyl acetate), followed by recrystallization four times from n-butyl acetate and sublimation under high vacuum. Yield: 7.9 g (15.1 mmol, 53%); Purity: >99.9% by HPLC.

[0337] The following compounds can be prepared similarly: purification can be carried out not only by column chromatography, but also by thermal extraction, or by using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-diethyl-2-ethylhexane, etc. The process can be carried out by recrystallization or thermal extraction of alkane, or by recrystallization using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347] P2a:

[0348]

[0349] The initial feed consisted of S6a (17.92 g, 61.5 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine [CAS-864377-31-1] (25.2 g, 65.0 mmol), and sodium tert-butoxide (13.4 g, 139.1 mmol) in o-xylene (550 mL). XPhos Pd G3 (1.70 g, 2.3 mmol) was then added, and the reaction mixture was heated to boiling for 24 hours. The reaction solution was cooled to room temperature, and the precipitated solid was filtered off and washed three times with ethanol (150 mL each time). The crude product was then subjected to basic thermal extraction three times with toluene on alumina, followed by extraction from 1,4-diphenyltriazine. The solution was recrystallized twice from the alkane and finally sublimated under high vacuum. Yield: 18.0 g (30.1 mmol, 49%); Purity: >99.9% as determined by HPLC.

[0350] The following compounds can be prepared similarly: the catalyst system can also use Pd2(dba)3 or Pd(OAc)2 with X-Phos or S-Phos. Purification can be carried out by column chromatography, thermal extraction or recrystallization. Recrystallization or thermal extraction can be performed using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-diethyl-2-ethylhexylene, etc. Alkane-based methods, or recrystallization, can be carried out using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360] P3a:

[0361]

[0362] Sodium tert-butoxide (6.34 g, 66.0 mmol) was added to the initial feed of S6a (17.48 g, 60.0 mmol) in DMSO (400 mL), and the mixture was stirred at room temperature for 30 min. Subsequently, 2-chloro-4-d5-phenylquinazoline (16.25 g, 66.0 mmol) [CAS-1614244-83-5] was added, and the reaction was stirred at room temperature for 24 h. The solvent was then removed under reduced pressure, and the residue was extracted with 1500 mL of hot ethanol under stirring. The crude product was subjected to three alkaline thermal extractions with o-xylene on alumina, recrystallized twice from DMF, and finally sublimated under high vacuum. Yield: 16.52 g (33.0 mmol, 55%); Purity: >99.9% by HPLC.

[0363] The following compounds can be prepared similarly: purification can be carried out using column chromatography, thermal extraction, or recrystallization. Recrystallization or thermal extraction can be performed using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane-based methods, or recrystallization, can be carried out using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0364]

[0365]

[0366]

[0367]

[0368] P4a:

[0369]

[0370] Potassium phosphate (38.20 g, 180.0 mmol) was added to the initial feed of S6a (17.48 g, 60.0 mmol) and 2-chloro-3-phenylquinoxaline (20.0 g, 60.0 mmol) [CAS-7065-92-1] in DMF (350 mL), and the mixture was refluxed and stirred for 24 hours. After cooling, the solvent was removed under reduced pressure, and the resulting residue was suspended in 250 mL of ethanol and 250 mL of water. The solid was filtered off and washed with ethanol (5 × 150 mL). The crude product was then subjected to two basic thermal extractions on alumina with toluene and two basic thermal extractions with n-butyl acetate, followed by sublimation under high vacuum.

[0371] Yield: 13.96 g (28.2 mmol, 47%); Purity: >99.9% as determined by HPLC.

