Material for organic electroluminescent device

文档序号：1116966 发布日期：2020-09-29 浏览：9次中文

阅读说明：本技术 用于有机电致发光器件的材料 (Material for organic electroluminescent device ) 是由鲁文·林格塞巴斯汀·迈耶拉拉-伊莎贝尔·罗德里格斯于 2019-03-04 设计创作，主要内容包括：本发明涉及适合用于电子器件、特别是有机电致发光器件的式(1)化合物,以及包含这些化合物的电子器件。(The present invention relates to compounds of formula (1) suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices comprising these compounds.)

1. A compound of the formula (1),

where the following applies to the symbols and labels used:

E¹、E²and E³Identically or differently selected from-C (R)⁰)₂-、–Si(R⁰)₂-, -S-and-O-;

Ar¹denotes, identically or differently on each occurrence, 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 R¹Substituted by groups; or Ar¹Represents ArL; wherein Ar is¹Optionally via a single bond or divalent group E with Ar²Group bonding, wherein E represents N (R)⁰)、O、S、C(R⁰)₂、C(R⁰)₂-C(R⁰)₂、Si(R⁰)₂Or B (R)⁰)；

ArL represents a group of the formula (B),

wherein the dashed bond indicates the bonding of the group to the structure of formula (1); wherein Ar is³、Ar⁴Denotes, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 25 aromatic ring atoms which may in each case be substituted by one or more R¹Substituted by groups; and wherein m is an integer from 1 to 20;

Ar²denotes, identically or differently on each occurrence, 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 R¹Substituted by groups; or Ar²Represents ArL or a group of formula (Ar2-1) or (Ar 2-2);

wherein the dashed bond indicates bonding to the structure of formula (1);

Ar^Srepresent, identically or differently on each occurrence, a single bond or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms which may in each case be substituted by one or more R¹Substituted by groups;

x represents CR²Or N; or if X and-Ar^S-NAr¹Ar²The radicals are bonded, X represents C;

R⁰、R¹、R²represented identically or differently at each occurrence: h, D, F, Cl, Br, I, CHO, CN, N (Ar)₂，C(＝O)Ar，P(＝O)(Ar)₂，S(＝O)Ar，S(＝O)₂Ar，NO₂，Si(R)₃，B(OR)₂，OSO₂R, ArL, 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 radicals may in each case be substituted by one or more R radicals, where in each case one or more non-adjacent CH' s₂The 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, an aryloxy group having from 5 to 40 aromatic ring atoms, which can be substituted by one or more R groups; wherein two R are⁰Radical, two R¹Group and/or two R²The groups may form a ring system with each other, which ring system may be substituted by one or more R groups;

r represents, identically or differently on each occurrence:H，D，F，Cl，Br，I，CHO，CN，N(Ar)₂，C(＝O)Ar，P(＝O)(Ar)₂，S(＝O)Ar，S(＝O)₂Ar，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 R groups can form a ring system with one another, which can be substituted by one or more R ' groups;

ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted in each case by one or more R' groups;

r' represents, identically or differently on each occurrence: 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;

q, r are equal to 0 or 1, identically or differently;

provided that q + r is 1 or 2.

2. The compound of claim 1, characterized in that said Ar is¹The radicals, identical or different on each occurrence, denote an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms which may in each case be substituted by one or more R¹Substituted by radicals, or represent an ArL radical of formula (B), and Ar²Denotes, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms which may in each case be substituted by one or more R¹Substituted by a group, or represents ArL of formula (B), or represents a group of formula (Ar2-1) or (Ar 2-2).

3. A compound according to claim 1 or 2, when Ar is present¹Or Ar²When an aromatic or heteroaromatic ring system is represented, then said aromatic or heteroaromatic ring system is selected from: benzene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, cis-or trans-indenofluorene, triindene, spirotriindene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, triazine, quinoline, acridine, phenanthridine, benzoquinoline, phenothiazine, thiophene

4. Compound according to one or more of the preceding claims, characterized in that q is equal to 0 and r is equal to 1, or q is equal to 1 and r is equal to 0, or q is equal to 1 and r is equal to 1.

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

wherein the symbol E³represents-O-or-S-and wherein the symbol and the label X, R⁰、Ar¹、Ar²、Ar^SQ and r have the same meanings as in claim 1.

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

wherein the symbol E³represents-O-or-S-,

wherein X represents CR²Or N, or if X is associated with NAr¹Ar²The N atom of the group is bonded, X represents C; and is

Wherein the symbol R⁰、Ar¹And Ar²Have the same meaning as in claim 1.

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

wherein the symbol E³represents-O-or-S-,

wherein X represents CR²Or N; and is

Wherein the symbol R⁰、Ar¹And Ar²Have the same meaning as in claim 1.

8. A compound according to claim 1, characterized in that q + r is equal to 1 and Ar²Is a group of formula (Ar2-1) or (Ar 2-2).

