CN114450286A

CN114450286A - Material of organic electroluminescent device

Info

Publication number: CN114450286A
Application number: CN202080064440.7A
Authority: CN
Inventors: 阿米尔·帕勒姆; 乔纳斯·克罗巴; 延斯·恩格哈特; 安雅·雅提斯奇; 克里斯蒂安·艾克霍夫; 克里斯蒂安·埃伦赖希; 詹斯·凯泽
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2019-09-16
Filing date: 2020-09-15
Publication date: 2022-05-06
Also published as: WO2021052924A1; EP4031546A1

Abstract

The present invention relates to compounds of formula (1), the use of the compounds in electronic devices, and electronic devices comprising compounds of formula (1). The invention also relates to a method for producing the compounds of formula (1) and to agents containing one or more compounds of formula (1).

Description

Material of organic electroluminescent device

The present invention relates to compounds of formula (1), the use of said compounds in electronic devices and electronic devices comprising compounds of formula (1). The invention also relates to a method for producing the compounds of formula (1) and to agents containing one or more compounds of formula (1).

The structure of organic electroluminescent devices (OLEDs) is described, for example, in US 4539507, wherein the organic semiconductor is used as a functional material. The light-emitting material used here is often an organometallic complex that exhibits phosphorescence. For quantum mechanical reasons, the efficiency can be increased up to four-fold using phosphorescent rather than fluorescent emitters. However, in general, there is still a need for improvement in the case of OLEDs, in particular also in the case of OLEDs which exhibit triplet emission (phosphorescence), for example in terms of efficiency, operating voltage and lifetime.

The properties of phosphorescent OLEDs are determined not only by the triplet emitters but also by other materials used together with the triplet emitters in the OLED, for example matrix materials, also referred to as host materials. Thus, improving these materials and their charge transport properties can also lead to significant improvements in OLED properties.

Thus, the choice of the matrix material in the light-emitting layer comprising phosphorescent emitters has a great influence on the properties of the OLED, in particular in terms of efficiency. The host material limits quenching of the excited state emitter molecules by energy transfer.

It is an object of the present invention to provide compounds suitable for use in OLEDs. More specifically, it was an object of the present invention to provide compounds which are particularly suitable as matrix materials for phosphorescent emitters in OLEDs and, depending on the specific structures and groups present in the compounds, also as Hole Transport Materials (HTM), Electron Blocking Materials (EBM), Electron Transport Materials (ETM), Hole Blocking Materials (HBM). It is another object of the present invention to provide other organic semiconductors for use in organic electroluminescent devices to provide those skilled in the art with more possible choices of materials for fabricating OLEDs.

Compounds comprising lactam derivatives and their use as OLED materials, more particularly as matrix materials for phosphorescent emitters, are known from the prior art (for example from WO 2013/064206).

It has now been unexpectedly found that specific compounds comprising a lactam moiety in combination with a naphthalene moiety, as described in more detail below, exhibit excellent properties when used in OLEDs, in particular when used as matrix materials for red phosphorescent emitters. In fact, these compounds lead to OLEDs which exhibit better properties with respect to lifetime and/or efficiency and/or electroluminescence. In addition, these compounds have a high glass transition temperature and good thermal stability, which are important properties for OLED materials, especially when the materials are vapor deposited by vacuum methods.

The invention therefore relates to these compounds and to electronic devices, in particular organic electroluminescent devices, comprising compounds of this type. The invention also relates to mixtures and formulations comprising the mixtures.

The invention relates to compounds of formula (1),

where the following applies to the symbols and labels used:

Ar^Son each occurrence, identically or differently, represents a single bond or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be substituted by one or more R groups;

X¹to X⁴At each occurrence, the same or different surfaceShow CR¹Or N;

Y¹to Y⁴At each occurrence, identically or differently representing CR²Or N; provided that Ar shown in formula (1)^SRadical and one Y representing C¹、Y²、Y³Or Y⁴Bonding of groups; and exactly two non-adjacent Y groups, i.e. Y¹And Y⁴、Y¹And Y³Or Y²And Y⁴Represents N;

the method is characterized in that:

Z¹to Z⁸At each occurrence, identically or differently representing CR³Or N; wherein is selected from Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁶-Z⁷And Z⁷-Z⁸At least two adjacent Z groups together form a heteroaromatic ring system selected from the group consisting of the formulae (Het-1) or (Het-2),

wherein, in (Het-1) and (Het-2), the symbols^*Indication and Z in formula (1)¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁶-Z⁷Or Z⁷-Z⁸The bonding position of (a);

Z⁹to Z¹²At each occurrence, identically or differently representing CR³Or N;

R^Non each occurrence, the same or different indicates: h, D, F, Cl, Br, I, CN, Si (R)₃Straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40C atoms, which may each be substituted by one or more R groups, where in each case one or more non-adjacent CH groups₂The radical may be substituted by RC ═ CR, C ≡ C, Si (R)₂、Ge(R)₂、Sn(R)₂、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO₂O, S or CONR, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which can be substituted in each case by one or more R groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more R groups;

and is selected from Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁶-Z⁷、Z⁷-Z⁸、Z⁹-Z¹⁰、Z¹⁰-Z¹¹And Z¹¹-Z¹²Together at least two adjacent Z groups form an aromatic ring of formula (Aro-1),

wherein Z¹³To Z¹⁶At each occurrence, identically or differently representing CR³Or N; and wherein the symbols^*Indication with Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁶-Z⁷、Z⁷-Z⁸、Z⁹-Z¹⁰、Z¹⁰-Z¹¹Or Z¹¹-Z¹²The bonding position of (a);

R¹、R²and R³On each occurrence, the same or different indicates: h, D, F, Cl, Br, I, CHO, CN, C (═ O) Ar, P (═ O) (Ar)₂，S(＝O)Ar，S(＝O)₂Ar，N(R)₂，N(Ar)₂，NO₂，Si(R)₃，B(OR)₂，OSO₂R, a linear alkyl, alkoxy or thioalkyl radical having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atomsThe thioalkyl groups can each be substituted by one or more R groups, where in each case one or more non-adjacent CH groups₂The radicals may be substituted by RC ═ CR, C ≡ C, Si (R)₂、Ge(R)₂、Sn(R)₂、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO₂O, S or CONR, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which can be substituted in each case by one or more R groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more R groups; wherein two adjacent R¹The radicals may together form an aliphatic or aromatic ring system which may be substituted by one or more R groups, where one R group²Group and one R¹The radicals may form a ring which may be substituted by one or more R groups, and wherein two adjacent R groups³The groups may together form an aliphatic or aromatic ring system, which may be substituted by one or more R groups;

r, on each occurrence, represents, identically or differently: h, D, F, Cl, Br, I, CHO, CN, C (═ O) Ar, P (═ O) (Ar)₂，S(＝O)Ar，S(＝O)₂Ar，N(R′)₂，N(Ar)₂，NO₂，Si(R′)₃，B(OR′)₂，OSO₂R 'is a linear alkyl, alkoxy or thioalkyl radical having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atoms, which may each be substituted by one or more R' radicals, where in each case one or more non-adjacent CH radicals₂The radicals may be substituted by R ' C ═ CR ', C ≡ C, Si (R ')₂、Ge(R′)₂、Sn(R′)₂、C＝O、C＝S、C＝Se、P(＝O)(R′)、SO、SO₂O, S or CONR' and in which one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, said aromatic or heteroaromatic ring systemsThe heteroaromatic ring systems may be substituted in each case by one or more R 'groups, or aryloxy groups having from 5 to 60 aromatic ring atoms, which may be substituted by one or more R' groups; wherein two adjacent R groups may together form an aliphatic or aromatic ring system, which may be substituted by one or more R' groups;

ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may also be substituted in each case by one or more R' groups;

r', at each occurrence, represents, identically or differently: h, D, F, Cl, Br, I, CN, a linear alkyl, alkoxy or thioalkyl radical having 1 to 20C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 20C atoms, where in each case one or more non-adjacent CH' s₂The radicals being selected from SO, SO₂O, S and in which one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having from 5 to 24 aromatic ring atoms.

Furthermore, the following definitions of chemical groups apply for the purposes of the present application:

adjacent groups in the sense of the present invention are groups which are bonded to atoms which are directly connected to one another or to the same atom.

An aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms; heteroaryl groups in the sense of the present invention contain 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and S. This represents a basic definition. If other preferences are indicated in the description of the invention, for example with respect to the number of aromatic ring atoms or heteroatoms present, these preferences apply.

An aryl group or heteroaryl group is here understood to mean a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine or thiophene, or a condensed (fused) aromatic or heteroaromatic polycyclic ring, for example naphthalene, phenanthrene, quinoline or carbazole. A condensed (fused) aromatic or heteroaromatic polycyclic ring in the sense of this application consists of two or more simple aromatic or heteroaromatic rings condensed with one another.

Aromatic or heteroaromatic radicals which may be substituted in each case by the abovementioned radicals and may be attached to the aromatic or heteroaromatic ring system via any desired position are to be understood as meaning in particular radicals derived from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chicory, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzopyrene, 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, thiophene

Oxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,

Azole, benzo

Azoles, naphtho

Azole, anthracenes

Azole, phenanthro

Oxazole, iso

Oxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarbazine, phenanthroline, 1,2, 3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-

Diazole, 1,2,4-

Oxadiazole, 1,2,5-

Oxadiazole, 1,3,4-

Oxadiazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizines and benzothiadiazoles.

An aryloxy group according to the definition of the present invention is taken to mean an aryl group as defined above bonded via an oxygen atom. Similar definitions apply to heteroaryloxy groups.

An aromatic ring system in the sense of the present invention contains 6 to 60C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of the present invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units (preferably less than 10% of atoms other than H), for example sp³-hybridized C, Si, N or O atoms, sp²-a hybridized C or N atom, or an sp-hybridized C atom. Thus, for example, systems such as 9,9 '-spirobifluorenes, 9' -diarylfluorenes, triarylamines, diaryl ethers, stilbenes, etc., are also intended to be considered aromatic ring systems in the sense of the present invention, and also systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, wherein two or more aryl or heteroaryl groups are linked to each other via a single bondLinked systems, for example, such as biphenyl, terphenyl or diphenyltriazine, are also to be regarded as aromatic or heteroaromatic ring systems in the sense of the present invention.

Aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may also be substituted in each case by a radical as defined above and may be attached to the aromatic or heteroaromatic radical via any desired position, are to be understood as meaning in particular radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, chicory, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, terphenyl subunit, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, triindene, isotridecyl, spiroisotridecyl, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, thiophene

Azole, benzo

Azoles, naphtho

Azoles, anthracenes

Azole, phenanthro

Oxazole, iso

Oxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza anthracene, 2, 7-diaza pyrene, 2, 3-diaza pyrene, 1, 6-diaza pyrene, 1, 8-diaza pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, thiophene

Oxazines, phenothiazines, fluoranthenes, naphthyridines, azacarbazoles, benzocarbazoles, phenanthrolines, 1,2, 3-triazoles, 1,2, 4-triazoles, benzotriazoles, 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, 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 combinations of these groups.

For the purposes of the present invention, where the individual H atoms or CH₂A straight-chain alkyl group having 1 to 40C atoms or a branched or cyclic alkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, which group may also be substituted by the groups mentioned above under the definition of said group, is preferably considered to mean the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-butyl, tert-butyl, 2-methylbutyl, neopentyl, or neopentylHeptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, or octynyl. Alkoxy or thioalkyl radicals having 1 to 40C atoms are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2, 2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2, 2-trifluoroethylylthio, An ethylenethio group, a propylenylthio group, a butylenylthio group, a pentenylthio group, a cyclopentenylthio group, a hexenylthio group, a cyclohexenylthio group, a heptenylthio group, a cycloheptenylthio group, an octenylthio group, a cyclooctenylthio group, an ethynylthio group, a propynylthio group, a butynylthio group, a pentynylthio group, a hexynylthio group, a heptynylthio group or an octynylthio group.

For the purposes of the present application, the expression that two groups may form a ring with one another is intended to be taken to mean, in particular, that the two groups are linked to one another by a chemical bond. This is illustrated by the following scheme:

furthermore, the above expression is also intended to be taken to mean that, in the case where one of the two groups represents hydrogen, the second group is bonded at the position to which the hydrogen atom is bonded, and forms a ring.

This is illustrated by the following scheme:

preferably, in the presence of Y¹To Y⁴In a six-membered ring of (2), Y⁴The radicals being N, Y³Radical with Ar^SThe radicals being bonded, thus Y³Represents C, and one Y¹Or Y²The radical corresponding to N and the other Y¹Or Y²Radical corresponds to CR². More preferably, Y⁴The radicals being N, Y³Radical with Ar^SThe radicals being bonded, thus Y³Represents C, Y²The radicals being N and Y¹The radical represents CR²。

Preferably, X¹To X⁴The radicals, on each occurrence, being identical or different, representing CR¹。

According to a preferred embodiment, Ar^SIs a single bond, such that the compound of formula (1) corresponds to a compound of formula (1A):

wherein the symbols have the same meaning as described above.

According to another preferred embodiment, Ar^SThe radicals are aromatic or heteroaromatic ring systems having from 5 to 18 aromatic ring atoms, which may also be substituted in each case by one or more R groups.

More preferably, Ar^SThe radicals represent, identically or differently on each occurrence, phenyl, biphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, benzopyridine, benzopyridazine, benzopyrimidine and quinazoline, each of which may be substituted by one or more R groups.

