CN115885599A

CN115885599A - Material for organic electroluminescent device

Info

Publication number: CN115885599A
Application number: CN202180048240.7A
Authority: CN
Inventors: 鲁文·林格; 米丽娅姆·恩盖尔; 塞巴斯汀·施托尔茨; 塞巴斯汀·迈耶
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2020-07-22
Filing date: 2021-07-19
Publication date: 2023-03-31
Also published as: KR20230039661A; TW202216953A; EP4186113A1; WO2022017998A1

Abstract

The present invention relates to compositions comprising a compound of formula (H1) and a compound of formula (H2). The invention also relates to formulations comprising a composition comprising a compound of formula (H1) and formula (H2) and a solvent. Finally, the invention relates to an electronic device comprising such a composition.

Description

Material for organic electroluminescent device

The development of functional compounds for electronic devices is currently the subject of intensive research. In particular, it is an object to develop compounds with which improved performance of electronic devices can be achieved in one or more relevant aspects, for example, improved power efficiency and lifetime of the devices and color coordinates of the emitted light.

According to the present invention, the term electronic device is considered to refer to inter alia Organic Integrated Circuits (OIC), organic Field Effect Transistors (OFET), organic Thin Film Transistors (OTFT), organic Light Emitting Transistors (OLET), organic Solar Cells (OSC), organic optical detectors, organic photoreceptors, organic Field Quench Devices (OFQD), organic light emitting electrochemical cells (OLEC), organic laser diodes (O-lasers) and organic electroluminescent devices (OLED).

Of particular interest is the provision of compounds for use in the last-mentioned electronic devices known as OLEDs. The general structural and functional principles of OLEDs are known to those skilled in the art and are described, for example, in US 4539507.

With regard to the performance data of OLEDs, further improvements are still needed, in particular in view of the wide commercial use, for example in display devices or as light sources. Of particular importance in this connection are the lifetime, efficiency and operating voltage of the OLEDs and the color values achieved. In particular, in the case of blue-emitting OLEDs, there is potential for improvement in the efficiency, lifetime and operating voltage of the devices.

An important starting point for achieving the improvement is the choice of emitter compound and host compound. In practice, the emitter compound is usually used in the light-emitting layer in combination with a second compound which serves as a matrix compound or a host compound. A luminophore compound is here understood to mean a compound which emits light during operation of an electronic device. In this case, host compounds are understood to mean compounds which are present in the mixture in a greater proportion than the emitter compounds. The terms matrix compound and host compound may be used synonymously. The host compound preferably does not emit light. Even if a plurality of different host compounds are present in the mixture of the light-emitting layer, their respective proportions are generally greater than the proportion of the emitter compounds, or if a plurality of emitter compounds are present in the mixture of the light-emitting layer, than the proportion of the individual emitter compounds.

Such embodiments have been described for a fluorescent light emitting layer, for example in US 4769292.

If a mixture of a plurality of compounds is present in the light-emitting layer, the emitter compound is generally a component which is present in smaller amounts (i.e. in smaller proportions) compared to the other compounds present in the light-emitting layer mixture. In this case, the emitter compound is also referred to as dopant.

Host compounds for fluorescent emitters known from the prior art are a variety of compounds. The light-emitting layer may comprise one or more host compounds.

Host compounds comprising phenanthrene groups have been disclosed in the prior art (e.g. in WO 2009/100925). Host compounds comprising dibenzofuran and anthracene groups have also been disclosed in the prior art (e.g. in KR 10-2017-0096860 and CN 109867646).

However, there is still a need for further host materials for fluorescent emitters which can be used in OLEDs and lead to OLEDs having very good performance with regard to lifetime, emission color and efficiency. More specifically, there is a need for host materials for fluorescent emitters that combine very high efficiency, very good lifetime and very good thermal stability.

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. Vapor deposition based processes lead to very good results, but they can be complex and expensive. Thus, there is also a need for compositions comprising OLED materials that can be easily and reliably processed from solution. More specifically, when processed from formulations, more specifically from solutions such as inks, there is a need for compositions comprising OLED materials that can be deposited as uniform films during the manufacture of OLEDs. In this case, the material should have good solubility in the solution containing it and the deposited film containing the OLED material should be as smooth as possible after the drying step leading to removal of the solvent. It is important that the deposited layer forms a smooth and uniform film, since uneven brightness distribution results from uneven layer thickness, wherein areas with a thinner film thickness show increased brightness and thicker areas have reduced brightness, resulting in a reduced quality of the OLED. At the same time, OLEDs comprising films processed from solution should show good properties, for example in terms of lifetime, operating voltage and efficiency.

Furthermore, there remains a need for methods of producing stable OLED materials that are easy to purify and easy to process. There is a need for a process that is economically and qualitatively interesting by providing OLED materials with acceptable purity and high yield.

The invention is therefore based on the following technical objects: compositions are provided comprising OLED materials suitable for use in electronic devices such as OLEDs, more particularly as matrix components for fluorescent emitters. The present invention is also based on the technical object of providing a composition comprising an OLED material, which is particularly suitable for solution processing. The invention is also based on the technical object of providing a method.

In the search for novel compositions for use in electronic devices, it has now been found that compositions comprising a compound of formula (H1) and a compound of formula (H2) as defined below are very suitable for use in electronic devices. In particular, they achieve one or more, preferably all, of the above technical objects.

The application therefore relates to a composition comprising a compound of formula (H1) and a compound of formula (H2),

where the following applies to the symbols and labels used:

e represents O or S, preferably O;

x in each case identically or differently represents CR ^X Or N; or if X is bonded to the group Ar ^S Or Ar ¹ Then X is C;

z represents in each case identically or differently CR ^Z Or N; or if Z is bonded to the group Ar ^S Or Ar ³ If Z is C;

Ar ¹ are in each case identically or differently aryl or heteroaryl radicals having from 10 to 60 aromatic ring atoms, which may also be substituted in each case by one or more radicals R ^V Substitution;

Ar ³ are in each case identically or differently aryl or heteroaryl radicals having from 10 to 60 aromatic ring atoms, which may also be substituted in each case by one or more radicals R ^Y Substitution;

Ar ² 、Ar ⁴ 、Ar ^S identically or differently on each occurrence is an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may also be substituted on each occurrence by one or more radicals R;

R ^V 、R ^X 、R ^Y 、R ^Z in each case identically or differently, represents H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R) ₃ ，B(OR) ₂ ，OSO ₂ R, a straight-chain 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, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH(s) ₂ The group may be substituted with RC = CR, C ≡ C, si (R) ₂ 、Ge(R) ₂ 、Sn(R) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO ₂ O, S or CONR and where one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may be substituted in each case by one or more radicals R, or aryloxy groups having from 5 to 60 aromatic ring atomsThe aryloxy group may be substituted by one or more groups R;

in which two radicals R ^V Two radicals R ^X Two radicals R ^Y Two radicals R ^Z May together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R;

r represents in each case identically or differently H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R′) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R′) ₃ ，B(OR′) ₂ ，OSO ₂ R ' is a straight-chain 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, each of which may be substituted by one or more radicals R ', where in each case one or more non-adjacent CH ' s ₂ The groups may be substituted with R ' C = CR ', C ≡ C, si (R ') ₂ 、Ge(R′) ₂ 、Sn(R′) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO ₂ O, S or CONR' and wherein one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, 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 radicals R ', or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R'; wherein two radicals R may together form an aliphatic or aromatic ring system which may be substituted by one or more radicals R';

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

r' represents in each case identically or differently H, D, F, cl, br, I, CN, a linear alkyl, alkoxy or thioalkyl radical having 1 to 20C atoms, orBranched or cyclic alkyl, alkoxy or thioalkyl groups of 3 to 20C atoms, in which in each case one or more non-adjacent CH ₂ The radicals being selected from SO, SO ₂ O, 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 5 to 24 aromatic ring atoms; and is

a. b, c and d are in each case identically or differently 0 or 1; wherein:

when a or b is 0, then the corresponding Ar ^S Is absent and the group Ar ¹ Is directly bonded to the group X,

when c or d is 0, then the corresponding Ar ^S Is absent and the group Ar ³ Directly bonded to the group Z;

p, q, r and s, identically or differently, represent 1,2 or 3.

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

an aryl group in the sense of the present invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 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 preferred features are indicated in the description of the invention, for example in terms of the number of aromatic ring atoms or the heteroatoms present, these preferred features apply.

Aryl or heteroaryl groups are here understood to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine or thiophene, or fused (annellated) aromatic or heteroaromatic polycyclic compounds, such as naphthalene, phenanthrene, quinoline or carbazole. Fused (fused) aromatic or heteroaromatic polycyclic compounds in the sense of the present application consist of two or more simple aromatic or heteroaromatic rings fused to one another.

In each case substituted by the abovementioned radicals and can be brought into contact with the stated radicals via any desired positionAromatic or heteroaromatic ring system-bound aryl or heteroaryl groups are in particular understood as meaning groups which derive 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, thiophene

Oxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxalines and/or>

Azole, benzo->

Azole, naphtho->

Azole, anthraco>

Azole, phenanthro->

Azole and iso-braor>

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- < - >, ion>

Diazoles, 1,2,4- & ltwbr/& gtbased on blood pressure>

Diazole, 1,2,5->

Diazole, 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.