[0372] The following compounds can be prepared similarly: purification can be carried out using column chromatography, thermal extraction, or recrystallization. Recrystallization or thermal extraction can be performed using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane-based methods, or recrystallization, can be carried out using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0373]

[0374]

[0375]

[0376]

[0377]

[0378] P5a:

[0379]

[0380] S13a (33.3 mmol), 2-[1,1'-biphenyl]-4-yl-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (35.0 mmol) [CAS-1955546-91-4] and K3PO4 (14.14 g, 66.6 mmol) were reacted in toluene / dimethylformamide. The initial feed in alkyl / water (200 mL / 200 mL / 100 mL) was inert for 30 min. Subsequently, triphenylphosphine (175 mg, 0.67 mmol) and Pd₂(dba)₃ (305 mg, 0.33 mmol) were added sequentially, and the mixture was refluxed and stirred for 16 h. The mixture was treated by extraction with toluene and water. The combined organic phases were dried over Na₂SO₄, and the solvent was removed on a rotary evaporator. The crude product was then subjected to three thermal extractions with toluene / heptane (1:1), recrystallized twice from n-butyl acetate, and finally sublimated under high vacuum. Yield: 10.6 g (15.7 mmol, 47%); Purity: >99.9% by HPLC.

[0381] Compounds can be prepared similarly using S-Phos or X-Phos or P(o-tol)3 with Pd2(dba)3 or Pd(OAc)2. Purification can be carried out using column chromatography, thermal extraction, or recrystallization. Recrystallization or thermal extraction can be performed using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, and 1,4-diethyl-2-ethylhexylene. Alkane-based methods, or recrystallization, can be carried out using high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0382]

[0383]

[0384]

[0385]

[0386]

[0387] OLED manufacturing

[0388] Pretreatment of Examples V1 to E5h: Before coating, a glass plate coated with a 50 nm thick structured ITO (indium tin oxide) was first treated with oxygen plasma, and then with argon plasma. These plasma-treated glass plates formed the substrate for applying the OLED.

[0389] OLEDs essentially have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally, a cathode. The cathode is formed from an aluminum layer with a thickness of 100 nm. The exact structure of an OLED can be seen in Table 1. Table 3 shows the materials required to manufacture an OLED. Table 2 lists the data for OLEDs.

[0390] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (host material) and a luminescent dopant (emitter), which is added to one or more matrix materials by co-evaporation in a specific volume ratio. Details given in the form of P1a:IC2:TER1 (57%:40%:3%) mean that material P1a is present in the layer at a volume ratio of 57%, IC2 at a volume ratio of 40%, and TER1 at a volume ratio of 3%. Similarly, the electron transport layer can also consist of a mixture of the two materials.

[0391] OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum was determined, the external quantum efficiency (EQE, expressed as a function of luminance, calculated from the current-voltage-luminance characteristics exhibiting Lambertian radiation, and the lifetime was determined. The electroluminescence spectrum was at 1000 cd / m². 2 The brightness was determined and used to calculate the CIE 1931 x and y color coordinates. The parameter U1000 in Table 3 refers to 1000 cd / m². 2 The voltage required for brightness. EQE1000 indicates the voltage required at 1000 cd / m². 2 The external quantum efficiency achieved. Lifetime LD is defined as the time it takes for the luminance to decrease from its initial value to a specific proportion L1 during operation at a constant current density j0. The figure L1 = 95% in Table 3 refers to the lifetime reported in the LD column corresponding to the time it takes for the luminance to decrease to 95% of its initial value.

[0392] Use of the mixture of the present invention in the light-emitting layer of a phosphorescent OLED

[0393] The materials of the present invention are used as matrix materials in the emissive layer of red phosphorescent OLEDs in Examples E1a-E1n, E2a-E2j, E3a-E3f, E4a-E4e, and E5a-E5h. Compared with the prior art (V1 to V5), a significant improvement in lifetime can be achieved while keeping other parameters comparable.

[0394] Table 1: Structure of OLED

[0395]

[0396]

[0397]

[0398]

[0399] Table 2: OLED Data

[0400]

[0401]

[0402] Table 3: Structural formulas of the OLED materials used, unless otherwise described above:

[0403]

[0404]

[0405]