9. Compound according to claim 1 or 8, characterized in that it is selected from the compounds of formulae (3A) to (3C),

wherein the symbol E³represents-O-or-S-;

wherein X represents CR²Or N; or X represents C if X is bonded to the nitrogen atom depicted in formulae (3A) to (3C); and is

Wherein the symbol R⁰And Ar¹Have the same meaning as in claim 1.

10. The compound according to claim 1,8 or 9, characterized in that the compound is selected from compounds of one of the formulae (3A-1) to (3C-1),

wherein the symbol E³represents-O-or-S-;

wherein X represents CR²Or N; and is

Wherein the symbol R⁰And Ar¹Have the same meaning as in claim 1.

11. Compound according to one or more of the preceding claims, characterized in that it comprises at least one R⁰、R¹、R²、Ar¹Or Ar²A radical representing a radical of formula (B) as defined in claim 1.

12. The compound according to claim 1, characterized in that it is selected from the compounds of formulae (2A-2-1) to (3C-2-1),

wherein the symbol E³represents-O-or-S-;

wherein X is CR²Or N; or if X and Ar³Or Ar⁴Bonded to or with Ar¹The N atom to which it is bonded, then X is C; and is

Wherein the symbol R⁰、Ar¹、Ar³、Ar⁴And the index m has the same meaning as in claim 1.

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 and selected from: organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, dye sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, organic laser diodes and organic plasma light emitting devices.

15. Electronic device according to claim 14, which is an organic electroluminescent device, characterized in that the compounds according to one or more of claims 1 to 12 are used as fluorescent light-emitting compounds in the light-emitting layer.

There are many compounds of blue fluorescent emitters known in the prior art. Arylamines containing one or more fused aryl groups are known in the art. Arylamines containing dibenzofuran groups (such as in US 2017/0012214) are also known in the art.

However, there is still a need for other fluorescent emitters, in particular blue fluorescent emitters, which can be used in OLEDs and which lead to OLEDs having very good properties with respect to lifetime, color emission and efficiency. More particularly, there is a need for a blue fluorescent emitter that combines high efficiency, good lifetime and appropriate color coordinates.

Furthermore, it is known that OLEDs can comprise different layers, which can be applied by vapor deposition in a vacuum chamber or by processing from solution. Processes based on vapor deposition yield good results, but such processes are rather complex and expensive. Therefore, there is also a need for OLED materials that can be easily and reliably processed from solution. In this case, the materials should have good solubility in the solution containing them.

The technical object on which the present invention is based is therefore to provide compounds which are suitable for use in electronic devices, such as OLEDs, more particularly as blue fluorescent emitters or matrix materials, and which are suitable for vacuum processing or solution processing.

In the search for novel compounds for use in electronic devices, it has now been found that the compounds of formula (1) as defined below are very suitable for use in electronic devices. In particular, they fulfill one or more, preferably all, of the technical objects mentioned above.

The invention therefore relates to compounds of the formula (1),

where the following applies to the symbols and labels used:

E¹、E²and E³Identically or differently selected from-C (R)⁰)₂-、–Si(R⁰)₂-, -S-and-O-;

Ar¹denotes, identically or differently on each occurrence, 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 R¹Substituted by groups; or Ar¹Represents ArL; and Ar¹Optionally via a single bond or a divalent group E with Ar²Group bonding, wherein E represents N (R)⁰)、O、S、C(R⁰)₂、C(R⁰)₂-C(R⁰)₂、Si(R⁰)₂Or B (R)⁰)；

ArL represents a group of the formula (B),

wherein the dashed bond indicates the bonding of the group to the structure of formula (1); wherein Ar is³、Ar⁴Denotes, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 25 aromatic ring atoms, which may be substituted in each case by one or more R¹Substituted by groups; and wherein m is an integer from 1 to 20;

wherein the dashed bond indicates bonding to the structure of formula (1);

Ar^Srepresent, identically or differently on each occurrence, a single bond or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which ring system may be substituted in each case by one or more R¹Substituted by groups;

x represents CR²Or N; or if X and-Ar^S-NAr¹Ar²N or Ar of radicals^SBonding, X represents C;

R⁰、R¹、R²represented identically or differently at each occurrence: h, D, F, Cl, Br, I, CHO, CN, N (Ar)₂，C(＝O)Ar，P(＝O)(Ar)₂，S(＝O)Ar，S(＝O)₂Ar，NO₂，Si(R)₃，B(OR)₂，OSO₂R, ArL, 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 radicals may in each case be substituted by one or more R radicals, where in each case one or more non-adjacent CH' s₂The 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 ring system may be substituted in each case by one or more R groups, an aryloxy group having from 5 to 40 aromatic ring atoms, which group may be substituted by one or more R groups; wherein two R are⁰Radical, two R¹Group and/or two R²The groups may form a ring system with each other, which ring system may be substituted by one or more R groups;

r represents, identically or differently on each occurrence: h, D, F, Cl, Br, I, CHO, CN, N (Ar)₂，C(＝O)Ar，P(＝O)(Ar)₂，S(＝O)Ar，S(＝O)₂Ar，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 ring system may in each case be substituted by one or more R ' groups, or an aryloxy group having from 5 to 60 aromatic ring atoms, which groups may be substituted by one or more R ' groups, wherein two R groups may form a ring system with one another, which ring system may be substituted by one or more R ' groups;

ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which ring system can also be substituted in each case by one or more R' groups;

q, r are equal to 0 or 1, identically or differently;

provided that q + r is 1 or 2.