An aryloxy group as defined according to 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. A heteroaromatic ring system in the sense of the present invention contains 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 heteroatoms are preferably selected from N, O and/or S. Aromatic or heteroaromatic ring systems in the sense of the present invention are intended to be taken to mean the following systems: it need not contain only aryl or heteroaryl groups, but wherein a plurality of aryl or heteroaryl groups may also be linked by a non-aromatic unit (preferably less than 10% of the atoms other than H), for example sp ³ Hybridized C, si, N or O atoms, sp ² A hybridized C or N atom, or an sp hybridized C atom. Thus, for example, systems such as 9,9 '-spirobifluorene, 9,9' -diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc., are likewise intended to be considered aromatic ring systems in the sense of the present invention, and systems in which two or more aryl groups are connected, for example, by straight-chain or cyclic alkyl, alkenyl or alkynyl groups or by silyl groups. Further, systems in which two or more aryl or heteroaryl groups are connected to one another via a single bond, e.g.Systems such as biphenyl, terphenyl or diphenyltriazine are also to be regarded as aromatic or heteroaromatic ring systems in the sense of the present invention.

An aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms which may in each case also be substituted by a group as defined above and may be attached to the aromatic or heteroaromatic group via any desired position, is to be understood as meaning in particular groups which derive from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, chicory, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, dibenzylidene, terphenyl, tetrabiphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, triindene, isotridenzene, spiroisotridenzene, furan, benzofuran, 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->

Azole, naphtho->

Azole, anthracon->

Azole, phenanthro->

Azole and iso-braor>

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-diaza pyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine>

Oxazines, phenothiazines, fluoranthenes, naphthyridines, azacarbazoles, benzocarbazoles, phenanthrolines, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3->

Diazole, 1,2,4->

Diazole, 1,2,5->

Diazole, 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 CH ₂ Straight-chain 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 in question, are preferably to be regarded as meaning the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexylAlkyl, 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. <xnotran> 1 40 C , , , , , , , , , , ,2- , , , , , , ,2- , , 5363 zxft 5363- , , , , , , , , , , , , , , , , ,2- , , , 3242 zxft 3242- , , , , , , , , , , , , , , , , , . </xnotran>

For the purposes of the present application, the expression that two or more 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 exemplified by the following scheme:

however, in addition, 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, thereby forming a ring. This is exemplified by the following scheme:

when two groups form a ring with each other, then preferably the two groups are adjacent groups. 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.

Preferably, the group Ar ¹ 、Ar ³ In each case identically or differently, represents a fused-on aryl radical having 10 to 18 aromatic ring atoms. More preferably, the group Ar ¹ 、Ar ³ In each case identically or differently, represents anthracene, naphthalene, phenanthrene, tetracene, chicory, benzanthracene, triphenylene, pyrene, perylene, terphenyl, benzopyrene or fluoranthene, each of which may be substituted in any free position by one or more radicals R ^V Substituted (in Ar) ¹ In the case of (A) or by one or more radicals R ^Y Substituted (at Ar) ³ In the case of (1). Very preferably, the group Ar ¹ 、Ar ³ Represents an anthracene group, which may be substituted in any free position by one or more radicals R ^V Substituted (for Ar) ¹ ) Or in any free position by one or more radicals R ^Y Substituted (for Ar) ³ )。

Suitable radicals Ar ¹ And Ar ³ Examples of (D) are groups of formulae (Ar 1-1) to (Ar 1-11) shown in the following tables:

/>

wherein

Dashed bonds indicate bonding to adjacent groups; and wherein the radicals of the formulae (Ar 1-1) to (Ar 1-11) may be substituted at each free position by a radical R ^V Substituted (in Ar) ¹ In the case of) or by a group R ^Y Substituted (in Ar) ³ In the case of (1), wherein R is ^V And R ^Y Have the same meaning as above.

Among the groups of the formulae (Ar 1-1) to (Ar 1-11), the group of the formula (Ar 1-1) is preferred.

Very suitable radicals Ar ¹ And Ar ³ Examples of (A) are groups of formulae (Ar 1-1-1) to (Ar 1-12-1) as shown in the following table:

wherein

Dashed bonds indicate bonding to adjacent groups; and wherein the radicals of the formulae (Ar 1-1-1) to (Ar 1-12-1) may be substituted at each free position by a radical R ^V Substituted (in Ar) ¹ In the case of) or by a group R ^Y Substituted (in Ar) ³ In the case of (1), wherein R is ^V And R ^Y Have the same meaning as above.

Among the groups of the formulae (Ar 1-1-1) to (Ar 1-12-1), the group of the formula (Ar 1-1-1) is preferred.

Preferably, the compound of formula (H2) is selected from compounds of formula (H2-1),

wherein:

y is CR ^Y Or N; or if Y is bonded to Ar ² 、Ar ^S Or a group Z, then Y is C; and wherein R ^Y And other symbols and indicia have the same meaning as above.

More preferably, the compound of formula (H2) is selected from compounds of formulae (H2-2-1), (H2-2-2) and (H2-2-3),

wherein the symbols and indices have the same meaning as above.

Even more preferably, the compound of formula (H2) is selected from the compounds of formulae (H2-3-1) to (H2-3-20),

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wherein the symbols and indices have the same meaning as above.

In the formulae (H2-3-1) to (H2-3-20), the hosts of the formulae (H2-3-1) to (H2-3-11) and (H2-3-13), (H2-3-14), (H2-3-16) and (H2-3-17) are preferred. The hosts of formulae (H2-3-1) to (H2-3-11), (H2-3-16) and (H2-3-17) are very preferred. The hosts of the formulae (H2-3-1) to (H2-3-10) are particularly preferred. A host of the formula (H2-3-1) is very particularly preferred.

Particularly preferably, the compound of formula (H2) is selected from the compounds of formulae (H2-3-30) to (H2-3-49),

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wherein the symbols and indices have the same meaning as above.

Among the formulae (H2-3-30) to (H2-3-49), the hosts of the formulae (H2-3-30) to (H2-3-40) and (H2-3-42), (H2-3-43), (H2-3-45) and (H2-3-46) are preferred. The hosts of formulae (H2-3-30) to (H2-3-40), (H2-3-45), and (H2-3-46) are highly preferred. The hosts of the formulae (H2-3-30) to (H2-3-39) are particularly preferred. A host of the formula (H2-3-30) is very particularly preferred.

Preferably, Z represents CR ^Z 。

Preferably, Y represents CR ^Y 。

Preferably, R ^Y 、R ^Z Represents H, D, F, in each case identically or differently, a straight-chain alkyl, alkoxy or thioalkyl radical having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH' s ₂ A group which may be replaced by RC = CR, C ≡ C, 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 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18, aromatic ring atoms which may be substituted in each case by one or more groups R. More preferably, R ^Y 、R ^Z In each case identically or differently, represents H, D, F, a straight-chain alkyl radical having 1 to 20, preferably 1 to 10, more preferably 1 to 6C atoms, or a branched or cyclic alkyl radical having 3 to 20, preferably 3 to 10, more preferably 3 to 6C atoms, each of which may be substituted by one or moreSubstituted by radicals R, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R.

More preferably, Z represents CR ^Z Wherein R is ^Z Is H.

More preferably, Y represents CR ^Y Wherein R is ^Y Is H.

Preferably, the compound of formula (H1) is selected from compounds of formula (H1-1),

wherein the symbol X, ar ^S 、Ar ⁴ And the indices a and b have the same meaning as above; and is

V is CR ^V Or N; or if V is bonded to Ar ⁴ 、Ar ^S Or a group X, then V is C; wherein R is ^V Have the same meaning as above.

Preferably, the indices a and b are equal to 0, thus the group Ar ^S Is absent and the anthracene moiety is directly bonded to the phenanthrene moiety.

More preferably, the compound of formula (H1) is selected from compounds of formula (H1-2),

of which X, ar ⁴ And V has the same meaning as above.

Even more preferably, the compound of formula (H1) is selected from compounds of formula (H1-3),

wherein the symbols have the same meaning as above.

Particularly preferably, the compound of formula (H1) is selected from compounds of formula (H1-4),

wherein the symbols have the same meaning as above.

Very particularly preferably, the compound of the formula (H1) is selected from compounds of the formula (H1-5),

wherein the symbols have the same meaning as in claim 1.

Examples of very suitable compounds of the formula (H1-5) are the compounds (H1-5-1) to (H1-5-4),

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wherein the symbols have the same meaning as above.

Preferably, R ^X 、R ^V Represents H, D, F, in each case identically or differently, a straight-chain alkyl, alkoxy or thioalkyl radical having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH' s ₂ Radicals which may be replaced by RC = CR, C ≡ C, O or S and in which one or more H atoms may be replaced by D or F, aromatic or heteroaromatic ring systems having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18, aromatic ring atoms which may in each case be substituted by one or more radicalsThe group R is substituted. More preferably, R ^X 、R ^V In each case identically or differently, represents H, D, F, a straight-chain alkyl radical having from 1 to 20, preferably from 1 to 10, more preferably from 1 to 6, C atoms, or a branched or cyclic alkyl radical having from 3 to 20, preferably from 3 to 10, more preferably from 3 to 6, C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R.

More preferably, R ^X 、R ^V In each case identically or differently, represents H, D, a linear alkyl radical having from 1 to 10, more preferably from 1 to 6, C atoms, or a branched or cyclic alkyl radical having from 3 to 10, more preferably from 3 to 6, C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R.