Claims

1. A compound of any one of formulas (5-1), (6-1), (7-1), or (8-1), in Y is NAr 1 ; Ar 1 Selected from groups R-47 to R-50, R-57, R-58, R-76, R-79, R-80, R-81 and R-82: Dashed lines indicate bonds that connect to carbon atoms in the basic framework of formulas (5-1), (6-1), (7-1), or (8-1); Ar 3 In each case, they may be the same or different, and they have 6 to 18 aromatic ring atoms and in each case can be one or more R 1 Divalent aromatic or heteroaromatic ring systems with substituted groups; A 1 The same or different in each case and is C(R) 1 2. NR 1 , O or S; p is 0 or 1; R is the same or different in each case and is: H, D, F, CN, OR 1 A straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 1 The substitution of groups, wherein one or more non-adjacent CH2 groups may be replaced by -O-, or an aromatic or heteroaromatic ring system selected from: phenyl, biphenyl, terphenyl, tetraphenyl, fluorene linked at positions 1, 2, 3, or 4, spirodifluorene linked at positions 1, 2, 3, or 4, naphthalene linked at positions 1 or 2, indole, benzofuran, benzothiophene linked at positions 1, 2, 3, or 4, dibenzofuran, carbazole linked at positions 1, 2, 3, or 4, dibenzothiophene linked at positions 1, 2, 3, or 4, indocarbazole, indolecarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene, biphenylene oxide, or combinations of two or three of these groups, each of which may be replaced by one or more R- groups. 1 Group substitution; R 1 In each case, they are the same or different and are: H, D, F, I, B (OR) 2 )2,N(R 2 )2, CHO, C(=O)R 2 CR 2 =C(R) 2 )2, CN, C(=O)OR 2 ,Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 SR 2 OR 2 S(=O)R 2 S(=O)2R 2 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 2 Group substitution, wherein one or more CH2 groups in the above groups can be -R 2 C = CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, NR 2 CONR 2 P(=O)(R) 2 The following groups may be replaced by -O-, -S-, SO, or SO2, and one or more hydrogen atoms in the above groups may be replaced by D, F, Cl, Br, I, CN, or NO2, or have 5 to 30 aromatic ring atoms and in each case may be replaced by one or more R... 2 Aromatic or heteroaromatic ring systems with substituted groups, wherein two or more R groups are present. 1 The groups can together form aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring systems; R 2 In each case, the same or different are: H, D, F, CN, or an aliphatic, aromatic, or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may also be replaced by D or F; and simultaneously, two or more R 2 Substituents can connect with each other and form rings.

2. The compound according to claim 1, wherein R 1 In each case, they may be the same or different and are selected from: H, D, F, CN, OR 2 A straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups may be replaced by O, or having 6 to 30 aromatic ring atoms and in each case being replaced by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

3. The compound according to claim 1, wherein R 2 In each case, the same or different are: H, F, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, said group being substituted by an alkyl group having 1 to 4 carbon atoms.

4. The compound according to claim 1, wherein the compound is selected from the group consisting of:

5. A formulation comprising at least one compound according to any one of claims 1 to 4 and at least one other compound, wherein the other compound is a luminescent compound or a matrix material.

6. The formulation according to claim 5, wherein the matrix material is an aromatic ketone, an aromatic phosphine oxide, an aromatic sulfoxide, an aromatic sulfone, a triarylamine, a carbazole, an indolocarbazole, an indocarbazole, an azacarbazole, a silane, a borazine, a borate ester, a triazine, a zinc complex, a diazacarbazole, a tetrazacarbazole, a phosphazacarbazole, a bridged carbazole, a tribenzoxylidene, or a dibenzofuran.

7. Use of the compound according to any one of claims 1 to 4 and / or the formulation according to claim 5 or 6 as a matrix material in electronic devices.

8. The use according to claim 7, wherein the compound according to any one of claims 1 to 4 is used in combination with a matrix material selected from: bicarbazole, bridged carbazole, triarylamine, dibenzofuranyl-carbazole, dibenzofuranyl-amine and carbazoleamine.

9. An electronic device comprising at least one compound according to any one of claims 1 to 4 or an agent according to claim 5 or 6.

10. The electronic device according to claim 9, wherein the electronic device is an organic electroluminescent device, characterized in that... The compound according to any one of claims 1 to 4 is used as a matrix material in the luminescent layer as a phosphorescent or fluorescent luminescent material or a luminescent material exhibiting TADF (thermally activated delayed fluorescence), or in an electron transport layer and / or a hole blocking layer and / or a hole transport layer and / or an exciton blocking layer.

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