The following chemical group definitions are suitable for the purposes of this application:

adjacent substituents in the sense of the present invention are substituents 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 a ring containing from 6 to 60 aromatic ring atoms, preferably from 6 to 40 aromatic ring atoms, more preferably from 6 to 20 aromatic ring atoms; heteroaryl groups in the sense of the present invention contain 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 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 fused (annellated) aromatic or heteroaromatic polycyclic ring, for example naphthalene, phenanthrene, quinoline or carbazole. Fused (fused) aromatic or heteroaromatic polycyclic rings in the sense of the present application consist of two or more simple aromatic or heteroaromatic rings fused to one another.

Aryl or heteroaryl groups which may be substituted in each case by the abovementioned groups and may be attached to the aromatic or heteroaromatic ring system via any desired position are in particular to be regarded as meaning groups which are derived from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chicory, perylene, fluoranthene, benzanthracene, triphenylene, 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, thiopheneOxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,Azole, benzo

Azoles, naphthoAzoles, anthracenesAzole, phenanthro

Oxazole, isoOxazole, 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-Oxadiazole, 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, preferably 6 to 40C atoms, more preferably 6 to 20C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 5 to 60 aromatic ring atomsPreferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 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, for example sp, preferably less than 10% of the atoms other than H³-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 linked, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are connected to one another via single bonds are also to be regarded as aromatic or heteroaromatic ring systems in the sense of the present invention, for example systems such as biphenyl, terphenyl or diphenyltriazine.

Aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms which may also be substituted in each case by a group as defined above and may be attached to the aromatic or heteroaromatic group via any desired position are to be understood as meaning in particular groups which are derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, chicory, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, dibenzylidene, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, triindene, isotridecyl indene, spiroisotridecyl indene, 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, thiopheneOxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,Azole, benzoAzoles, naphthoAzoles, anthracenesAzole, phenanthro

Oxazole, isoOxazole, 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 CH₂Linear alkyl groups having 1 to 40C atoms or branched or cyclic alkyl groups having 3 to 40C atoms or alkenyl or alkynyl groups having 2 to 40C atoms which groups may also be substituted by the groups mentioned above under the definition of the groups, are preferably taken 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-heptyl, 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, Vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthioA cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or 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:

however, in addition, the above wording 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 Ar¹The radicals, identical or different on each occurrence, denote an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be substituted in each case by one or more R¹Substituted by a group, or represents an ArL group of formula (B).

Further preferred is Ar²The radicals, identical or different on each occurrence, denote an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be substituted in each case by one or more R¹Substituted by a group, or represents ArL of formula (B), or represents a group of formula (Ar2-1) or (Ar 2-2).

When Ar is¹Or Ar²Selected from aromatic or heteroaromatic ring systems, for Ar¹And Ar²Suitable aromatic or heteroaromatic ring systems are benzene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, cis-or trans-indenofluorene, triindene, spirotriindene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, triazine, quinoline, acridine, phenanthrenePyridine, benzoquinoline, phenothiazine, thiophene

Oxazines, benzopyrimidines, quinoxalines, pyrazines, phenazines, each of which may be substituted by one or more R¹Substituted with groups, or combinations of these groups.

When Ar is¹Or Ar²Selected from aromatic or heteroaromatic ring systems, for Ar¹And Ar²Very suitable aromatic or heteroaromatic ring systems are the radicals of the formulae (A-1) to (A-54),

wherein the dotted bonds in formulae (A-1) to (A-54) are indicated with-NAr¹Ar²The bond to which the nitrogen atom of the group is attached,

wherein the radicals of formulae (A-1) to (A-54) may also be substituted at each free position by R as defined above¹Are substituted, and wherein R in formulae (A-31) to (A-34), (A-41), (A-42), (A-44), and (A-49) to (A-54)⁰The radicals have the same meanings as defined above.

When Ar is¹Or Ar²Selected from aromatic or heteroaromatic ring systems of the formulae (A-1) to (A-54) for Ar¹And Ar²Particularly suitable aromatic or heteroaromatic ring systems are the (Ar-1) to (Ar-202) groups,

wherein the dotted bonds in formulae (Ar-1) to (Ar-202) are indicated with-NAr¹Ar²A bond to the nitrogen atom of the group, and

wherein the radicals of formulae (Ar-1) to (Ar-202) may also be substituted at each free position by R as defined above¹And (4) substituting the group.