Preferably, the group Ar ² 、Ar ⁴ Are selected, identically or differently on each occurrence, from aromatic or heteroaromatic ring systems having from 5 to 30, preferably from 5 to 25, aromatic ring atoms, which may be substituted in each case by one or more radicals R. More preferably, the group Ar ² 、Ar ⁴ Selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, terphenyl, fluoranthene, tetracene, chicory, benzanthracene, triphenylene, pyrene, perylene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinolone, benzopyridine, benzopyridazine, benzopyrimidine, benzimidazole and quinazoline, each of which may be substituted by one or more groups R; wherein Ar ² 、Ar ⁴ Combinations of two or more of the foregoing groups are also possible. Particularly preferably, the group Ar ² 、Ar ⁴ Selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, tetracene, chicory, benzanthracene, triphenylene, pyrene or perylene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted in any free position by one or more groups R; and wherein Ar ² 、Ar ⁴ Combinations of two or more of the foregoing groups are also possible. Very particularly preferably, the group Ar ² 、Ar ⁴ Selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted at any free position by one or more groups R; and wherein Ar ² 、Ar ⁴ Combinations of two or more of the foregoing groups are also possible.

Suitable radicals Ar ² And Ar ⁴ Examples of (A) are groups of formulae (Ar 2-1) to (Ar 2-27) as depicted in the following table:

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wherein the dotted bond indicates a bond to an adjacent group and wherein the group R ⁰ Have the same meaning as above; and wherein the groups of formulae (Ar 2-1) to (Ar 2-27) may be substituted at each free position by a group R, which group R has the same meaning as above.

Among the groups of formulae (Ar 2-1) to (Ar 2-27), the groups of formulae (Ar 2-1), (Ar 2-2), (Ar 2-3), (Ar 2-4), (Ar 2-5), (Ar 2-8), (Ar 2-18), (Ar 2-19) are preferred. The groups of the formulae (Ar 2-1), (Ar 2-2), (Ar 2-3), (Ar 2-4), (Ar 2-5) are very preferred.

Preferably, the group Ar ^S In each case identically or differently represents phenyl, biphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, dibenzofuranFurans, dibenzothiophenes, carbazoles, pyridines, pyrimidines, pyrazines, pyridazines, triazines, benzopyridines, benzopyridazines, benzopyrimidines and quinazolines, each of which may be substituted with one or more groups R.

Suitable radicals Ar ^S Examples of (A) are groups of the formulae (ArS-1) to (ArS-26) as shown in the following table:

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wherein the dotted bond in formula (H1) or (H2) indicates a bond to an adjacent group;

wherein the radicals of formulae (ArS-1) to (ArS-26) may be substituted in each free position by a radical R which has the same meaning as defined above; and is

Wherein the radicals E are in each case selected identically or differently from-BR ⁰ -、-C(R ⁰ ) ₂ -、-Si(R ⁰ ) ₂ -、-C(＝O)-、-O-、-S-、-S(＝O)-、-SO ₂ -、-N(R ⁰ ) -and-P (R) ⁰ )-，

Wherein R is ⁰ Represent in each case identically or differently H, D, F, a straight-chain alkyl radical having from 1 to 20, preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 20, preferably from 3 to 10, C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH' s ₂ The radicals may be replaced by O or S and in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms which may in each case be substituted by one or more radicals R, where two adjacent radicals R ⁰ May together form an aliphatic or aromatic ring system which may be substituted by one or more radicalsGroup R.

Among the groups of the formulae (ArS-1) to (ArS-26), the groups of the formulae (ArS-1), (ArS-2), (ArS-3), (ArS-11) and (ArS-12) are preferred. The radicals of the formulae (ArS-1), (ArS-2), (ArS-3) are very particularly preferred.

Preferably, R represents in each case identically or differently H, D, F, CN, N (Ar) ₂ Straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms, or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms, each of which may be substituted by one or more radicals R ', where in each case one or more non-adjacent CH' s ₂ The radicals may be replaced by R ' C = CR ', C ≡ C, O or S and in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 6 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R '.

Preferably, ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 25, very preferably from 6 to 18, aromatic ring atoms, which may in each case also be substituted by one or more radicals R';

preferably, R' represents in each case identically or differently H, D, F, cl, br, I, CN, a linear alkyl radical having from 1 to 10C atoms or a branched or cyclic alkyl radical having from 3 to 10C atoms, where in each case one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having from 5 to 18C atoms.

The following compounds are examples of compounds of formula (H1):

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the following compounds are examples of compounds of formula (H2):

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according to a preferred embodiment, the composition comprises a compound of formula (H1), a compound of formula (H2) and at least one fluorescent emitter. The expression "at least one fluorescent emitter" means "one, two, three or more fluorescent emitters"

Preferably, the composition comprises at least one fluorescent emitter comprising at least one of the following groups:

arylamines containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen;

-a bridging triarylamine;

-a fused aromatic or heteroaromatic ring system having at least 14 aromatic ring atoms;

-indenofluorene, indenofluorenamine or indenofluorenediamine;

-a benzindenofluorene, benzindenofluorene amine or benzindenofluorene diamine;

-dibenzoindenofluorene, dibenzoindenofluorene amine or dibenzoindenofluorene diamine;

-indenofluorenes containing a fused aryl group having at least 10 aromatic ring atoms;

-bisindeno indenofluorenes;

-indenodibenzofuran; indenofluorenamines or indenofluorenediamines;

-fluorene dimer;

-thiophen

A oxazine; or

-a boron derivative.

More preferably, the composition comprises at least one fluorescent emitter of one of the following formulae (E-1), (E-2), (E-3) or (E-4) as depicted below:

wherein

Ar ¹⁰ 、Ar ¹¹ 、Ar ¹² Identically or differently on each occurrence is an aromatic or heteroaromatic ring system having from 6 to 60 aromatic ring atoms, which may also be substituted on each occurrence by one or more radicals R; with the proviso that at least one group Ar ¹⁰ 、Ar ¹¹ 、Ar ¹² Is an aromatic or heteroaromatic ring system having 10 to 40 aromatic ring atoms which contains at least one fused aryl or heteroaryl group consisting of 2 to 4 aromatic rings fused to one another, wherein the aromatic or heteroaromatic ring system can be substituted by one or more radicals R;

r has the same definition as above; and is

e is 1,2,3 or 4; more preferably, e is 1;

wherein

Ar ²⁰ 、Ar ²¹ 、Ar ²² Identically or differently on each occurrence is an aryl or heteroaryl radical having from 6 to 30 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;

E ²⁰ in each case identically or differently, is selected from BR, C (R) ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、C＝O、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、O、S、S＝O、SO ₂ 、NR ⁰ 、PR ⁰ 、P(＝O)R ⁰ Or P (= S) R ⁰ A group of (a); wherein Ar is ²⁰ 、Ar ²¹ And E ²⁰ Together form a five-or six-membered ring, and Ar ²¹ 、Ar ²³ And E ²⁰ Together form a five-membered or six-membered ring;

R ⁰ in each case identically or differently, represents H, D, F, a straight-chain alkyl radical having 1 to 20, preferably 1 to 10C atoms, or a branched or cyclic alkyl radical having 3 to 20, preferably 3 to 10C atoms, andeach of the radicals mentioned may be substituted by one or more radicals R, where in each case one or more non-adjacent CH groups ₂ The radicals may be replaced by O or S and in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms which may in each case be substituted by one or more radicals R, where two adjacent radicals R ⁰ May together form an aliphatic or aromatic ring system which may be substituted by one or more radicals R,

r has the same definition as above;

p, q are in each case identically or differently 0 or 1, with the proviso that p + q =1;

r is 1,2 or 3;

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wherein

Ar ³⁰ 、Ar ³¹ 、Ar ³² Represent, identically or differently on each occurrence, a substituted or unsubstituted aryl or heteroaryl radical having from 5 to 22, preferably from 5 to 18, more preferably from 6 to 14, aromatic ring atoms;

E ³⁰ represents B or N;

E ³¹ 、E ³² 、E ³³ in each case identically or differently represents O, S, C (R) ⁰ ) ₂ 、C＝O、C＝S、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、BR ⁰ 、NR ⁰ 、PR ⁰ 、SO ₂ 、SeO ₂ Or a chemical bond, provided that if E ³⁰ Is B, then the group E ³¹ 、E ³² 、E ³³ At least one of them represents NR ⁰ And if E ³⁰ Is N, then the radical E ³¹ 、E ³² 、E ³³ At least one of them represents BR ⁰ ；

R ⁰ Have the same definitions as above;

s, t, u are in each case identically or differently 0 or 1, with the proviso that s + t + u.gtoreq.1;

wherein

Ar ⁴⁰ 、Ar ⁴¹ 、Ar ⁴² Represent, identically or differently on each occurrence, a substituted or unsubstituted aryl or heteroaryl radical having from 5 to 22, preferably from 5 to 18, more preferably from 6 to 14, aromatic ring atoms;

E ⁴¹ 、E ⁴² 、E ⁴³ in each case identically or differently represents O, S, C (R) ⁰ ) ₂ 、C＝O、C＝S、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、BR ⁰ 、NR ⁰ 、PR ⁰ 、SO ₂ 、SeO ₂ Or a chemical bond, provided that the group E ⁴¹ 、E ⁴² 、E ⁴³ Is present and represents a chemical bond;

R ⁰ have the same definitions as above;

i. g, h are in each case, identically or differently, 0 or 1, with the proviso that i + g + h.gtoreq.1.