According to a very preferred embodiment, Ar^SThe radicals, on each occurrence, being identical or different, representing phenyl, biphenyl, fluorene, dibenzofuran, bisBenzothiophenes and carbazoles, each of which may be substituted with one or more R groups.

Suitable Ar^SExamples of radicals are those shown in the following table (Ar)^S-1) to (Ar)^S-22) a group:

wherein the dotted bond indicates a bond to the structure of formula (1), and wherein (Ar)^S-1) to (Ar)^S-22) the group can be substituted with an R group at each free position, and wherein:

R^N0、R^C0the same or different at each occurrence is: h, D, F, Cl, Br, I, CN, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms or a cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms, each of which may be substituted by one or more R groups, wherein one or more non-adjacent CH's may be present₂The radicals may be replaced by (R) C ═ C (R), C ≡ C, O or S and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead of, or as aromatic or heteroaromatic ring systems having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, very preferably from 5 to 18, aromatic ring atoms, which may in each case be substituted by one or more R groups, where optionally two adjacent R groups^C0The radicals can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

Very suitable Ar^SExamples of radicals are shown in the table below (Ar)^S-23) to (Ar)^S-67) a group:

wherein the dotted bond indicates a bond to the structure of formula (1), and wherein (Ar)^S-23) to (Ar)^S-67) the group can be substituted with an R group in each free position.

Preferably, R^NA radical denotes an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 24, very preferably from 6 to 18, aromatic ring atoms, which ring system may be substituted in each case by one or more R groups.

More preferably, R^NThe radicals, on each occurrence, being identical or different, represent: phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, indolocarbazole, phenanthroline, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinolone, benzopyridine, benzopyridazine, benzopyrimidine, quinazoline, benzimidazole, or a combination of two or three of these groups, each of which may be substituted with one or more R groups.

Very suitable R^NExamples of radicals are the radicals of the formulae (RN-1) to (RN-22) shown in the following table:

wherein:

-the dashed bond indicates the bond to the nitrogen group of the lactam ring in formula (1);

-R^C0and R^N0The radicals have the same meanings as described above; and is

The radicals of the formulae (RN-1) to (RN-22) may be substituted by an R radical in each free position.

Among the groups of formulae (RN-1) to (RN-22), preferred are the groups of formulae (RN-1), (RN-2), (RN-3), (RN-4), (RN-5), (RN-6), (RN-7), (RN-8), (RN-9) and (RN-10).

According to a preferred embodiment, the compound of formula (1) is selected from the compounds of formulae (2) to (13),

wherein

-symbol X¹-X⁴、Ar^SAnd R^NHave the same meanings as described above;

-Z¹-Z¹²at each occurrence, identically or differently representing CR³Or N;

-in formulae (2), (3), (6) and (7), selected from Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁹-Z¹⁰、Z¹⁰-Z¹¹And Z¹¹-Z¹²At least two adjacent Z groups together form an aromatic ring of formula (Aro-1) as defined in claim 1;

-in formulae (4), (5), (8) and (9), selected from Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁷-Z⁸、Z⁹-Z¹⁰、Z¹⁰-Z¹¹And Z¹¹-Z¹²At least two adjacent Z groups together form an aromatic ring of formula (Aro-1) as defined in claim 1; and wherein

-in formulae (10), (11), (12) and (13), selected from Z¹-Z²、Z²-Z³、Z³-Z⁴、Z⁹-Z¹⁰、Z¹⁰-Z¹¹And Z¹¹-Z¹²At least two adjacent Z groups together form an aromatic ring of formula (Aro-1) as defined in claim 1;

-one Y¹Or Y²The radical corresponding to N and the other Y¹Or Y²Radical corresponds to CR²。

According to a very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (2-1) to (2-7) or (3-1) to (3-7),

wherein

X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

one Y¹Or Y²The radical corresponding to N and the other Y¹Or Y²Radical corresponds to CR²；

p is an integer of 0 to 2;

m is an integer of 0 to 4; and is

n is an integer of 0 to 6.

According to another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (4-1) to (4-7) or (5-1) to (5-7),

wherein

X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

p is an integer of 0 to 2;

m is an integer of 0 to 4; and is

n is an integer of 0 to 6.

According to another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (6-1) to (6-7) or (7-1) to (7-7),

wherein

-X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

-one Y¹Or Y²The radical corresponding to N and the other Y¹Or Y²Radical corresponds to CR²；

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

According to yet another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (8-1) to (8-7) or (9-1) to (9-7),

wherein

-X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

According to yet another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (10-1) to (10-6) or (11-1) to (11-6),

wherein

-X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

According to another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (12-1) to (12-6) or (13-1) to (13-6),

wherein

-X¹-X⁴、Ar^S、R³And R^NHave the same meanings as described above;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

According to a particularly preferred embodiment, the compound of formula (1) is selected from compounds of formulae (2-1a) to (2-7a) or (3-1a) to (3-7a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

According to another particularly preferred embodiment, the compound of formula (1) is selected from compounds of formulae (4-1a) to (4-7a) or (5-1a) to (5-7a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

According to another particularly preferred embodiment, the compound of formula (1) is selected from compounds of formulae (6-1a) to (6-7a) or (7-1a) to (7-7a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

According to yet another particularly preferred embodiment, the compound of formula (1) is selected from compounds of formulae (8-1a) to (8-7a) or (9-1a) to (9-7a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

According to yet another particularly preferred embodiment, the compound of formula (1) is selected from compounds of formulae (10-1a) to (10-6a) or (11-1a) to (11-6a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

According to another very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (12-1a) to (12-6a) or (13-1a) to (13-6a),

wherein R is¹、R²、R³And R^NHave the same meanings as described above.

Preferably, R¹、R³On each occurrence, the same or different indicates: h, D, F, CN, a straight-chain alkyl radical having 1 to 20C atoms or a branched or cyclic alkyl radical having 3 to 20C atoms, which radicals may each be substituted by one or more R radicals, where in each case one or more non-adjacent CH radicals₂Radicals may be replaced by RC ═ CR, C ≡ C, O or S and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, aromatic or heteroaromatic ring systems having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may be substituted in each case by one or more R groups, or aryloxy groups having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may be substituted by one or more R groups, where two R groups¹The radicals can form mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring systems with one another, which may be substituted by one or more R groups, and where two R groups³The radicals may form a single ring with one another orPolycyclic aliphatic, aromatic or heteroaromatic ring systems, which may be substituted by one or more R groups. When two R are¹Or R³When the groups form a ring, they preferably form a condensed benzene ring as exemplified below:

more preferably, R¹、R³On each occurrence, the same or different indicates: h, D, CN, a straight-chain alkyl radical having 1 to 10C atoms or a branched or cyclic alkyl radical having 3 to 10C atoms, each of which may be substituted by one or more R groups, an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may be substituted in each case by one or more R groups, where two R groups¹The radicals can form a condensed benzene ring with one another, which may be substituted by one or more R groups, and where two R groups³The groups may form condensed benzene rings with each other, which may be substituted with one or more R groups.