According to a preferred embodiment of the present invention, Ar¹The radicals being linked to Ar via a single bond or a divalent bridging group E as defined above²And bonding the groups.

When Ar is¹Via a single or divalent bridging group E with Ar²When bound, the appropriate-NAr¹Ar²Examples of radicals are radicals of the formulae (E-1) to (E-25),

wherein the dotted bonds indicate bonding to the structure of formula (1) and wherein the (E-1) to (E-25) groups may be defined as R above at each free position¹And (4) substituting the group.

Preferably, Ar^SThe radicals, identically or differently on each occurrence, being selected from aromatic or heteroaromatic ring systems having from 5 to 18 aromatic ring atoms, which may also be substituted by one or more R¹And (4) substituting the group. More preferably, Ar^SThe group is selected from benzene, naphthalene, biphenyl, fluorene, spirobifluorene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, carbazole, pyridine, pyrimidine or triazine, each of which may be substituted by one or more R¹And (4) substituting the group.

According to the inventionIn the formula, X represents CR²Or N; or if X and-Ar^S-NAr¹Ar²N or Ar in the radical^SAnd bonded, X represents C. Preferably, in each 6-membered ring containing an X group, 0, 1,2 or 3 of the groups X represent N. Very preferably, X represents CR²Or if X and-Ar^S-NAr¹Ar²N or Ar in the radical^SAnd bonded, X represents C.

According to a preferred embodiment, the index q is equal to 0 and the index r is equal to 1. According to another preferred embodiment, the index q is equal to 1 and the index r is equal to 0. According to another preferred embodiment, the index q is equal to 1 and the index r is equal to 1.

Preferably, the compound of formula (1) is selected from compounds of formula (2),

wherein the symbol E³represents-O-or-S-, preferably-O-, and wherein the symbol and the label X, R⁰、Ar¹、Ar²、Ar^SQ and r have the same meanings as described above.

Very preferably, the compound of formula (1) is selected from compounds of one of formulae (2A) to (2C),

wherein the symbol E³represents-O-or-S-, preferably-O-, and wherein the symbol X, R⁰、Ar¹And Ar²Have the same meanings as described above.

Particularly preferably, the compound of formula (1) is selected from one of formulae (2A-1) to (2C-1),

wherein the symbol E³represents-O-or-S-, preferably-O-, and wherein the symbol X, R⁰、Ar¹And Ar²Have the same meanings as described above.

According to a preferred embodiment q + r is equal to 1 and Ar²Is a group of formula (Ar2-1) or (Ar 2-2).

According to a very preferred embodiment, the compound of formula (1) is selected from compounds of formulae (3A) to (3C),

wherein the symbol E³represents-O-or-S-, preferably-O-,

wherein X is CR²Or N; or if X is bonded to N, then X is C; and is

Wherein the symbol R⁰And Ar¹Have the same meanings as described above.

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

wherein the symbol E³represents-O-or-S-, preferably-O-, and wherein the symbol X, R⁰And Ar¹Have the same meanings as described above.

According to a preferred embodiment, the compound of formula (1) comprises at least one R⁰、R¹、R²、Ar¹Or Ar²A group representing a group of formula (B) as defined above. More preferably, the compound of formula (1) comprises at least one Ar¹Or Ar²A group representing a group of formula (B) as defined above.

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

wherein the symbol E³represents-O-or-S-, preferably-O-;

wherein X is CR²Or N; or if X and N, Ar³Or Ar⁴Bonded, then X is C; and is

Wherein the symbol R⁰、Ar¹、Ar³、Ar⁴And the index m has the same meaning as described above.

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

wherein the symbol E³represents-O-or-S-, preferably-O-;

and wherein the symbol X, R⁰、Ar¹、Ar³、Ar⁴And the index m has the same meaning as described above.

Preferably, Ar in formula (B)³The group is selected from the group of formulae (Ar3-1) to (Ar3-26),

wherein the dotted bond indicates the structure of formula (1) and Ar³Or Ar⁴Bonding of groups, and groups of the formulae (Ar3-1) to (Ar3-26) may be substituted by R at each free position¹Is substituted by the radicals R¹The radicals have the same meanings as defined above, and wherein

E⁴Is selected from-B (R)⁰)-、-C(R⁰)₂-、-C(R⁰)₂-C(R⁰)₂-、-Si(R⁰)₂-、-C(＝O)-、-C(＝NR⁰)-、-C＝(C(R⁰))₂-、-O-、-S-、-S(＝O)-、-SO₂-、-N(R⁰)-、-P(R⁰) -and-P ((═ O) R⁰) -, wherein R⁰The substituents have the same definitions as above.

Preferably, Ar in formula (B)⁴The radicals, which are identical or different on each occurrence, are selected from radicals of the formulae (Ar4-1) to (Ar4-28),

wherein the dotted bond indicates with Ar³And wherein E⁴Have the same definitions as above, and the groups of formulae (Ar4-1) to (Ar4-28) may be substituted by R at each free position¹Is substituted by the radicals R¹The radicals have the same meanings as defined above.