Preferably, the fluorescent emitter of formula (E-1) comprises at least one group Ar ¹⁰ 、Ar ¹¹ Or Ar ¹² Preferably Ar ¹⁰ Selected from the group consisting of formula (Ar) ¹⁰ -1) to (Ar) ¹⁰ -24) of:

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wherein the group Ar ¹⁰ -1 to Ar ¹⁰ -24 can be substituted in all free positions by one or more radicals R; and wherein

E ¹⁰ Are in each case identically or differently selected from BR ⁰ 、C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、C＝O、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、O、S、S＝O、SO ₂ 、NR ⁰ 、PR ⁰ 、P(＝O)R ⁰ Or P (= S) R ⁰ Preferably E ¹⁰ Is C (R) ⁰ ) ₂ ；

Wherein R is ⁰ Have the same definitions as above;

E ¹¹ in each case identically or differently, is selected from C = O, O, S, S = O or SO ₂ Preferably O or S, more preferably O; and is

Ar ¹³ Identical or different on each occurrence are aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may also be substituted in each case by one or more radicals R.

According to a preferred embodiment, the luminophore of formula (E-1) comprises a compound selected from formula (Ar) ¹⁰ -15) to (Ar) ¹⁰ Group Ar of the group of-22) ¹⁰ Wherein d is preferably equal to 1 and wherein preferably at least one group Ar ¹¹ 、Ar ¹² Selected from the formula (Ar) ¹⁰ -15) to (Ar) ¹⁰ -22).

According to a very preferred embodiment, the luminophore of the formula (E-1) is selected from luminophores of the formulae (E-1-1) to (E-1-6),

wherein the symbols have the same meaning as above and wherein:

f is 0, 1 or 2; and is

The phenyl rings shown above in the compounds of the formulae (E-1-1) to (E-1-6) may be substituted in all free positions by one or more radicals R.

Particularly preferably, the compound of formula (E-1) is selected from the compounds of formulae (E-1-1-A) to (E-1-6-A),

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wherein the symbols and indices have the same meaning as above and wherein the phenyl rings shown above in the compounds of the formulae (E-1-1-A) to (E-1-6-A) may be substituted in all free positions by one or more radicals R.

Preferably, the fluorescent emitter of formula (E-2) is selected from the fluorescent emitters of formulae (E-2-1) to (E-2-43),

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wherein the radicals of the formulae (E-2-1) to (E-2-43) may be substituted in all free positions by one or more radicals R; and wherein E ²⁰ Have the same definitions as above. Preferably, E ²⁰ Is C (R) ⁰ ) ₂ 。

The compound of formula (E-2) is preferably selected from compounds of formulae (E-2-32) to (E-2-43). More preferably, the compound of formula (E-2) is selected from the compounds (E-2-32-A) to (E-2-43-A):

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wherein the symbols have the same meaning as above and wherein the benzene and naphthalene rings shown above in the compounds of the formulae (E-2-32-A) to (E-2-43-A) may be substituted in all free positions by one or more radicals R.

Preferably, the fluorescent emitter of formula (E-3) is selected from the fluorescent emitters of formula (E-3-1),

wherein the symbols and indices have the same meaning as above.

More preferably, the fluorescent emitter of formula (E-3) is selected from the fluorescent emitters of formula (E-3-2),

wherein the symbol E ³⁰ To E ³³ Have the same meaning as above; wherein t is 0 or 1, wherein when t is 0, the radical E ³² Is absent and the group R ¹⁰ Exist instead of E ³² A linked key; and isWherein

R ¹⁰ In each case identically or differently, represents H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R′) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R′) ₃ ，B(OR′) ₂ ，OSO ₂ R' 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, it being possible for each of said radicals to be substituted by one or more radicals R ^′ Substitution, wherein in each case one or more non-adjacent CH ₂ The groups may be substituted with R ' C = CR ', C ≡ C, si (R ') ₂ 、Ge(R′) ₂ 、Sn(R′) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO ₂ O, S or CONR' and where one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, 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 radicals R ', or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R'; wherein two adjacent substituents R ¹⁰ May together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R'; wherein R' has the same definition as above.

Even more preferably, the fluorescent emitter of formula (E-3) is selected from the fluorescent emitters of formulae (E-3-3) and (E-3-4),

wherein the symbols and indices have the same meaning as above.

Preferably, the fluorescent emitter of formula (E-4) is selected from the fluorescent emitters of formulae (E-4-1) or (E-4-2),

wherein

E ⁴¹ And E ⁴² In each case identically or differently represents O, S, C (R) ⁰ ) ₂ 、C＝O、C＝S、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、BR ⁰ 、NR ⁰ 、PR ⁰ 、SO ₂ 、SeO ₂ Or a chemical bond, wherein E ⁴¹ Preferably a bond;

R ²⁰ in each case identically or differently, represents H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R′) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R′) ₃ ，B(OR′) ₂ ，OSO ₂ R ' is a straight-chain 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, each of which may be substituted by one or more radicals R ', where in each case one or more non-adjacent CH ' s ₂ The groups may be substituted with R ' C = CR ', C ≡ C, si (R ') ₂ 、Ge(R′) ₂ 、Sn(R′) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO ₂ O, S or CONR' and wherein one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, 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 radicals R ', or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R'; wherein two adjacent substituents R ²⁰ May together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R'; wherein R' has the same definition as above;

g is 0 or 1.

More preferably, the fluorescent emitter of formula (E-4) is selected from fluorescent emitters of formula (E-4-1-A) or (E-4-2-A),

wherein the symbols have the same meaning as above.

According to a preferred embodiment, said fluorescent luminophore of formula (E-1), (E-2), (E-3) or (E-4) comprises a group RS, wherein said group RS is selected from:

a branched or cyclic alkyl group represented by a group of the following general formula (RS-a),

wherein

R ²² 、R ²³ 、R ²⁴ Are in each case identically or differently selected from H, straight-chain alkyl radicals having from 1 to 10 carbon atoms, or branched or cyclic alkyl radicals having from 3 to 10 carbon atoms, where the abovementioned radicals may each be substituted by one or more radicals R ²⁵ And wherein the radical R is substituted ²² 、R ²³ 、R ²⁴ Two or all radicals R in ²² 、R ²³ 、R ²⁴ May be joined to form a (poly) cyclic alkyl group, which may be substituted by one or more groups R ²⁵ Substitution;

R ²⁵ in each case identically or differently selected from straight-chain alkyl groups having from 1 to 10 carbon atoms, or branched or cyclic alkyl groups having from 3 to 10 carbon atoms;

with the proviso that in each case a radical R is present ²² 、R ²³ And R ²⁴ Is not H, with the proviso that in each case all radicals R are ²² 、R ²³ And R ²⁴ Together having at least 4 carbon atoms, and with the proviso that in each case if the radical R is ²² 、R ²³ 、R ²⁴ Are H, the remaining groups are not straight-chain; or

-a branched or cyclic alkoxy group represented by the following general formula (RS-b),

wherein

R ²⁶ 、R ²⁷ 、R ²⁸ Are in each case selected, identically or differently, from H, straight-chain alkyl radicals having from 1 to 10 carbon atoms, or branched or cyclic alkyl radicals having from 3 to 10 carbon atoms, where the abovementioned radicals may each be substituted by one or more radicals R as defined above ²⁵ And wherein the radical R ²⁶ 、R ²⁷ 、R ²⁸ Two or all radicals R in ²⁶ 、R ²⁷ 、R ²⁸ May be joined to form a (poly) cyclic alkyl group, which may be substituted by one or more groups R as defined above ²⁵ Substitution;

with the proviso that in each case a radical R ²⁶ 、R ²⁷ And R ²⁸ Only one of which may be H;

an aralkyl group represented by the following general formula (RS-c),

wherein

R ²⁹ 、R ³⁰ 、R ³¹ Are in each case identically or differently selected from H, straight-chain alkyl radicals having from 1 to 10 carbon atoms, or branched or cyclic alkyl radicals having from 3 to 10 carbon atoms, where the abovementioned radicals may each be substituted by one or more radicals R ³² Substituted, or having from 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R ³² And wherein the radical R ²⁹ 、R ³⁰ 、R ³¹ May be joined to form a (poly) cyclic alkyl group or an aromatic ring system, each of which may be substituted with one or more groups R ³² Substitution;

R ³² in each case identically or differently selected from straight-chain alkyl radicals having from 1 to 10 carbon atoms, or branched or cyclic alkyl radicals having from 3 to 10 carbon atoms, or aromatic ring systems having from 6 to 24 aromatic ring atoms;

with the proviso that in each case a radical R is present ²⁹ 、R ³⁰ And R ³¹ Is not H and in each case a radical R ²⁹ 、R ³⁰ And R ³¹ Is an aromatic ring system having at least 6 aromatic ring atoms or contains an aromatic ring system having at least 6 aromatic ring atoms;

-an aromatic ring system represented by the following general formula (RS-d),

wherein

R ⁴⁰ To R ⁴⁴ Are selected identically or differently in each case from H, straight-chain alkyl radicals having from 1 to 10 carbon atoms, or branched or cyclic alkyl radicals having from 3 to 10 carbon atoms, where the abovementioned radicals may each be substituted by one or more radicals R ³² Substituted, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R ³² And wherein the radical R ⁴⁰ To R ⁴⁴ Two or more of which may be joined to form a (poly) cyclic alkyl group or aromatic ring system, each of which may be substituted by one or more groups R as defined above ³² Substitution; or

-a group of formula (RS-e),

wherein the dotted bond in formula (RS-e) indicates bonding to a fluorescent emitter, wherein Ar ⁵⁰ 、Ar ⁵¹ Represent, identically or differently on each occurrence, an aromatic or heteroaromatic ring having 5 to 60 aromatic ring atomsAn aromatic ring system, which may be substituted in each case by one or more radicals R; and wherein m is an integer selected from 1 to 10.

