KR20230043106A - Materials for organic electroluminescent devices - Google Patents

Abstract

The present invention relates to compounds of formula (1) suitable for use in electronic devices, in particular organic electroluminescent devices, and electronic devices comprising these compounds.

Description

Materials for organic electroluminescent devices

The present invention relates to compounds of formula (1), uses of compounds in electronic devices, and electronic devices comprising compounds of formula (1). The present invention also relates to compositions and formulations comprising one or more compounds of formula (1).

Currently, the development of functional compounds for use in electronic devices is a subject of intensive research. The aim is, in particular, the development of compounds by which improved properties of electronic devices can be achieved in one or more relevant respects, such as, for example, the power efficiency and lifetime of the device and the color coordinates of the emitted light.

According to the present invention, the term electronic device refers in particular to an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), an organic optical detector, organic photoreceptors, organic field-quench devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O lasers) and organic electroluminescent devices (OLEDs).

It is of particular interest to provide compounds for use in the last mentioned electronic device, referred to as an OLED. The general structure and functional principles of OLEDs are known to the person skilled in the art and are described, for example, in US Pat. No. 4,539,507.

In particular, further improvements in the performance data of OLEDs are still desired in terms of their vast commercial applications, for example in display devices or as light sources. In this respect, the lifetime, efficiency and operating voltage of the OLED achieved and the color values are of particular importance. In particular, in the case of blue emitting OLEDs, there is potential for improvement regarding the efficiency, lifetime and operating voltage of the device.

An important starting point for achieving these improvements is the selection of host materials (also called matrix materials) for emitters as well as emitter compounds used in electronic devices.

Host materials for fluorescent emitters known from the prior art are a number of compounds. Compounds comprising at least one anthracene group and at least one dibenzofuran or dibenzothiophene group are known from the prior art (eg from KR 20170096860 and CN 109867646).

However, there is still a need for additional fluorescent emitters and additional host materials for fluorescent emitters, which may be employed in OLEDs and lead to OLEDs with very good properties in terms of lifetime, color emission 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.

It is also known that OLEDs may include different layers, which may be applied by deposition in a vacuum chamber or by treatment from solution. Evaporation-based processes lead to very good results, but such processes can be complex and expensive. Therefore, there is also a need for OLED materials that can be easily and reliably processed from solution. In this case, the material must have good solubility properties in the solution containing the material.

In addition, there is still a need for processes leading to stable OLED materials that are easy to refine and process. An economical and qualitatively interesting process is needed by providing OLED materials in acceptable purity and high yield.

Accordingly, the present invention is based on the technical object of providing a compound suitable for vacuum treatment or solution treatment, which is suitable as a host material for or as a fluorescent emitter in an electronic device, such as an OLED, more specifically for a fluorescent emitter. The present invention is also based on the technical object of providing methods and intermediate compounds for the production of OLED materials.

In the search for new compounds for use in electronic devices, it has now been found that compounds of formula (1) defined below are exceptionally suitable for use in electronic devices. In particular, they achieve one or more, preferably all, of the aforementioned technical objectives.

Accordingly, the present invention relates to compounds of formula (1)

The following applies to the symbols and indices used in expressions:

E represents O or S, preferably O;

X at each occurrence, identically or differently, represents CR ^X or N;

Y at each occurrence, identically or differently, represents CR ^Y or N; or Y is Ar ^S , Ar ¹ or C when bonded to Ar ² or heterocycle represented in formula (1) when Ar ^S is absent;

Ar ¹ , Ar ² on each occurrence, identically or differently, represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which on each occurrence may be substituted by one or more radicals R;

Ar ^S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may on each occurrence be substituted by one or more radicals R;

R ^X , R ^Y are at each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, C(=0)Ar, P(=0)(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, 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups are RC=CR, C≡C, Si(R) ₂ , Ge(R) ₂ , Sn(R) ₂ , C=O, C=S, C=Se, P(=O)(R), may be replaced by SO, SO ₂ , O, S or CONR, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), in each case by one or more radicals R represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;

wherein the two radicals R ^X may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; Two radicals R ^Y may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R;

R is at each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, C(=0)Ar, P(=0)(Ar) ₂ , S(=0)Ar , S(=O) ₂ Ar, N(R´) ₂ , N(Ar) ₂ , NO ₂ , Si(R ^´ ) ₃ , B(OR´) ₂ , OSO ₂ ^R´ , 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R', wherein in each case one or more Nonadjacent CH ₂ groups are 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 one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R ^′ , or 5 to 60 ring systems, which may be substituted by one or more radicals R ^′ represents an aryloxy group having two aromatic ring atoms; wherein the two radicals R may together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R ^' ;

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

R ^´ is at each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms a branched or cyclic alkyl, alkoxy or thioalkyl group having, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by SO, SO ₂ , O, S and one or more H atoms are D, F, Cl, Br or I), or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.

n and m represent integers selected from 0, 1 and 2; provided that n = m;

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

Adjacent radicals in the meaning of the present invention are radicals bonded to atoms directly linked to each other or bonded to the same atom.