Preferably, the ArL group of formula (B) comprises at least one Ar representing a group of formula (Ar3-2)³A group and/or at least one Ar representing a group of formula (Ar4-2)⁴The radical(s) is (are),

wherein

The dotted bond in the formula (Ar3-2) indicates a bond with the structure of the formula (1) and with Ar³Or Ar⁴Bonding of groups;

dotted bond in formula (Ar4-2) indicates with Ar³Bonding of (1);

E⁴have the same definitions as above; and is

Wherein the groups of formulae (Ar3-2) and (Ar4-2) may be substituted at each free position by R as defined above¹And (4) substituting the group.

More preferably, the ArL group of formula (B) comprises at least one Ar representing a group of formula (Ar3-2-1)³A group and/or at least one Ar representing a group of formula (Ar4-2-1)⁴The radical(s) is (are),

wherein

The dotted bond in the formula (Ar3-2-1) indicates a bond with the structure of the formula (1) and with Ar³Or Ar⁴Bonding of groups;

the dotted bond in formula (Ar4-2-1) indicates a bond with Ar³Bonding of (1);

E⁴have the same definitions as above;

and the groups of formulae (Ar3-2-1) and (Ar4-2-1) may be substituted by R at each free position¹Is substituted by the radicals R¹The radicals have the same meanings as defined above.

Very preferably, the ArL group of formula (B) comprises at least one Ar representing a group of formula (Ar3-2-1B)³A group and/or Ar of at least one group representing formula (Ar4-2-1b)⁴The radical(s) is (are),

wherein

The dotted bond in the formula (Ar3-2-1b) indicates a bond with the structure of the formula (1) and with Ar³Or Ar⁴Bonding of groups;

the dotted bond in formula (Ar4-2-1b) indicates a bond with Ar³Bonding of (1);

R⁰have the same definitions as above; and is

The groups of the formulae (Ar3-2-1b) and (Ar4-2-1b) may be substituted by R at each free position¹Is substituted by the radicals R¹The radicals have the same meanings as defined above.

Preferably, R⁰The radicals represent, at each occurrence: h, D, F, CN, ArL, a linear 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 being optionally substituted by RC ═ CR, Si (R)₂、C＝O、C＝S、SO、SO₂An aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted in each case by one or more R groups, in which one or more H atoms may be replaced by D or F; wherein two adjacent R⁰The groups may form a ring system with each other, which may be substituted by one or more R groups.

More preferably, R⁰The radicals are represented, identically or differently on each occurrence: h, D, F, a linear alkyl radical having 1 to 10C atoms or a branched or cyclic alkyl radical having 3 to 10C atoms, which radicals may in each case be substituted by one or more R groups, where one or more H atoms may be replaced by D or F, 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, where two adjacent R groups⁰The groups may together form an aliphatic or aromatic ring system, which may be substituted by one or more R groups.

When two adjacent R⁰When the groups form a ring system with one another, they preferably form a ring which results in the formation of a spiro ring structure as follows:

wherein the dotted lines indicate adjacent aromatic or heteroaromatic rings, and wherein the phenyl rings in the spiro ring structure may be substituted at any free position with one or more R groups.

Preferably, R¹、R²Represented identically or differently at each occurrence: h, D, F, CN, N (Ar)₂，Si(R)₃ArL, 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, which radicals may in each case 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、C＝O、C＝S、SO、SO₂An aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted in each case by one or more R groups, in which one or more H atoms may be replaced by D or F; wherein two R are¹Group and/or two R²The groups may form a ring system with each other, which may be substituted by one or more R groups.

More preferably, R¹、R²Represented identically or differently at each occurrence: h, D, F, CN, ArL, a linear alkyl radical having 1 to 10C atoms or a branched or cyclic alkyl radical having 3 to 10C atoms, which radicals may each be substituted by one or more R radicals, where in each case one or more non-adjacent CH radicals₂A group which may be substituted by RC ═ CR, O or S and in which one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 25, preferably 6 to 18, aromatic ring atoms, which ring system may be substituted in each case by one or more R groups; wherein two R are¹Group and/or two R²The groups may form a ring system with each other, which may be substituted by one or more R groups. Very preferably, R²Represents H.

Preferably, R represents, identically or differently on each occurrence: h, D, F, CN, a linear 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 30, preferably 6 to 18, aromatic ring atoms, which ring system may in each case be substituted by one or more R' groups.

Preferably, the Ar group is an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which ring system can also be substituted in each case by one or more R' groups.

Preferably, R', equal or different at each occurrence, represents: h, D, F, Cl, Br, I, CN, a linear alkyl, alkoxy or thioalkyl group having 1 to 10C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 10C atoms, or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms.

The following compounds are examples of compounds of formula (1):

the compounds according to 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 generally depicted in schemes 1 to 3 below.