Preferably, the index m in the group of formula (RS-e) is an integer selected from 1 to 6, very preferably from 1 to 4.

Preferably, ar ⁵⁰ 、Ar ⁵¹ Represent, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms, which may be substituted in each case by one or more radicals R. More preferably, ar ⁵⁰ 、Ar ⁵¹ Selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, dibenzofuran, carbazole and dibenzothiophene, which may in each case be substituted by one or more radicals R. Very preferably, at least one group Ar ⁵⁰ Or Ar ⁵¹ Is fluorene, which may be substituted by one or more groups R.

More particularly, it is preferred that at least one group Ar ⁵⁰ A group representing formula (Ar 50-2) and/or at least one group Ar ⁵¹ A group represented by the formula (Ar 51-2),

wherein

The dotted bonds in formula (Ar 50-2) indicate bonding to the fluorescent emitter and to the group Ar ⁵⁰ Or Ar ⁵¹ Bonding of (1); and the dotted bond in formula (Ar 51-2) indicates with Ar ⁵⁰ Bonding of (1);

E ⁴ is selected from-C (R) ^0a ) _2- 、-Si(R ^0a ) _2- -O-, -S-or-N (R) ^0a ) -, preferably-C (R) ^0a ) ₂ ；

R ^0a Represent in each case identically or differently H, D, F, CN, a straight-chain alkyl radical having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms, or a linear alkyl radical having 3 to 40, preferably 3 to 20,More preferably 3 to 10C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R; wherein two adjacent substituents R ^0a May form a mono-or polycyclic, aliphatic or aromatic ring system, which may be substituted by one or more radicals R having the same meaning as above; and is

The groups of formulae (Ar 50-2) and (Ar 51-2) may be substituted at each free position by a group R which has the same meaning as above.

The radical RS is preferably located in its place R, R ⁰ Or the position of R'.

Examples of fluorescent emitters which can be used in the composition comprising the compounds of formulae (H1) and (H2) are aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chicoric amines or aromatic chicoric diamines. Aromatic anthracenamines are understood to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9 position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are bonded directly to the anthracene group, preferably at the 9,10 position. Aromatic pyrene amines, pyrene diamines, chicory amines and chicory diamines are similarly defined, wherein the diarylamino group is preferably bonded to pyrene at position 1 or at

position

1,6. Also preferred emitters are bridged triarylamines, for example according to WO 2019/111971, WO2019/240251 and WO 2020/067290. Also preferred luminophores are indenofluorenylamines or indenofluorenyldiamines, for example according to WO 2006/108497 or WO 2006/122630; a benzindenofluorenamine or a benzindenofluorenediamine, for example according to WO 2008/006449; and dibenzoindenofluorenamines or dibenzoindenofluorenediamines, for example according to WO 2007/140847; and indenofluorene derivatives containing fused aryl groups as disclosed in WO 2010/012328. Further preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, linked via a heteroaryl group as in WO 2016/150544Grafted fluorene dimers or thiophenes as disclosed in WO 2017/028940 and WO 2017/028941

An oxazine derivative. Also preferred are pyrene arylamines disclosed in WO 2012/048780 and WO 2013/185871. Benzoindenofluorenamines as disclosed in WO 2014/037077, benzofluorenamines as disclosed in WO 2014/106522 and indenofluorenes as disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421 are likewise preferred. Also preferred are luminophores comprising a dibenzofuran or indenodibenzofuran moiety, as disclosed in WO 2018/095888, WO 2018/095940, WO 2019/076789, WO 2019/170572 and unpublished applications PCT/EP2019/072697, PCT/EP2019/072670 and PCT/EP 2019/072662. Also preferred are boron derivatives, as disclosed in e.g. WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 and unpublished applications EP 19168728.4, EP 19199326.0 and EP 19208643.7.

Very suitable fluorescent emitters in the context of the present invention are indenofluorene derivatives as disclosed in WO 2018/007421 and dibenzofuran derivatives as disclosed in WO 2019/076789.

Examples of preferred fluorescent light-emitting compounds that can be used in compositions comprising compounds of formulae (H1) and (H2) are shown in the following table:

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according to the invention, the compound of formula (H1) and the compound of formula (H2) are present together in the composition, preferably in a homogeneous mixture.

Preferably, the compound of the formula (H1) is present in the composition according to the invention in a proportion of from 1 to 60%, preferably from 5 to 50%, more preferably from 10 to 50%, particularly preferably from 5 to 40%, more particularly preferably from 10 to 40% and very particularly preferably from 20 to 40%.

Preferably, the compound of the formula (H2) is present in the composition in a proportion of from 30 to 99%, preferably from 50 to 95%, more preferably from 50 to 90%, particularly preferably from 60 to 95%, more particularly preferably from 60 to 90% and very particularly preferably from 60 to 80%.

According to a preferred embodiment, the composition according to the invention further comprises at least one fluorescent emitter. In this case, it is preferred that the fluorescent emitter is present in the composition in a proportion of 0.1% to 50.0%, preferably 0.5% to 20.0%, particularly preferably 1.0% to 10.0%.

For the purposes of the present application, 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 the solution.

For processing the compounds according to the invention from the liquid phase, for example by coating processes such as spin coating or by printing processes, formulations of the compositions according to the invention are required. These preparations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. The solvent is preferably selected fromOrganic and inorganic solvents, more preferably selected from organic solvents. The solvent is very preferably selected from the group consisting of hydrocarbons, alcohols, esters, ethers, ketones and amines. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, bis-xylene

Alkanes, phenoxytoluenes, particularly 3-phenoxytoluene, (-) -fenchytone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 1-ethylnaphthalene, decylbenzene, phenylnaphthalene, menthyl isovalerate, p-tolylisobutyrate, cyclohexyl hexanoate, ethyl p-toluate, ethyl o-toluate, ethyl m-toluate, decalin, ethyl 2-methoxybenzoate, dibutylaniline, dicyclohexylketone, isosorbide dimethyl ether, decahydronaphthalene, 2-methylbiphenyl, ethyl octanoate, octyl octanoate, diethyl sebacate, 3,3-dimethylbiphenyl, 1,4-dimethylnaphthalene, 2,2' -dimethylbiphenyl, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylbenzyl ether, 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 mixtures of these solvents.

The invention therefore also relates to formulations comprising a compound of formula (H1) and a compound of formula (H2) according to the invention and at least one solvent. The solvent may be one of the above solvents or a mixture of these solvents.

The proportion of organic solvent in the formulation according to the invention is preferably at least 60% by weight, preferably at least 70% by weight and more preferably at least 80% by weight, based on the total weight of the formulation.

The formulations according to the invention can be used for producing layers or multilayer structures in which organic functional materials are present in the layer, as is required for producing preferred electronic or optoelectronic components, such as OLEDs.

The formulations of the invention can preferably be used to form a functional layer comprising the composition according to the invention on a substrate or on one of the layers applied to the substrate.

Another object of the invention is a method for producing an electronic device, wherein at least one layer is obtained from the application of the formulation of the invention. Preferably, the formulation according to the invention is applied to a substrate or another layer and then dried.

The functional layer obtained from the formulation according to the invention can be produced, for example, by: flow coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roll coating, flexographic printing, offset printing or nozzle printing, preferably ink jet printing on the substrate or one of the layers applied to the substrate.

After the application of the formulation according to the invention to a substrate or to an already applied functional layer, a drying step can be carried out to remove the solvent. Preferably, the drying step comprises vacuum drying, preferably followed by annealing of the layer. Vacuum drying here may preferably be at 10 ^-7 In the range from mbar to 1 bar, particularly preferably 10 ^-6 At a pressure in the range from mbar to 1 bar. The vacuum drying is preferably carried out at a temperature in the range of 10 ℃ to 50 ℃, more preferably 15 to 30 ℃. The vacuum drying step is preferably followed by thermal annealing of the layer. The thermal annealing of the layer is preferably carried out at a temperature of 120 ℃ to 180 ℃, preferably 130 ℃ to 170 ℃, more preferably 140 ℃ to 160 ℃.

The present invention therefore relates to a process for manufacturing an electronic device comprising at least one layer comprising a composition according to the invention, wherein the process comprises the steps of:

a) Preparing a formulation according to the invention;

b) Applying the formulation prepared in step a) on a substrate or on another layer to form a layer comprising a composition according to the invention;

c) The layer is dried to remove the solvent.

Preferably, in step b), the formulation is applied by processing from a liquid phase, more preferably via a coating process or a printing process, very more preferably by a printing process, particularly preferably by an inkjet printing process.

Another object of the present invention is an electronic device comprising an anode, a cathode and at least one functional layer therebetween, wherein said functional layer comprises a composition according to the present invention. Preferably, at least one functional layer comprising the composition according to the invention is a light-emitting layer.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), 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. More preferably, the electronic device is an organic electroluminescent device (OLED).

The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer comprising a composition according to the invention. 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 herein may include 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 maxima between 380nm and 750nm in total, so that white emission as a whole occurs, i.e. a plurality of light-emitting compounds capable of fluorescence or phosphorescence are used in the light-emitting layers. Particular preference is given to systems having three light-emitting layers, wherein the three layers exhibit blue, green and orange or red emission (see, for example, WO 2005/011013, regarding the basic structure). 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.