Preferably, R²On each occurrence, the same or different indicates: h, D, F, a straight-chain alkyl radical having 1 to 20C atoms or a branched or cyclic alkyl radical having 3 to 20C atoms, which radicals may each be substituted by one or more R radicals, where in each case one or more non-adjacent CH radicals₂The radicals may be replaced by RC ═ CR, C ≡ C, O or S and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, aromatic or heteroaromatic ring systems having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may be substituted in each case by one or more R groups, or aryloxy groups having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may be substituted by one or more R groups.

More preferably, R²On each occurrence, the same or different indicates: h, D, F, a straight-chain alkyl group having 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 10C atomsA group, which each may be substituted by one or more R groups, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, very preferably from 5 to 18, aromatic ring atoms, which may in each case be substituted by one or more R groups.

Very preferably, R²On each occurrence, identically or differently, denotes an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, very preferably from 5 to 18, aromatic ring atoms, which may be substituted in each case by one or more R groups.

Particularly preferably, R²Represents an aromatic or heteroaromatic ring system selected from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, terphenylene (also known as triphenylene), pyrene, chicory, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, dibenzylidene, terphenyl, terphenylene, tetrabiphenyl, fluorene, spirobifluorene, indenofluorene, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzoquinoline, phenothiazine, thiophene

Oxazines, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyrimidines, benzopyrimidines, quinoxalines, pyrazines, phenazines, thiophenes

Oxazines, phenothiazines, azacarbazoles, triazines, or combinations of these groups. Very particularly preferably, R²The groups are selected from the following: benzene, naphthalene, phenanthrene, terphenylene, fluoranthene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, indenofluorene, dibenzofuran, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, benzoquinoline, pyrimidine, benzopyrimidine, quinoxaline, thiophene

Oxazines, phenothiazines, azacarbazoles,Pyrazine, triazine or combinations of these groups.

Preferably, R, on each occurrence, represents, identically or differently: h, D, F, CN, a linear alkyl or alkoxy group having 1 to 20C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20C atoms, which groups may each be substituted by one or more R ' groups, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which ring system may in each case be substituted by one or more R ' groups, wherein two R groups may form a ring with one another, which ring may be substituted by one or more R ' groups. More preferably, R, on each occurrence, represents, identically or differently: h, D, F, CN, a straight-chain alkyl group having 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 10C atoms, which groups may each be substituted by one or more R 'groups, an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which ring system may in each case be substituted by one or more R' groups.

Preferably, Ar is an aromatic or heteroaromatic ring system having from 5 to 18 aromatic ring atoms, which ring system may also be substituted in each case by one or more R' groups.

Preferably, R', at each occurrence, represents, identically or differently: h, D, F, Cl, Br, I, CN, a linear alkyl or alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 5C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20, preferably 1 to 10, more preferably 1 to 5C atoms, wherein one or more H atoms may be substituted by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24C atoms, preferably 5 to 18C atoms.

Examples of suitable compounds of the present invention are the structures shown in the following table:

the compounds of the invention can be prepared by synthetic procedures known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, and the like. Examples of suitable synthetic methods are depicted generally in schemes 1-3.

Scheme 1

Scheme 2

Scheme 3

In schemes 1,2 and 3:

X¹、X²(ii) a leaving group, more preferably halogen

Quin ═ quinazoline or quinoxaline derivatives

Ar ═ aromatic or heteroaromatic ring systems

Ar¹、Ar²And Ar³An aromatic or heteroaromatic ring system.

Furthermore, the compounds shown in the above schemes may be substituted at any free position with any organic group.

Accordingly, the present invention relates to a method of synthesizing a compound of the present invention, said method comprising:

(i) synthesizing a polycyclic compound comprising at least three aryl or heteroaryl groups, wherein two aryl or heteroaryl groups are linked via a six-membered lactam ring and two aryl or heteroaryl groups are linked via a pyrrole ring;

(ii) (ii) introducing a quinazoline or quinoxaline group by a C-N coupling reaction between the nitrogen atom of the compound obtained in step (i) and the quinazoline or quinoxaline group.

Accordingly, the present invention relates to a further process for the synthesis of a compound of the invention, said process comprising:

(i) a C-C coupling reaction between a carbazole derivative comprising a quinazoline or quinoxaline group and an aryl or heteroaryl group;

(ii) (ii) forming a lactam bridge between the carbazole derivative of step (i) and the aryl or heteroaryl group.

In order to process the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, a formulation of the compounds of the invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can preferably be used. The solvent is preferably selected from organic and inorganic solvents, more preferably an organic solvent. The solvent is very preferably selected from the group consisting of hydrocarbons, alcohols, esters, ethers, ketones and amines. A suitable and preferred solvent is, for example, tolueneAnisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dioxane

Alkanes, phenoxytoluenes, in particular 3-phenoxytoluene, (-) -fenchone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 1-ethylnaphthalene, decylbenzene, phenylnaphthalene, menthyl isovalerate, p-tolylisobutyrate, cyclohexylhexanoate, ethyl p-toluate, ethyl o-toluate, ethyl m-toluate, decalin, ethyl 2-methoxybenzoate, dibutylaniline, dicyclohexylketone, isosorbide dimethyl ether, decalin, 2-methylbiphenyl, ethyl octanoate, octyl octanoate, diethyl sebacate, 3, 3-dimethylbiphenyl, 1, 4-dimethylnaphthalene, 2, 2' -dimethylbiphenyl, 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, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.

Thus, the invention also relates to a formulation comprising a compound of the invention and at least one other compound. The further compound may be, for example, a solvent, in particular one of the solvents mentioned above or a mixture of these solvents. However, the further compound may also be at least one of other organic or inorganic compounds which are likewise used in electronic devices, for example a luminescent compound, in particular a phosphorescent dopant, and/or other matrix materials. Suitable light-emitting compounds and other matrix materials are indicated below in connection with organic electroluminescent devices. The other compounds may also be polymeric.

The compounds and mixtures of the invention are suitable for use in electronic devices. Electronic devices are herein understood to mean devices comprising at least one layer containing at least one organic compound. However, the elements may also comprise inorganic materials here or may also comprise layers built up entirely from inorganic materials.

The invention therefore also relates to the use of the compounds or mixtures according to the invention in electronic devices, in particular in organic electroluminescent devices.

The invention furthermore relates to electronic devices comprising at least one of the above-described compounds or mixtures according to the invention. The preferences stated above for the compounds also apply to the electronic device.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLED, PLED), 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 dye sensitized solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), light emitting electrochemical cells (LEC), organic laser diodes (O-laser) and "organic plasma light emitting devices" (d.m. koller et al, Nature Photonics, 2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), in particular phosphorescent OLEDs.