Scheme 1

E is O or S or C (R)₂Wherein R is a substituent

X¹And X³Is a leaving group (e.g. halogen or boronic acid derivative)

Ar is an aromatic or heteroaromatic ring system (identical or different at each occurrence)

Scheme 2

E is O or S or C (R)₂Wherein R is a substituent

X¹And X³Is a leaving group (e.g. halogen or boronic acid derivative)

Ar is an aromatic or heteroaromatic ring system (identical or different at each occurrence)

The compounds of formula (1) may be synthesized as described above, wherein a truxene derivative comprising a divalent bridging group-O-or-S-is first synthesized using a dibenzofuran or dibenzothiophene derivative comprising a reactive leaving group, such as a halogen or boronic acid, as a precursor, and at least one arylamine is bonded to the truxene derivative via a C-N coupling reaction.

For processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds of the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, bis-xyleneAlkanes, phenoxytoluenes, especially 3-phenoxytoluene, (-) -fenchone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 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 can also be at least one further organic or inorganic compound which is likewise used in electronic devices, for example a matrix material, in particular for fluorescent dopants and/or further light-emitting compounds. Suitable matrix materials and other light-emitting compounds are indicated below in connection with the organic electroluminescent device. The other compound may also be a polymer.

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 component may also comprise inorganic materials here or may also comprise layers which are constructed 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 preferred forms described above for the compounds also apply to the electronic device.

The electronic device is preferably selected from: 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, they 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). They may be fluorescent or phosphorescent light-emitting layers, or mixed systems in which fluorescent and phosphorescent light-emitting layers are combined with each other.

The compounds of the present invention according to the above embodiments may be used in a variety of layers depending on the exact structure and substitution. It is preferred that the organic electroluminescent device comprises said compound of formula (1) or according to a preferred embodiment as a fluorescent emitter, an emitter exhibiting TADF (thermally activated delayed fluorescence), a host material for a fluorescent emitter. It is particularly preferred that the organic electroluminescent device comprises said compound of formula (1) or according to a preferred embodiment as a fluorescent emitter, more particularly as a fluorescent compound emitting blue light.

Depending on the exact substitution, the compounds of the formula (1) can also be used in electron transport layers and/or in electron-blocking layers or exciton-blocking layers and/or in hole transport layers. The preferred embodiments indicated above are also suitable for the use of the materials in organic electronic devices.

The compounds according to the invention are particularly suitable as blue-emitting emitter compounds. The electronic device of interest may comprise a single light-emitting layer comprising the compound of the invention, or it may comprise two or more light-emitting layers. The further light-emitting layer may here comprise one or more compounds according to the invention or further compounds.

If the compound of the invention is used as a fluorescent light-emitting compound in the light-emitting layer, it is preferably used in combination with one or more host materials. A host material is here understood to mean a material which is preferably present as a main component in the light-emitting layer and which does not emit light during operation of the device.

The proportion of the luminescent compound in the luminescent-layer mixture is between 0.1% and 50.0%, preferably between 0.5% and 20.0%, particularly preferably between 1.0% and 10.0%. Accordingly, the proportion of matrix material is between 50.0% and 99.9%, preferably between 80.0% and 99.5%, particularly preferably between 90.0% and 99.0%.

For the purposes of the present application, the specification of the proportion in% is taken to mean volume% if the compound is applied from the gas phase and weight% if the compound is applied from a solution.

Preferred host materials for use in combination with the fluorescent light-emitting compound are selected from the following classes: oligomeric aromatic subunits (for example 2,2',7,7' -tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), in particular oligomeric aromatic subunits containing fused aromatic groups, oligomeric aromatic subunits vinylene subunits (for example DPVBi or spiro-DPVBi according to EP 676461), polypental metal complexes (for example according to WO 2004/081017), hole-conducting compounds (for example according to WO 2004/058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (for example according to WO 2005/084081 and WO 2005/084082), atropisomers (for example according to WO 2006/048268), boronic acid derivatives (for example according to WO 2006/117052) or benzanthracenes (for example according to WO 2008/145239). Particularly preferred matrix materials are selected from the following classes: oligomeric aromatic subunits including naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligomeric aromatic subunits vinylidenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the group of oligomeric aromatic subunits, including anthracene, benzanthracene, triphenylene and/or pyrene or atropisomers of these compounds. Oligomeric arylidene in the sense of the present invention is intended to be taken to mean a compound in which at least three aryl or arylidene groups are bonded to each other.

Particularly preferred host materials for use in combination with the compounds of formula (1) in the light-emitting layer are depicted in the following table.

If the compound of the present invention is used as a fluorescent light-emitting compound in a light-emitting layer, it may be used in combination with one or more other fluorescent light-emitting compounds.