The electronic device concerned may comprise a single light-emitting layer comprising the composition according to the invention, or it may comprise two or more light-emitting layers.

The composition according to the invention may comprise one or more additional matrix materials.

Preferred additional matrix materials are selected from the following classes: oligoarylene (e.g. 2,2',7,7' -tetraphenylspirobifluorene, or dinaphthylanthracene according to EP 676461), in particular oligoarylene containing fused aromatic groups, oligoarylenevinylene (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodle metal complexes (e.g. according to WO 2004/081017), hole-conducting compounds (e.g. according to WO 2004/058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), boronic acid derivatives (e.g. according to WO 2006/117052) or benzanthracene (e.g. according to WO 2008/145239). Particularly preferred matrix materials are selected from the following classes: oligoarylene, including naphthalene, anthracene, benzanthracene and/or pyrene or these compounds of atropisomers, oligoarylene vinylene, ketone, phosphine oxide and sulfoxide. Very particularly preferred matrix materials are selected from the following classes: oligoarylene, including anthracene, benzanthracene, triphenylene, and/or pyrene or atropisomers of these compounds. An oligoarylene in the sense of the present invention is intended to be taken to mean a compound in which at least three aryl or arylene groups are bonded to one another.

Generally preferred classes of materials for use as corresponding functional materials in the organic electroluminescent device according to the invention are as follows.

Suitable charge transport materials which can be used in the hole injection or hole transport layer or the electron blocking layer or the electron transport layer of the electronic device according to the invention are the compounds disclosed in, for example, y.shirota et al, chem.rev.2007,107 (4), 953-1010, or other materials employed 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 such as Alq ₃ Zirconium complexes such as Zrq ₄ Lithium 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-slow derivatives and phosphine oxide derivatives. Furthermore, suitable materials are derivatives of the above-mentioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred hole transport materials which can be used for the hole transport, hole injection or electron blocking layer in the electroluminescent device according to the invention are indenofluorenamine derivatives (for example according to WO 06/122630 or WO 06/100896), amine derivatives disclosed in EP 1661888, hexaazaterphenyl fork derivatives (for example according to WO 01/049806), amine derivatives containing fused aromatic rings (for example according to US 5,061,569), amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (for example according to WO 08/006449), dibenzoindenofluorenamines (for example according to WO 07/140847), spirobifluorenylamines (for example according to WO 2012/034627 or WO 2013/120577), fluorenamines (for example according to application EP 2875092, EP 2875699 and EP 2875004), spirodibenzopyranamines (for example according to WO 2013/03216) and dihydroacridine derivatives (for example according to WO 2012/083001). The compounds according to the invention can also be used as hole transport materials.

The cathode of the organic electroluminescent device preferably comprises a metal having a low work function, a metal alloy or a multilayer structure comprising a plurality of metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (for exampleSuch as Ca, ba, mg, al, in, mg, yb, sm, etc.). Also suitable are alloys comprising an alkali 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 metals are generally used, such as Ca/Ag, mg/Ag or Ag/Ag. It may also be preferred to introduce a thin intermediate layer of a material with 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) ₂ O、BaF ₂ 、MgO、NaF、CsF、Cs ₂ CO ₃ Etc.). In addition, lithium quinolinate (LiQ) may be used for this purpose. The layer thickness of this layer is preferably between 0.5 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. On the one hand, metals with a high redox potential, such as Ag, pt or Au, are suitable for this purpose. On the other hand, metal/metal oxide electrodes (e.g., al/Ni/NiO) _x 、Al/PtO _x ) May also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to facilitate illumination of the organic material (organic solar cells) or coupling out light (OLEDs, O-lasers). Preferred anode materials herein are conductive mixed metal oxides. Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) is particularly preferable. Preference is furthermore given to conductively doped organic materials, in particular conductively doped polymers.

The device is suitably (depending on the application) structured, contact-connected and finally sealed, since the lifetime of the device according to the invention is shortened in the presence of water and/or air.

In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that the layer or layers are applied by a sublimation process, wherein the material is in a range of less than 10 ^-5 Mbar, preferably less than 10 ^-6 At an initial pressure of mbar, applied by vapor deposition in a vacuum sublimation unit. However, the initial pressure hereThe force may also be lower, e.g. less than 10 ^-7 Millibar.

Preference is likewise given to 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 the material is between 10 ^-5 At a pressure between mbar and 1 bar. A particular example of such a process is the OVJP (organic vapor jet printing) process, in which the material is applied directly through a nozzle and is thus structured (e.g. m.s. Arnold et al, 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, soluble compounds of formula (I) are required. High solubility can be achieved by appropriate substitution of the compounds.

Hybrid processes are also possible, in which one or more layers are applied, for example, from solution and one or more further 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 therefrom without inventive effort to organic electroluminescent devices comprising the compounds according to the invention.

According to the invention, electronic devices comprising one or more compounds according to the invention can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (e.g. phototherapy).

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

Synthesis example

Synthesis of Int-1

11.0g (32 mmol) of CAS2377545-68-9 are dissolved in 130mL of THF and cooled to-78 deg.C, and 25mL of a 1.6M solution of n-butyllithium in hexane are added and the reaction mixture is stirred for one hour. Then, 19g (0.1 mol) of triisopropoxyboron was added thereto and stirred for one hour. The reaction mixture was warmed to room temperature and stirred for one hour, and 480mL of a 1N hydrochloric acid solution was added and stirred for 30 minutes. The organic phase of the resulting reaction mixture was extracted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by column chromatography. Yield: 6.4g (21mmol, 66%).

Synthesis of compound A1:

7.9g (32 mmol) 3,6-dichloro-phenanthrene (20851-90-5), 30.4g (80 mmol) 4,4,5,5-tetramethyl-2- (10-phenyl-9-anthracenyl) -1,3,2-dioxaborolan (460347-59-5), 29.5g (128 mmol) potassium phosphate monohydrate were dissolved in 750ml THF/water (2:1). 813mg (0.96 mmol) of XPhos Palladacycle Gen.3 are added and the mixture is stirred at 65 ℃. After 16 hours, the reaction mixture was allowed to reach room temperature. The reaction mixture was filtered and washed with cold THF. The precipitate was purified by thermal extraction through alumina (toluene) and further purified to purity by crystallization from toluene/ethanol and toluene/heptane>99.9 (according to HPLC). By heating at 300 ℃ at 10 ^-5 The remaining solvent was removed by a 2 hour bar temper.

Yield: 4.9g (7.2mmol, 23%) of a pale yellow solid

The following compounds can be synthesized in a similar manner:

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synthesis of compound I1:

9.3g (32 mmol) of 3-bromo-6-chloro-phenanthrene (892550-44-6), 13.3g (35 mmol) of 4,4,5,5-tetramethyl-2- (10-phenyl-9-anthryl) -1,3,2-dioxaborolan (460347-59-5), 11.5g (50 mmol) of potassium phosphate monohydrate were dissolved in 750ml of THF/water (2:1). 813mg (0.96 mmol) of XPhos Palladacycle Gen.3 are added and the mixture is stirred at 65 ℃. After 16 hours, the reaction mixture was allowed to reach room temperature. The mixture was diluted with 300ml of toluene. The aqueous phase was extracted with toluene (2X 200 ml) and the combined organic phases were washed with water (2X 200 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure. The remaining solid was filtered through silica (toluene) and crystallized from toluene/ethanol to a purity of 98% (according to HPLC).

Yield 10.7g (23mmol, 72%)

The following compounds can be synthesized in a similar manner:

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synthesis of Compound B1:

9.3g (20 mmol) of I1, 16.0g (30 mmol) of 4,4,5,5-tetramethyl-2- (10- { 5-phenyl- [1,1' -biphenyl]-3-yl } anthracen-9-yl) -1,3,2-dioxaborolane (1016653-38-5), 11.5g (50 mmol) potassium phosphate monohydrate were dissolved in 750ml THF/water (2:1). 813mg (0.96 mmol) of XPhos Palladacycle Gen.3 are added and the mixture is stirred at 65 ℃. After 16 hours, the reaction mixture was allowed to reach room temperature.The mixture was diluted with 300ml of toluene. The aqueous phase was extracted with toluene (2X 200 ml) and the combined organic phases were washed with water (2X 200 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure. The remaining solid was purified by thermal extraction through alumina (toluene) and crystallized from toluene/ethanol and toluene/heptane to purity>99.9% (according to HPLC). By heating at 300 ℃ and 10 DEG C ^-5 The remaining solvent was removed by a bar tempering for 2 hours.

Yield: 7.5g (9mmol, 45%)

The following compounds can be synthesized in a similar manner:

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synthesis of compound C1:

15g (38 mmol) of trifluoro-methanesulfonic acid 8-bromo-dibenzofuran-1-yl ester, 43.3g (114 mmol) of 4,4,5,5-tetramethyl-2- (10-phenyl-anthracen-9-yl) - [1,3,2]Dioxolane, 35.5g (167 mmol) potassium phosphate and 1.6g (1, 9 mmol) XPhos Palladacycle Gen.3 were dissolved in 450ml THF/water (2:1). The mixture was stirred at 90 ℃ for 16 hours. After cooling to room temperature, 300ml of ethanol were added and the mixture was stirred for one hour. The precipitate was filtered off and washed with ethanol. The starting material was dissolved in toluene and filtered through a filter rod (silica, toluene) to give a yellow solid which was further purified by several crystallizations from toluene/heptane to give a pale yellow solid (HPLC)>99.9). By sublimation (10) ^-5 Bar, at 330 ℃) to remove the remaining solvent.