The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. It is likewise possible to introduce an intermediate layer having, for example, an exciton blocking function between the two light-emitting layers. However, it should be noted that each of these layers need not necessarily be present. The organic electroluminescent device may here comprise one light-emitting layer or a plurality of light-emitting layers. If a plurality of light-emitting layers are present, these preferably have a plurality of emission peaks generally between 380nm and 750nm, so that the overall result is white emission, i.e., a plurality of light-emitting compounds capable of fluorescence or phosphorescence are used in the light-emitting layers. Particularly preferred are systems with three light-emitting layers, wherein the three layers exhibit blue, green and orange or red emission (see for example WO 2005/011013 for basic structures). These may be fluorescent or phosphorescent light-emitting layers, or mixed systems in which fluorescent and phosphorescent light-emitting layers are combined with one another.

Depending on the exact structure, the compounds of the invention according to the embodiments indicated above can be used in different layers. Preferred are organic electroluminescent devices as described below: which comprise the compounds of the formula (1) or according to the preferred embodiments in the light-emitting layer as matrix materials for fluorescent emitters, phosphorescent emitters or emitters which exhibit TADF (thermally excited delayed fluorescence), in particular phosphorescent emitters, and/or, depending on the exact substitution, in the electron transport layer and/or in the electron-blocking layer or exciton-blocking layer and/or in the hole transport layer. The preferred embodiments indicated above are also suitable for the use of the materials in organic electronic devices.

In a preferred embodiment of the present invention, the compounds of the formula (1) or according to the preferred embodiment are used as matrix materials for fluorescent or phosphorescent compounds, in particular phosphorescent compounds, in the light-emitting layer. The organic electroluminescent devices here may comprise a light-emitting layer or a plurality of light-emitting layers, wherein at least one light-emitting layer comprises at least one compound according to the invention as matrix material.

If the compound of the formula (1) or according to the preferred embodiment is used as a matrix material for a light-emitting compound in a light-emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of the present invention is understood to mean light emission from an excited state with a spin multiplicities >1, in particular from an excited triplet state. For the purposes of the present application, all luminescent transition metal complexes or luminescent lanthanide complexes, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

Preferably, when the compounds of the formula (1) or according to the preferred embodiments are used as matrix materials for light-emitting compounds in light-emitting layers, they are preferably used in combination with one or more phosphorescent materials (triplet emitters).

The mixture comprising the compound of the formula (1) or according to the preferred embodiment and the luminescent compound comprises between 99% and 1% by volume, preferably between 98% and 10% by volume, particularly preferably between 97% and 60% by volume, in particular between 95% and 80% by volume of the compound of the formula (1) or according to the preferred embodiment, based on the entire mixture comprising the emitter and the matrix material. Accordingly, the mixture comprises between 1% and 99% by volume, preferably between 2% and 90% by volume, particularly preferably between 3% and 40% by volume, in particular between 5% and 20% by volume, of luminophores, based on the total mixture comprising luminophores and matrix material.

Suitable phosphorescent compounds (═ triplet emitters) are in particular the following compounds: which emits light when appropriately excited, preferably in the visible region, and also contains at least one atom having an atomic number of greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal having this atomic number. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered to be phosphorescent compounds.

The following applications disclose examples of such emitters: 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 2014/094962, WO 2014/094961, WO 2014/094960, WO 2016/124304, WO 2016/125715, WO 2017/032439, as well as the unpublished applications WO 2018/011186 and WO 2018/041769. In general, all phosphorescent complexes which are used in accordance with the prior art for phosphorescent OLEDs and are known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art is able to use further phosphorescent complexes without inventive effort.

Examples of suitable phosphorescent emitters are the phosphorescent emitters listed in the following table:

as mentioned above, suitable phosphorescent materials that can be advantageously combined with said compounds of formula (1) (═ triplet emitters) are compounds that emit red light under appropriate excitation, which means that the excited triplet level (T1) of the phosphorescent material is between 550nm and 800nm, more particularly between 550nm and 680 nm.

Another preferred embodiment of the present invention is the use of the compounds of the formula (1) or according to the preferred embodiments in combination with other matrix materials as matrix materials for phosphorescent emitters. Particularly suitable matrix materials which can be used in combination with the compounds of the formula (1) or according to the preferred embodiments are, for example, aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680; triarylamines, carbazole derivatives, such as CBP (N, N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851; indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746; indenocarbazole derivatives, for example according to WO 2010/136109 and WO 2011/000455; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160; bipolar matrix materials, for example according to WO 2007/137725; for example silanes according to WO 005/111172; for example azaborol or boronate according to WO 2006/117052; triazine derivatives, for example according to WO 2010/015306, WO 2007/063754 or WO 2008/056746; zinc complexes, for example according to EP 652273 or WO 2009/062578; for example diazasilacyclopentadiene or tetraazasilacyclopentadiene derivatives according to WO 2010/054729; diazaphosphole derivatives, for example according to WO 2010/054730; for example bridged carbazole derivatives according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or according to EP 11003232.3; for example a terphenyl fork derivative according to WO 2012/048781; or lactams, for example according to WO 2011/116865 or WO 2011/137951. Likewise, a further phosphorescent emitter having an emission wavelength shorter than the actual emitter may also be present as a co-host in the mixture.

Preferred co-host materials are triarylamine derivatives, lactams, carbazole derivatives, and indenocarbazole derivatives. Preferred co-host materials are very particularly carbazole derivatives and indenocarbazole derivatives.

The compounds of the formula (1) or according to the preferred embodiments are particularly suitable as matrix materials alone or in combination with other matrix materials of phosphorescent emitters.

In another embodiment of the present invention, the organic electroluminescent device of the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the hole injection layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, for example as described in WO 2005/053051. It is also possible to use the same or similar metal complex as that in the light-emitting layer as the hole-transporting or hole-injecting material directly adjacent to the light-emitting layer, for example as described in WO 2009/030981.

The compounds of the invention can also be used in hole blocking layers or electron transport layers. This applies in particular to the compounds of the invention which do not have a carbazole structure. These compounds may also preferably be substituted with one or more other electron transport groups, such as a benzimidazole group.

In the other layers of the organic electroluminescent device of the present invention, any material generally used in the art may be used. The person skilled in the art is therefore able to use any material known for use in organic electroluminescent devices in combination with the compounds of the formula (1) or the preferred embodiments without inventive effort.