Preferred fluorescent emitters, in addition to the compounds of the present invention, are selected from the group consisting of arylamines. Arylamines in the sense of the present invention are understood to mean compounds which contain three substituted or unsubstituted aromatic or heteroaromatic ring systems which are bonded directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, particularly preferably a fused ring system having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chicory amines or aromatic chicory diamines. Aromatic hydrocarbonA dianthramine is understood to mean a compound in which one diarylamino group is directly bonded to an anthracene group, preferably in the 9 position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 position. Aromatic pyrene amines, pyrene diamines, chicory amines and chicory diamines are defined analogously, wherein the diarylamino group is preferably bonded to pyrene in position 1 or in position 1, 6. Other preferred luminophores are indenofluoreneamines or indenofluorenediamines, e.g. according to WO 2006/108497 or WO 2006/122630, benzindenofluoreneamines or benzindenofluorenediamines, e.g. according to WO 2008/006449, and dibenzoindenofluoreneamines or dibenzoindenofluorenediamines, e.g. according to WO 2007/140847, and indenofluorene derivatives containing fused aryl groups as disclosed in WO 2010/012328. Still other preferred luminophores are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers as disclosed in WO 2016/150544 or phenols as disclosed in WO 2017/028940 and WO 2017/028941An oxazine derivative. Also preferred are pyrene arylamines as disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are the benzindenofluorenes disclosed in WO 2014/037077, the benzindenofluorenes disclosed in WO 2014/106522, and the indenofluorenes disclosed in WO 2014/111269 or WO 2017/036574.

Examples of preferred fluorescent light-emitting compounds other than the compounds of the present invention, which may be used in combination with the compounds of the present invention in the light-emitting layer or in other light-emitting layers of the same device, are depicted in the following table:

the compounds according to the invention can also be used in other layers, for example as hole-transport materials in hole-injection or hole-transport layers or electron-blocking layers or as matrix materials in light-emitting layers, preferably as matrix materials for phosphorescent emitters.

If the compound of formula (1) is used as a hole-transporting material in a hole-transporting layer, a hole-injecting layer or an electron-blocking layer, the compound can be used as a pure material, i.e. in a proportion of 100%, in the hole-transporting layer, or it can be used in combination with one or more other compounds. According to a preferred embodiment, the organic layer comprising the compound of formula (1) then additionally comprises one or more p-type dopants. The p-type dopant used in the present invention is preferably an organic electron acceptor compound capable of oxidizing one or more other compounds in the mixture.

particularly preferred embodiments of p-type dopants are the compounds disclosed in WO 2011/073149, EP 1968131, EP2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US8057712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US 2010/0096600 and WO 2012/095143.

If the compounds of the formula (1) are used in the light-emitting layer as matrix materials in combination with phosphorescent emitters, the phosphorescent emitters are preferably selected from the classes and embodiments of phosphorescent emitters indicated below. Furthermore, in this case, it is preferred that one or more further matrix materials are present in the light-emitting layer.

So-called mixed matrix systems of this type preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. It is preferable here that one of the two materials is a material having a hole-transporting property, and the other material is a material having an electron-transporting property. The compound of formula (1) is preferably a material having a hole transporting property.

However, the desired electron transporting and hole transporting properties of the mixed matrix component may also be combined predominantly or completely in a single mixed matrix component, wherein the other mixed matrix components fulfill other functions. The two different matrix materials can be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, very particularly preferably 1:4 to 1: 1. The mixed matrix system is preferably used in phosphorescent organic electroluminescent devices. Further details regarding mixed matrix systems are contained in the application WO 2010/108579, among others.

Particularly suitable matrix materials which can be used in combination with the compounds of the invention as matrix components of a mixed matrix system are selected from the preferred matrix materials for phosphorescent emitters indicated below, or the preferred matrix materials for fluorescent emitters, depending on what type of emitter compound is employed in the mixed matrix system.

The following indicates the generally preferred classes of materials for use as corresponding functional materials in the organic electroluminescent device of the present invention.

Suitable phosphorescent emitters are in particular compounds which: which, when excited appropriately, emits light, preferably in the visible region, and also contains at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. 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, platinum or copper.

For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

Applications WO 2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373 and US 2005/0258742 disclose examples of such phosphorescent emitters. 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 in the field of organic electroluminescent devices are suitable for use in the devices of the invention. The person skilled in the art is also able to use other phosphorescent complexes in combination with the compounds according to the invention in OLEDs without inventive effort.

Preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP2004/288381, 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, WO 2011/000455 or WO 2013/041176, azacarbazole derivatives, for example according to EP 1617710, EP1617711, EP 1731584, JP 35 2005/347160, bipolar matrix materials, for example according to WO 2007/137725, silanes, for example according to WO 2005/111172, borazazepins or borates, for example 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, silazazepins or silatetraazazepins derivatives, for example according to WO 2010/054729, phosphorodiazepine derivatives, for example according to WO 2010/054730, bridged carbazole derivatives, for example according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or WO2012/143080, triphenylidene derivatives, for example according to WO 2012/048781, or lactams, for example according to WO2011/116865 or WO 2011/137951.