Yield: 15.2g (22.6mmol, 60%)

The following compounds can be synthesized in a similar manner:

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synthesis of compound Int 1:

10g (25.3 mmol) of trifluoro-methanesulfonic acid 8-bromo-dibenzofuran-1-yl ester, 11.5g (25.31 mmol) 4,4,5,5-tetramethyl-2- [3- (10-phenylanthren-9-yl) phenyl ] -1,3,2-dioxaborolan, 7.7g (55.7 mmol) potassium carbonate, 1.16g (1.3 mmol) tris (dibenzylidene-acetone) dipalladium and 324mg (0.76 mmol) 1,4-bis (diphenylphosphino) butane were dissolved in 250ml THF/water (4:1). The mixture was stirred at 100 ℃ for 16 hours. After cooling to room temperature, 100ml of toluene and 100ml of water are added and the two phases are separated. The organic phase was washed twice with water and the combined aqueous phases were extracted 2 times with toluene. The combined organic phases were filtered through a silica filter plug using toluene as eluent and concentrated under reduced pressure. The residue was purified by several crystallizations from toluene/heptane to give a pale yellow solid (HPLC > 98).

Yield: 6.3g (11mmol

The following compounds can be synthesized in a similar manner:

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synthesis of compound D1:

10g (17.4 mmol) of the compound Int1, 5.5g (18.5 mmol) of 10-phenyl-anthracene-9-boronic acid, 8.1g (38.3 mmol) of potassium phosphate and 0.8g (1 mmol) of XPhos Palladacycle Gen.3 are dissolved in 450ml of THF/water (2:1). The mixture was stirred at 90 ℃ for 16 hours. After cooling to room temperature, 300ml of ethanol were added and the mixture was stirred for one hour. The precipitate was filtered off and washed with ethanol. The starting material was dissolved in toluene and filtered through a filter rod (silica, toluene) to give a yellow solid which was further purified by crystallization from toluene/heptane several times to give a pale yellow solid (HPLC)>99.9). By sublimation (10) ^-5 Bar, at 330 ℃) to remove the remaining solvent.

Yield: 6.8g (9.1mmol, 52%)

The following compounds can be synthesized in a similar manner:

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device embodiment

Preparation of films and devices

The glass substrate covered with pre-structured ITO (50 nm) and pixel isolation bevel build material was cleaned using ultrasonic treatment in de-ionized water. Next, the substrate was dried using an air gun, followed by annealing on a hot plate at 225 ℃ for 2 hours.

All the following process steps were carried out in yellow light.

The following layer sequence is shown in fig. 4a and 4 b.

For the preparation of the device according to fig. 4a, a Hole Injection Layer (HIL) was inkjet printed on a substrate with a thickness of 20nm and dried in vacuum. For this purpose, the HIL ink had a solids concentration of 6 g/l. The HIL was then annealed at 220 ℃ for 30 minutes. Ink jet printing and annealing of the HIL was performed in air. As HIL materials, hole transporting, cross-linkable polymers and p-type dopant salts were dissolved in 3-phenoxytoluene. Such materials are described in WO2016/107668, WO2013/081052 and EP 2325190.

On top of the HIL, a hole transport layer was ink-jet printed at ambient conditions, dried in vacuum and annealed at 225 ℃ for 30 minutes in an argon atmosphere. The hole transport layer is a polymer of the structure shown in table 1 (HTM 1) synthesized according to WO2013156130 or a polymer HTM2 (table 1) synthesized according to WO 2018/114882.

The polymer is dissolved in 3-phenoxytoluene, so the solution usually has a solids content of about 5g/l, if as here a layer thickness of 20nm typical of devices is achieved by ink-jet printing. The layers were applied by inkjet printing in ambient atmosphere, dried in vacuum and annealed by heating at 210 ℃ for 30 minutes in an argon atmosphere.

The light emitting layer includes the following:

-a host material (host material) H1 and a luminescent dopant (emitter) D;

-a host material (host material) H2 and a luminescent dopant (emitter) D; or

Two host materials (host material 1 and host material 2) H1, H2 and a luminescent dopant (emitter) D.

The ratio is shown below.

The mixture for the light-emitting layer was dissolved in 3-phenoxytoluene. The solids content of such solutions is about 10mg/ml, and if as here, a typical layer thickness of 30nm of the device is achieved by ink-jet printing. The blue light emitting layer (B-EML) was also inkjet printed, and then vacuum dried and annealed at 150 ℃ for 10 minutes. Ink jet printing is performed in an ambient atmosphere and annealing is performed in an argon atmosphere.

A device according to fig. 4a was prepared to evaluate EML film uniformity.

For the preparation of the device according to fig. 4b, the above sample was then transferred into a vacuum deposition chamber where the deposition of the two electron transport layers (ETL 1, ETL 2), the Electron Injection Layer (EIL) and the cathode (Al) was performed using thermal evaporation. Thus, ETL1 consists of ETM1 (10 nm film thickness), while ETL2 consists of a 1:1 volume% mixture of ETM1 and ETM2 (35 nm film thickness). The electron injection layer consisted of ETM2 (1 nm) and the cathode was aluminum (100 nm). The results are shown in Table 1. After evaporation, the device was sealed in a glove box under an argon atmosphere.

Table 1: structural formula of material of solution processing layer

Evaluation of uniformity of luminescent film

For the manufacture of displays it is important to obtain very good pixel uniformity while having good device performance. The layer thickness non-uniformity results in a non-uniform brightness distribution, where areas of the film with a lower thickness show increased brightness and thicker areas have reduced brightness. This non-uniformity varies from pixel to pixel, preventing the appearance from being reproducible from pixel to pixel. In combination, this leads to a negative view of the quality of such displays. The present invention thus addresses the subject of EML film uniformity and device performance. Thus, the first step in the evaluation was to check the film uniformity. For this purpose, the stack shown in fig. 4a is used. And processing is stopped after EML deposition.

Films were prepared as described in section a). The composition of the EML is shown in table 2.

To evaluate the uniformity of the printed films, their topography was characterized along a 7.5 μm profile by a profilometer and the Rp-v (peak-to-valley) values and the root mean square difference of roughness were calculated. A profilometer Alpha-step D120 from KLA-Tencor with a 2 μm stylus was used to measure the film profile. The value Rp-v corresponds to the difference in height of the measured maximum and minimum peaks within the measured profile. For ease of viewing, the baseline of the film profile is subtracted so that the minimum peak corresponds to a height of 0nm, and the axis scale is the same for all graphs.

The following two equations were used to determine film uniformity. Peak to valley difference R _p-v Indicating the maximum height difference within the layer (equation 1); and root mean square roughness RMS, wherein z _i Corresponds to the profile height at position i and

corresponding to the average profile height (equation 2). />

R _p-v = Rp-Rv formula 1

Table 2: contour measurement results

Example PE1, which comprises a host mixture according to the invention, shows a significantly reduced R compared to PR2 _p-v And RMS and corresponds to a smoother film (fig. 2 and 3), while the performance of the OLED is comparable in both cases, as shown below (see table 5f, reference example 10 and example 10).

In addition, example PE1 also shows a reduced R compared to PR1 _p-v And RMS, while leading to better OLEDs, as shown below (see table 5f, reference example 9, and example 10).

In summary, a smooth film with good uniformity and good device performance (EQE and LT) can be obtained simultaneously with only a mixed host system.

Additional film uniformity for the additional light emitting layer (EML) is shown in table 2b.

TABLE 2b additional film profiles

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Device results

The device as shown in fig. 4b was prepared as described in section a). The host materials are shown in table 3 and the luminophores are shown in table 4. Blue EML inks were mixed as shown in tables 5 a-j. Tables 5a-j also summarize the various embodiments at 1000cd/m ² Relative external quantum efficiency (relative EQE) at 1000cd/m ² Relative device lifetime (relative LT 90).

Table 3: examples main body

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Table 4: example light emitter

After sealing in a glove box, the OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current/voltage/brightness characteristic (IUL characteristic) which exhibits lambertian luminescence characteristics and the (operating) lifetime are determined. The IUL characteristic is used to determine a characteristic figure of merit, such as external quantum efficiency (in%) at a particular luminance. At each step of the applied ramp voltage, the device is driven at a constant voltage. Device lifetime is measured at a given current with an initial brightness. The brightness is then measured over time by a calibrated photodiode.

Table 5a: blue EML mixture for device embodiments having 1%

Table 5b: blue EML mixture for device embodiments having 3% E1

Table 5c: blue EML mixture for device embodiments having 3% E1

Table 5d: blue EML mixture for device embodiments having 3% E2

Table 5e: blue EML mixture for device embodiments having 5% E2

Table 5f: blue EML mixture for device embodiments having 1% E3

Table 5g: blue EML mixture for device embodiments having 1% E3

Table 5i: blue EML mixture for device embodiments having 3% E4

Table 5j: blue EML mixture for device embodiments having 5% E4

Table 5k: blue EML mixture for device embodiments having 1% E3

Table 5l: blue EML mixture for device embodiments having 5% E2

All of the examples of the shown mixed host system show improved device performance compared to the single host H1 type (i.e., type a or B), while similar performance to the host H2 type can be achieved. This is independent of the luminophore used and of the luminophore concentration used.

As discussed above, the profiles of reference examples 11, 12 and example 11 from table 5f have been determined (see fig. 1-3).

Examples 11 to 13 according to the present invention showed improved device performance in terms of efficiency and lifetime compared to reference example 11. The film comprising the hybrid body according to the present invention was very uniform while showing similar device performance, compared to reference example 12 showing a highly non-uniform film.