For example, the compounds of the present invention may also be used as a host for semiconductor light-emitting nanoparticles. In the context of the present invention, the term "nano" means in the size range from 0.1nm to 999nm, preferably from 1nm to 150 nm. In a preferred embodiment, the semiconductor luminescent nanoparticles are quantum materials ("quantum sized materials"). The term "quantum material" in the sense of the present invention refers to the size of the semiconductor material itself without further connection or further surface modification, which shows the so-called quantum confinement effect, as described for example in ISBN 978-3-662-44822-9. In one embodiment of the invention, the total size of the quantum material is in the range of 1nm to 100nm, more preferably 1nm to 30nm, particularly preferably 5nm to 15 nm. In this case, the core of the semiconductor luminescent nanoparticle may vary. Suitable examples are CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS、ZnTe、ZnO、GaAs、GaP、GaSb、HgS、HgSe、HgSe、HgTe、InAs、InP、InPS、InPZnS、InPZn、InPGa、InSb、AlAs、AlP、AlSb、Cu₂S、Cu₂Se、CuInS₂、CuInSe₂、Cu₂(ZnSn)S₄、Cu₂(InGa)S₄、TiO₂Or a combination of said materials. In a preferred embodiment, the core of the semiconductor light-emitting particle contains one or more elements of group 13 and one or more elements of group 15 of the periodic system of elements, such as GaAs, GaP, GaSb, InAs, InP zns, InP zn, InP ga, InSb, AlAs, AlP, AlSb, CuInS₂、CuInSe₂、Cu₂(InGa)S₄Or combinations of the mentioned materials. Particularly preferably, the core contains In atoms and P atoms, such as InP, InP zns, InP zn or InP ga. In another embodiment of the invention, the nanoparticle contains one or more shell layers comprising a first element from group 12, 13 or 14 of the periodic table and a second element from group 15 or 16 of the periodic table. Preferably, all shell layers contain a first element from group 12, 13 or 14 of the periodic system and a second element from group 15 or 16 of the periodic system. In a preferred embodiment of the invention, at least one of the shell layers contains a first element from group 12 and a second element from group 16 of the periodic table, such as CdS, CdZnS, ZnS, ZnSe, ZnSSe, ZnSSeTe, CdS/ZnS, ZnSe/ZnS or ZnS/ZnSe. Particularly preferably, all shell layers contain a first element from group 12 and a second element from group 16 of the periodic table.

Also preferred are organic electroluminescent devices which are characterized in that one or more layers are applied by a sublimation process in which less than 10 times are present in a vacuum sublimation apparatus^-5Mbar, preferably less than 10^-6The material was vacuum deposited at an initial pressure of mbar. However, the initial pressure may also be even lower or higher, e.g. less than 10^-7Millibar.

Also preferred are organic electroluminescent devices which are characterized by being produced by the OVPD (organic vapor deposition) method or by means of a carrierGas sublimation is applied to one or more layers, where 10^-5The material is applied at a pressure between mbar and 1 bar. One special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and is structured thereby (for example m.s. arnold et al, appl.phys.lett.2008, 92, 053301).

Also preferred are organic electroluminescent devices which are characterized in that one or more layers are produced from solution, for example by spin coating, or by any desired printing method, for example ink-jet printing, LITI (photo-induced thermal imaging, thermal transfer), screen printing, flexographic printing, offset printing, or nozzle printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.

Hybrid methods are also possible, for example, in which one or more layers are applied from solution and one or more other layers are applied by vapor deposition. Thus, for example, the light-emitting layer may be applied from solution and the electron-transporting layer applied by vapor deposition.

These methods are generally known to the person skilled in the art and can be applied without inventive effort to the organic electroluminescent devices comprising the compounds according to the invention.

The compounds according to the invention generally have very good properties when used in organic electroluminescent devices. In particular, the lifetime is significantly better when the compounds according to the invention are used in organic electroluminescent devices than comparable compounds according to the prior art. Other properties of the organic electroluminescent device, in particular efficiency and voltage, are equally better or at least comparable. In addition, the compounds have high glass transition temperatures and high thermal stability.

The invention will now be illustrated in more detail by the following examples, without wishing to limit the invention thereto.

A) Synthesis example

Unless otherwise stated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. The compounds of the present invention can be synthesized by synthetic methods known to those skilled in the art.

a)5- (2-Chloroanilino) benzo [ c ] fluoren-7-one

43g (140mmol) of 5-bromobenzo [ c ] fluoren-7-one, 17.9g (140mmol) of 2-chloroaniline, 68.2g (710mmol) of sodium tert-butoxide, 613mg (3mmol) of palladium (II) acetate and 3.03g (5mmol) of dppf were dissolved in 1.3L of toluene and stirred at reflux for 5 hours. The reaction mixture was cooled to room temperature, mixed with toluene and filtered through celite. The filtrate was concentrated in vacuo and the residue of toluene/heptane was crystallized. The product was isolated as a colorless solid. Yield: 38g (107mmol), 77% of theory.

The following compounds can be made analogously:

b) cyclization of

36.2g (102mmol) of 5- (2-chloroanilino) benzo [ c ] fluoren-7-one, 56g (409mmol) of potassium carbonate, 4.5g (12mmol) of tricyclohexylphosphine tetrafluoroborate and 1.38g (6mmol) of palladium (II) acetate are suspended in 500ml of dimethylacetamide and stirred under reflux for 6 hours. After cooling, the reaction mixture was mixed with 300ml of water and 400ml and stirred for 30 minutes. The organic phase was then separated and filtered through a short bed of celite. The solvent was then removed in vacuo. The crude product was extracted by thermal extraction with toluene and recrystallized from toluene. The product was isolated as a beige solid (21g, 66mmol, corresponding to 65% of theory).

The following compounds can be made analogously:

c)5- (2-nitrophenyl) benzo [ c ] fluoren-7-one

30g (183.8mmol) of B- (2-nitrophenyl) -phenylboronic acid, 57g (184mmol) of 5-bromobenzo [ c ]]A thoroughly stirred degassed suspension of fluoren-7-one and 66.5g (212.7mmol) potassium carbonate in a mixture of 250ml water and 250ml THF was mixed with 1.7g (1.49mmol) Pd (PPh)₃)₄Mixed and heated at reflux for 17 hours. After cooling, the organic phase is separated, washed 3 times with 200ml of water, 1 time with 200ml of saturated saline solution, dried over magnesium sulfate and spun to dryness. The grey residue was recrystallized from hexane. The precipitated crystals were extracted, washed with MeOH and dried in vacuo; yield 58.9g (167mmol), 91% of theory.

The following compounds can be made analogously:

d) carbazole synthesis

A mixture of 84.2g (240mmol) of 5- (2-nitrophenyl) benzo [ c ] fluoren-7-one and 290.3ml (1669mmol) of triethyl phosphite is heated at reflux for 12 hours. The remaining triethyl phosphite was then distilled off (72-76 ℃ C./9 mmHg). To the residue was added a mixture of water/MeOH (1:1), followed by filtration and recrystallization.

Yield: 53.5g (168mmol), 70% of theory.