Suitable charge transport materials which, in addition to the compounds of the invention, can be used in the hole injection or hole transport layer or in the electron blocking layer or in the electron transport layer of the electronic devices of the invention are, for example, the compounds disclosed in y.shirota et al, chemical reviews (chem.rev.)2007, 107(4), 953-1010, or else the materials used in these layers according to the prior art.

Materials which can be used for the electron transport layer are all materials which are used according to the prior art as electron transport materials in electron transport layers. Particularly suitable are aluminum complexes, for example Alq₃Zirconium complexes, e.g. Zrq₄Lithium complexes, such as LiQ, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives,oxadiazole derivatives, aromatic ketones, lactams, boranes, phosphorus diazacyclo-derivatives and phosphine oxide derivatives. Further, suitable materials are derivatives of the above compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred hole transporting materials which can be used in the hole transporting, hole injecting or electron blocking layer of the electroluminescent device of the invention are indenofluorenamine derivatives (e.g. according to WO 06/122630 or WO 06/100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylidene derivatives (e.g. according to WO 01/049806), amine derivatives containing fused aromatic rings (e.g. according to US 5,061,569), amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (e.g. according to WO 08/006449), dibenzoindenofluorenamines (e.g. according to WO 07/140847), spirobifluorinamines (e.g. according to WO 2012/034627 or WO 2013/120577), fluorenamines (e.g. according to the as yet unpublished applications EP12005369.9, EP 12005370.7 and EP 12005371.5), spirodibenzopyranamines (e.g. according to WO 2013/083216), and dihydroacridine derivatives (e.g. according to WO 2012/150001). The compounds of the present invention may also be used as hole transport materials.

The cathode of the organic electroluminescent device preferably comprises a compound having a low work functionA metal, a metal alloy, or a multilayer structure comprising a plurality of metals such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or alkaline earth metal and silver, for example alloys comprising magnesium and silver. In the case of a multilayer structure, in addition to the metals, other metals having a relatively high work function may be used, such as Ag or Al, in which case combinations of the metals, such as Ca/Ag, Mg/Ag or Ag/Ag, are generally used. It may also be preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline earth metal fluorides, and also the corresponding oxides or carbonates (e.g. LiF, Li)₂O、BaF₂、MgO、NaF、CsF、Cs₂CO₃Etc.). Furthermore, lithium quinolate (LiQ) can be used for this purpose. The layer thickness of this layer is preferably between 0.5nm and 5 nm.

The anode preferably comprises a material having a high work function. The anode preferably has a work function greater than 4.5eV relative to vacuum. Suitable for this purpose are, on the one hand, metals having a high redox potential, such as Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (e.g., Al/Ni/NiO) may also be preferred_x、Al/PtO_x). For some applications, at least one of the electrodes must be transparent or partially transparent in order to facilitate the illumination of the organic material (organic solar cells) or the coupling-out of light (OLEDs, O-lasers). Preferred anode materials herein are conductive mixed metal oxides. Particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO). Preference is furthermore given to conductively doped organic materials, in particular conductively doped polymers.

Since the lifetime of the device of the invention is shortened in the presence of water and/or air, the device is suitably (depending on the application) structured, placed in contact and finally sealed.

In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that the one or more layers are applied by a sublimation process, wherein the organic electroluminescent device is applied in situIn the air sublimation device, the temperature is less than 10 DEG^-5Mbar, preferably less than 10^-6The material is applied by vapour deposition at an initial pressure of mbar. However, the initial pressure may also be even lower here, for example less than 10^-7Millibar.

Also preferred are organic electroluminescent devices which are characterized in that one or more layers are applied by the OVPD (organic vapor deposition) method or sublimation with the aid of a carrier gas, where 10 is the range^-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, apply physical flash (appl. phys. lett.)2008, 92, 053301).

Preference is furthermore given to 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 screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (photo-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, a soluble compound of said formula (1) is required. High solubility can be obtained by appropriate substitution of the compounds.

Hybrid processes 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 those skilled in the art and can be applied without inventive effort to organic electroluminescent devices comprising the compounds according to the invention.

According to the present invention, electronic devices comprising one or more compounds of the invention can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications, such as phototherapy.

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

A) Synthesis example

Synthetic example scheme of intermediate VII-a

Synthesis of intermediate I-a:

117.9g (401mmol) of starting material a, 100g (401mmol) of starting material b and 203.1g (882mmol) of potassium phosphate monohydrate in 1.6L of toluene/water/bisAlkyl (2:1:1) and degassed the mixture was added palladium acetate (0.9g, 4mmol) and tri-o-tolylphosphine (2.44g, 8mmol) and the mixture was stirred under reflux for 16 h after cooling the mixture to room temperature the phases were separated the aqueous phase was further extracted with ethyl acetate (2 × 300mL), the combined organic phases were washed with water multiple times, dried over sodium sulphate and finally removed in vacuo the crude product was passed through SiO using ethyl acetate as solvent₂/Al₂O₃And (4) filtering by using a plug. After removal of the solvent in vacuo, an oil was obtained in quantitative yield.