The same discussion is valid for the devices according to the invention shown in tables 5a to 5 l.

By means of the present invention, good OLED device performance can be achieved while ensuring uniform film quality.

Claims

1. A composition comprising a compound of formula (H1) and a compound of formula (H2),

where the following applies to the symbols and labels used:

e represents O or S;

z in each case identically or differently represents CR ^Z Or N; or if Z is bonded to the group Ar ^S Or Ar ³ Z is C;

R ^V 、R ^X 、R ^Y 、R ^Z in each case identically or differently, represents H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R) ₃ ，B(OR) ₂ ，OSO ₂ R, straight-chain alkyl, alkoxy having 1 to 40C atomsA radical or thioalkyl radical or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH groups ₂ The group may be substituted with RC = CR, C ≡ C, si (R) ₂ 、Ge(R) ₂ 、Sn(R) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO ₂ O, S or CONR and where one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, 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 radicals R, or an aryloxy group having from 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R;

in which two radicals R ^V Two radicals R ^X Two radicals R ^Y Two radicals R ^Z May together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

r represents in each case identically or differently H, D, F, cl, br, I, CHO, CN, C (= O) Ar, P (= O) (Ar) ₂ ，S(＝O)Ar，S(＝O) ₂ Ar，N(R′) ₂ ，N(Ar) ₂ ，NO ₂ ，Si(R′) ₃ ，B(OR′) ₂ ，OSO ₂ R ' is a straight-chain 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, each of which may be substituted by one or more radicals R ', where in each case one or more non-adjacent CH ' s ₂ The groups may be substituted with R ' C = CR ', C ≡ C, si (R ') ₂ 、Ge(R′) ₂ 、Sn(R′) ₂ 、C＝O、C＝S、C＝Se、P(＝O)(R′)、SO、SO ₂ O, S or CONR' and where one or more H atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may be substituted by one in each caseOr a plurality of radicals R 'or an aryloxy radical having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R'; wherein two radicals R may together form an aliphatic or aromatic ring system which may be substituted by one or more radicals R';

r 'represents in each case 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' s ₂ The radicals being selected from SO, SO ₂ O, 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; and is

a. b, c and d are in each case identically or differently 0 or 1;

wherein:

when a or b is 0, then the corresponding Ar ^S Is absent and group Ar ¹ Is directly bonded to the group X,

when c or d is 0, then the corresponding Ar ^S Is absent and group Ar ³ Directly bonded to the group Z;

p, q, r and s, equal or different, represent 1,2 or 3.

2. Composition according to claim 1, characterized in that the compound of formula (H2) is selected from compounds of formula (H2-1),

wherein:

y is CR ^Y Or N; or if the Y bondTo Ar ² 、Ar ^S Or a group Z, then Y is C; wherein R is ^Y And other symbols and signs also have the same meaning as in claim 1.

3. Composition according to claim 1 or 2, characterized in that the compound of formula (H2) is selected from the compounds of formulae (H2-2-1), (H2-2-2) and (H2-2-3),

wherein Ar is ^S 、Ar ² Z and the indices c and d have the same meaning as in claim 1 and Y has the same meaning as in claim 2.

4. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H2) is chosen from compounds of formulae (H2-3-1) to (H2-3-20),

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wherein the symbols and indices have the same meaning as in claim 1.

5. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H1) is chosen from compounds of formula (H1-1),

of which X, ar ^S 、Ar ⁴ And the indices a and b have the same meaning as in claim 1; and is

V is CR ^V Or N; or if V is bonded to Ar ⁴ 、Ar ^S Or a group X, then V is C; wherein R is ^V Have the same meaning as in claim 1.

6. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H1) is chosen from compounds of formula (H1-2),

wherein X and Ar ⁴ Has the same meaning as in claim 1; and is

V has the same meaning as in claim 5.

7. The composition according to one or more of the preceding claims, the compound of formula (H1) being selected from compounds of formula (H1-3),

wherein the symbols have the same meaning as in claims 1 and 5.

8. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H1) is chosen from compounds of formula (H1-4),

wherein the symbols have the same meaning as in claim 1.

9. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H1) is chosen from compounds of formula (H1-5),

wherein the symbols have the same meaning as in claim 1.

10. Composition according to one or more of the preceding claims, characterized in that the group Ar ² 、Ar ⁴ In each case identically or differently selected from phenyl, biphenyl, terphenyl, tetrabiphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, terphenyl, fluoranthene, tetracene, chicory, benzanthracene, triphenylene, pyrene or perylene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted in any free position by one or more radicals R; and wherein Ar ² 、Ar ⁴ Combinations of two or more of the foregoing groups are also possible.

11. Composition according to one or more of the preceding claims, characterized in that it further comprises a fluorescent emitter.

12. Composition according to one or more of the preceding claims, characterized in that it comprises a fluorescent emitter chosen from:

-a bridged triarylamine;

-indenofluorene, indenofluorenamine or indenofluorenediamine;

-a benzindenofluorene, benzindenofluorene amine or benzindenofluorene diamine;

-bisindeno indenofluorenes;

-indenodibenzofuran; indenofluoreneamine or indenofluorenediamine;

-a fluorene dimer;

-thiophen

An oxazine; and

-a boron derivative.

13. Composition according to one or more of the preceding claims, characterized in that it comprises a fluorescent emitter of formula (E-1), (E-2), (E-3) or (E-4),

wherein

Ar ¹⁰ 、Ar ¹¹ 、Ar ¹² Identically or differently on each occurrence is an aromatic or heteroaromatic ring system having from 6 to 60 aromatic ring atoms, which may also be substituted on each occurrence by one or more radicals R; with the proviso that at least one group Ar ¹⁰ 、Ar ¹¹ 、Ar ¹² Is aromatic or hetero having 10 to 40 aromatic ring atomsAn aromatic ring system containing at least one fused aryl or heteroaryl group consisting of 2 to 4 aromatic rings fused to each other, wherein the aromatic or heteroaromatic ring system may be substituted by one or more groups R;

r has the same definition as in claim 1; and is

e is 1,2,3 or 4; more preferably, e is 1;

wherein

E ²⁰ in each case, identically or differently, is selected from BR, C (R) ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、C＝O、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、O、S、S＝O、SO ₂ 、NR ⁰ 、PR ⁰ 、P(＝O)R ⁰ Or P (= S) R ⁰ A group of (a); wherein Ar is ²⁰ 、Ar ²¹ And E ²⁰ Together form a five-or six-membered ring, and Ar ²¹ 、Ar ²³ And E ²⁰ Together form a five-membered or six-membered ring;

R ⁰ represent in each case identically or differently H, D, F, a straight-chain alkyl radical having from 1 to 20, preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 20, preferably from 3 to 10, C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH' s ₂ The radicals may be replaced by O or S and in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms which may in each case be substitutedSubstituted by one or more radicals R, two adjacent radicals R ⁰ May together form an aliphatic or aromatic ring system which may be substituted by one or more radicals R,

r has the same definition as in claim 1;

p, q are in each case, identically or differently, 0 or 1, with the proviso that p + q =1;

r is 1,2 or 3;

wherein

E ³⁰ represents B or N;

E ³¹ 、E ³² 、E ³³ in each case identically or differently represents O, S, C (R) ⁰ ) ₂ 、C＝O、C＝S、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、BR ⁰ 、NR ⁰ 、PR ⁰ 、SO ₂ 、SeO ₂ Or a chemical bond, provided that if E ³⁰ Is B, then the radical E ³¹ 、E ³² 、E ³³ At least one of them represents NR ⁰ And if E ³⁰ Is N, then the radical E ³¹ 、E ³² 、E ³³ At least one of them represents BR ⁰ ；

R ⁰ Have the same definitions as above;

wherein

E ⁴¹ 、E ⁴² 、E ⁴³ in each case identically or differently represents O, S, C (R) ⁰ ) ₂ 、C＝O、C＝S、C＝NR ⁰ 、C＝C(R ⁰ ) ₂ 、Si(R ⁰ ) ₂ 、BR ⁰ 、NR ⁰ 、PR ⁰ 、SO ₂ 、SeO ₂ Or a chemical bond, provided that the group E ⁴¹ 、E ⁴² 、E ⁴³ At least one of which is present and represents a chemical bond;

R ⁰ have the same definitions as above;

14. Composition according to one or more of the preceding claims, characterized in that the compound of formula (H1) is present in the composition in a proportion ranging from 1% to 60% and the compound of formula (H2) is present in the composition in a proportion ranging from 30% to 99%.

15. A formulation comprising at least one composition according to one or more of claims 1 to 14 and at least one solvent.

16. A process for manufacturing an electronic device comprising at least one layer comprising a composition according to one or more of claims 1 to 14:

a) Preparing a formulation comprising at least one composition according to one or more of claims 1 to 14 and at least one solvent;

b) Applying the formulation prepared in step a) on a substrate or another layer to form a layer;

c) Drying the layer to remove the solvent.

17. The method according to claim 16, characterized in that the formulation is applied by a coating method or a printing method.

18. The method according to claim 16 or 17, characterized in that the formulation is applied by flow coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, roll coating, ink jet printing, rotary printing, flexographic printing, offset printing, slot die coating or nozzle printing.

19. An electronic device comprising an anode, a cathode and at least one light emitting layer, wherein the light emitting layer comprises a composition according to one or more of claims 1 to 14.

20. The electronic device according to claim 19, 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.