The following compounds can be made analogously:

e)2- [11- (4-Phenylquinazolin-2-yl) benzo [ a ] carbazol-5-yl ] benzoic acid methyl ester

35g (70mmol) of 5-bromo-11- (4-phenylquinazolin-2-yl) benzo [ a ] carbazole, 13.4g (75mmol) of (2-methoxycarbonylphenyl) boronic acid and 14.7g (139mmol) of sodium carbonate were suspended in 200mL of toluene, 52mL of ethanol and 100mL of water. Then, 80mg (0.69mmol) tetraphenylphosphine-palladium (0) were added to the suspension and the reaction mixture was heated at reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200mL of water and then concentrated to dryness. The residue was recrystallized from heptane/dichloromethane.

The yield was 31.8g (57mmol), corresponding to 81% of theory.

The following compounds can be made analogously:

f) ketone synthesis:

24.4g (44mmol) of 2- [11- (4-phenylquinazolin-2-yl) benzo [ a ]]Carbazol-5-yl]Introduction of methyl benzoate into 220ml of concentrated H₂SO₄Neutralized and stirred for 2 hours. When the reaction was complete, the mixture was carefully poured onto ice and extracted with toluene, separated and concentrated with a rotary evaporator, the precipitated solid was aspirated off, washed with water and ethanol.

The yield was 18.8g (36mmol), corresponding to 82% of theory.

The following compounds can be prepared analogously:

g) ketoxime synthesis

76.8g (147mmol) of compound (f) were introduced into 300ml of pyridine/200 ml of methanol. Then, 20.5g hydroxylammonium chloride was slowly added to the mixture and heated at 60 ℃ for 3.5 hours. When the reaction was complete, the precipitated solid was aspirated, washed with water and 1mol of HCl, then with methanol.

The yield was 71g (132mmol), corresponding to 90% of theory.

The following compounds can be prepared analogously:

h) lactam synthesis (Beckmann rearrangement)

75g (141mmol) of the compound (g) are placed in 300ml of polyphosphoric acid and heated to 170 ℃ for 12 hours. When the reaction was complete, the mixture was placed on ice and extracted with ethyl acetic acid, separated and concentrated. The precipitated solid was aspirated and washed with ethanol.

The isomers were separated by chromatography.

Yield: 70g (130mmol) of a mixture h (a) + h (b), corresponding to 94% of theory, the purity by HPLC: 98.0 percent. After recrystallization from ethyl acetate/toluene (1: 2): 32g (43%) of i (a) and 38g (51.6%) of i (b) are obtained.

The following compounds can be prepared analogously:

j) ullmann reaction

13.5g (25mmol, 1.00eq.) of compound h (a), 21.3ml (128mmol, 5.2eq.) of 3-bromobiphenyl and 7.20g of potassium carbonate (52.1mmol, 2.10eq.) are mixed in 220ml of dry DMF and inertized under argon. Then, 0.62g (2.7mmol, 0.11eq) of 1, 3-bis (2-pyridyl) -1, 3-propanedione and 0.52g (2.7mmol, 0.11eq.) of copper (I) iodide were added to the mixture, which was heated at 140 ℃ for three days. When the reaction was complete, the mixture was carefully concentrated using a rotary evaporator, and the precipitated solid was aspirated off and washed with water and ethanol. The crude product was purified twice with a hot extractant (toluene/heptane 1:1) and the resulting solid was recrystallized from toluene. After sublimation, 8.2g (12mmol, 48% of theory) of the expected target compound are obtained.

The following compounds can be made analogously:

i) nucleophilic substitution:

20.3g (61mmol) of the lactam compound (8h) are dissolved in 300ml of dimethylformamide under an inert atmosphere and mixed with 3g of NaH in mineral oil (60%, 75 mmol). After 1 hour at room temperature, 24g (63mmol) of 2-chloro-4-phenyl-benzo [ h ]]A solution of quinazoline in 150mL of dimethylformamide was added dropwise to the mixture. The reaction mixture was stirred at room temperature for 12 hours. After this time, the reaction mixture was poured onto ice and extracted 3 times with dichloromethane. The combined organic phases are passed over Na₂SO₄Dried and concentrated. The residue was recrystallized from toluene.

Yield: 28.9g (49mmol), corresponding to 81% of theory.

The following compounds can be made analogously:

B) fabrication of OLEDs

The following examples E4 to E12 (see Table 1) describe the use of the materials of the invention in OLEDs.

Pretreatment of examples E1 to E12:

the glass plate coated with structured ITO (indium tin oxide, 50nm) was first treated with an oxygen plasma and then with an argon plasma before coating. These plasma treated glass plates form the substrate to which the OLED is applied.

In principle, the OLED has the following layer structure: substrate/optional Interlayer (IL)/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/Electron Blocking Layer (EBL)/emissive 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 a 100nm thick layer of aluminum. The exact structure of the OLED is shown in table 1. Table 2 lists the materials used for OLED fabrication. Tables 3 and 4 list the OLED data.

All materials were applied by thermal vapor deposition in a vacuum chamber. The luminescent layer is always composed of at least one host material (host material) and a luminescent dopant (emitter) which is mixed with the host material in a certain volume proportion by co-evaporation.

Expressions such as IC1: EG1: TER1 (45%: 45%: 10%) here mean that the material IC1 is present in the layer in a proportion by volume of 45%, EG1 is present in the layer in a proportion by volume of 45%, and TER1 is present in the layer in a proportion by volume of 10%. Similarly, the electron transport layer may also be composed of a mixture of two materials.

The OLEDs are characterized in a standard way.

For this purpose, the electroluminescence spectra, the current efficiency (CE, measured in cd/A) and the external quantum efficiency (EQE, measured in%) as a function of the luminescence density, calculated from the current-voltage-luminescence density characteristic lines which exhibit Lambertian luminescence characteristics, were determined. At 1000cd/m²The electroluminescence spectrum was measured at the luminescence density of (1), and the CIE 1931x and y color coordinates were measured. In Table 3 below, U1000 corresponds to up to 1000cd/m²eEQE 1000 corresponds to 1000cd/m²External quantum efficiency.

Lifetime LT is defined as the current density j at constant₀Time in hours (h) until the lower initial luminous density falls to a specific level L1 in% of the initial luminous density.

L1 ═ 95% in table 3 below means that the given lifetime LT corresponds to the time until the luminous density falls to 95% of its initial value.

The results are shown in Table 3.

Use of the inventive materials in OLEDs

The compounds EG1 to EG6 according to the invention can be used as matrix materials in the light-emitting layers of red-phosphorescent OLEDs in examples E4 to E11.

Table 4 summarizes the results of some examples. The use of the compounds of the invention as matrix material for phosphorescent OLEDs leads to better performance of the OLEDs in terms of operating voltage, external quantum efficiency and lifetime compared to OLEDs comprising the comparative compounds V1 and V2.

Table 1: structure of OLED

Table 2: structure of materials used in OLED

Table 3: OLED data

Claims

1. A compound of the formula (1),

where the following applies to the symbols and labels used:

X¹to X⁴At each occurrence, identically or differently representing CR¹Or N;

the method is characterized in that:

wherein

(symbol)^*Indication and Z in formula (1)¹-Z²、Z²-Z³、Z³-Z⁴、Z⁵-Z⁶、Z⁶-Z⁷Or Z⁷-Z⁸The bonding position of (a);

Z⁹to Z¹²At each occurrence, identically or differently represents CR³Or N;

R^Non each occurrence, the same or different indicates: h, D, F, Cl, Br, I, CN, Si (R)₃Straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40C atoms, which may each be substituted by one or more R groups, where in each case one or more non-adjacent CH groups₂The radicals may be substituted by RC ═ CR, C ≡ C, Si (R)₂、Ge(R)₂、Sn(R)₂、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO₂O, S or CONR and in which one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may be substituted in each case by one or more R groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which may be substituted by one or more R groups;

R¹、R²and R³On each occurrence, the same or different indicates: h, D, F, Cl, Br, I, CHO, CN, C (═ O) Ar, P (═ O) (Ar)₂，S(＝O)Ar，S(＝O)₂Ar，N(R)₂，N(Ar)₂，NO₂，Si(R)₃，B(OR)₂，OSO₂R, a linear alkyl, alkoxy or thioalkyl radical having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atoms, which may each be substituted by one or more R radicals, where in each case one or more non-adjacent CH radicals₂The radicals may be substituted by RC ═ CR, C ≡ C, Si (R)₂、Ge(R)₂、Sn(R)₂、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO₂O, S or CONR and in which one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which can be substituted in each case by one or more R groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more R groups; wherein two adjacent R¹The radicals may together form an aliphatic or aromatic ring system which may be substituted by one or more R groups, where one R group²Group and one R¹The radicals may form a ring which may be substituted by one or more R groups, and wherein two adjacent R groups³The groups may together form an aliphatic or aromatic ring system, which may be substituted with one or more R groups;

r, on each occurrence, represents, identically or differently: h, D, F, Cl, Br, I, CHO, CN, C (═ O) Ar, P (═ O) (Ar)₂，S(＝O)Ar，S(＝O)₂Ar，N(R′)₂，N(Ar)₂，NO₂，Si(R′)₃，B(OR′)₂，OSO₂R 'is a linear alkyl, alkoxy or thioalkyl radical having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atoms, which may each be substituted by one or more R' radicals, where in each case one or more non-adjacent CH radicals₂The radicals may be substituted by R ' C ═ CR ', C ≡ C, Si (R ')₂、Ge(R′)₂、Sn(R′)₂、C＝O、C＝S、C＝Se、P(＝O)(R′)、SO、SO₂O, S or CONR' and in which one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂Instead, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which can be substituted in each case by one or more R 'groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more R' groups; wherein two adjacent R groups may together form an aliphatic or aromatic ring system, which may be substituted by one or more R' groups;

2. The compound of claim 1, wherein:

-Y⁴represents N;

-Y³and Ar in formula (1)^SThe radicals are bonded and represent C;

3. Compound according to claim 1 or 2, characterized in that Y²Represents N and Y¹Represents CR²。

4. Compound according to one or more of the preceding claims, characterized in that X¹To X⁴At each occurrence, identically or differently representing CR¹。

5. The compound according to one or more of the preceding claims, characterized in that it is selected from the compounds of formulae (2) to (13),

wherein

-symbol X¹-X⁴、Ar^SAnd R^NHas the same meaning as in claim 1;

-Z¹-Z¹²at each occurrence, identically or differently representing CR³Or N;

6. The compound according to one or more of the preceding claims, characterized in that it is selected from the compounds of formulae (2-1) to (2-7) or (3-1) to (3-7),

wherein

X¹-X⁴、Ar^S、R³And R^NHas the same meaning as in claim 1;

p is an integer of 0 to 2;

m is an integer of 0 to 4; and is

n is an integer of 0 to 6.

7. Compound according to one or more of claims 1 to 5, characterized in that it is selected from the compounds of formulae (4-1) to (4-7) or (5-1) to (5-7),

wherein

X¹-X⁴、Ar^S、R³And R^NHas the following advantagesThe same meaning as in claim 1;

p is an integer of 0 to 2;

m is an integer of 0 to 4; and is

n is an integer of 0 to 6.

8. The compound according to one or more of claims 1 to 5, characterized in that the compound is selected from compounds of formulae (6-1) to (6-7) or (7-1) to (7-7),

wherein

-X¹-X⁴、Ar^S、R³And R^NHas the same meaning as in claim 1;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

9. The compound according to one or more of claims 1 to 5, characterized in that the compound is selected from compounds of formulae (8-1) to (8-7) or (9-1) to (9-7),

wherein

-X¹-X⁴、Ar^S、R³And R^NHas the same meaning as in claim 1;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

10. The compound according to one or more of claims 1 to 5, characterized in that the compound is selected from compounds of formulae (10-1) to (10-6) or (11-1) to (11-6),

wherein

-X¹-X⁴、Ar^S、R³And R^NHas the same meaning as in claim 1;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

11. The compound according to one or more of claims 1 to 5, characterized in that it is selected from the compounds of formulae (12-1) to (12-6) or (13-1) to (13-6),

wherein

-X¹-X⁴、Ar^S、R³And R^NHas the same meaning as in claim 1;

-p is an integer from 0 to 2;

-m is an integer from 0 to 4; and is

-n is an integer from 0 to 6.

12. Compound according to one or more of the preceding claims, characterized in that R^NOn each occurrence, the same or different indicates: phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, indolocarbazole, phenanthroline, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinolone, benzopyridine, benzopyridazine, benzopyrimidine, quinazoline, benzimidazole, or a combination of two or three of these groups, each of which may be substituted with one or more R groups.

13. A formulation comprising at least one compound according to one or more of claims 1 to 12 and at least one solvent.

14. An electronic device comprising at least one compound according to one or more of claims 1 to 12.

15. Electronic device according to claim 14, characterized in that the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, dye sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light emitting electrochemical cells, organic laser diodes and organic plasma light emitting devices.

16. Electronic device according to claim 14 or 15, which is an organic electroluminescent device, characterized in that the compounds according to one or more of claims 1 to 12 are used as matrix material, hole-transport material or electron-transport material for light emitters.

17. Electronic device according to claim 16, characterized in that the compound according to one or more of claims 1 to 12 is used as a matrix material in a light-emitting layer comprising at least one compound according to one or more of claims 1 to 12 and at least one emitter.

18. Electronic device according to claim 17, characterized in that the light-emitting layer comprises:

-as a first matrix material a compound according to one or more of claims 1 to 12;

-a second matrix material different from the first matrix material;

and at least one light emitter.

19. Electronic device according to claim 18, characterized in that the second host material is selected from the group consisting of lactams, carbazole derivatives and indenocarbazole derivatives.

20. Electronic device according to one or more of claims 17 to 19, characterised in that the light emitter is a phosphorescent material.