Moreover, the definitions of the chemical groups below apply for the purposes of this application:

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. . Heteroatoms are preferably selected from N, O and S. This represents the default definition. Where other preferences are indicated in the description of the invention, they apply, for example with respect to the number of aromatic ring atoms or heteroatoms present.

wherein the aryl group or heteroaryl group is a simple aromatic ring, ie benzene, or a simple heteroaromatic ring, eg pyridine, pyrimidine or thiophene, or a condensed (annealed) aromatic or heteroaromatic polycyclic ring, eg naphthalene, phenanthrene, quinoline or carbazole. Condensed (annealed) aromatic or heteroaromatic polycycles in the meaning of the present application consist of two or more simple aromatic or heteroaromatic rings condensed with one another.

Aryl or heteroaryl groups, which may also in each case be substituted by the above-mentioned radicals and linked to the aromatic or heteroaromatic ring system through any desired positions, are, in particular, benzene, naphthalene, anthracene, phenanthrene, pyrene, Dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, iso Benzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, Benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole , pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxa Sol, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole , benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4oxa Diazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiazole Diazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5 - groups derived from tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole Let's go

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

An aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 20 carbon 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. . Heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the context of the present invention does not necessarily contain aryl or heteroaryl groups, but instead, in addition, a plurality of aryl or heteroaryl groups are formed from non-aromatic units (preferably less than 10% other than H). atoms of), such as, for example, sp ³ -hybridized C, Si, N or O atoms, sp ² -hybridized C or N atoms or sp-hybridized C atoms. is intended to Thus, systems such as, for example, 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc., also have two or more aryl groups, for example linear or systems linked by cyclic alkyl, alkenyl or alkynyl groups, or by silyl groups, in the context of the present invention are intended to be considered aromatic ring systems. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to each other via a single bond are also within the meaning of the present invention aromatic or heteroaromatic ring systems, such as systems such as, for example, biphenyls, terphenyls or diphenyltriazines. It is considered to be

Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms which may also in each case be substituted by the radicals defined above and which may be linked to the aromatic or heteroaromatic group via any desired positions, in particular benzene, naphthalene , anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, Fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, thruxen, isotruxen, spirotruxen, spiroisotruxen, furan, benzofuran , isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole , benzimidazole, naphthymidazole, phenanthrimidazole, pyridimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthoxazole, phenanthroxa sol, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2 ,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazafe Rylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluororubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, Benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3- Thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-tri Azine, 1,2,3-triazine, tetrazole, 1,2,4,5 - groups derived from tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or a combination of these groups are taken to mean

For the purposes of this invention, a straight chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms (where also the individual H atoms or CH ₂ groups may be substituted by the groups mentioned above under the definition of radicals) are preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl , s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclo Octyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl , heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. Alkoxy or thioalkyl groups having 1 to 40 carbon atoms are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-part Toxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, Cycloctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctyl Thio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclophene tenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, It is taken to mean heptinylthio or octinylthio.

A formulation in which two or more radicals are capable of forming a ring with one another is understood for the purposes of the present application to mean, inter alia, that two radicals are linked to one another by means of a chemical bond. This is illustrated by the diagram below:

But moreover, the formulation described above is also intended to mean that, in case one of the two radicals represents hydrogen, a second radical is bonded to the position where the hydrogen atom was bonded to form a ring. This is illustrated by the diagram below:

When two radicals form a ring with each other, it is preferred that the two radicals are adjacent radicals. As mentioned above, adjacent radicals in the sense of the present invention are radicals bonded to atoms directly linked to each other or bonded to the same atom.

According to a preferred embodiment, the compound of formula (1) is selected from compounds of formulas (2), (3), (4) or (5),

In the expression, the symbol and index have the same meaning as above.

According to a more preferred embodiment, the compound of formula (1) is selected from compounds of formulas (2-1), (3-1), (4-1) or (5-1),

In the expression, the symbol and index have the same meaning as above.

According to an even more preferred embodiment, the compound of formula (1) is selected from compounds of formulas (2-1-1) to (2-1-5):

In the expression, the symbol and index have the same meaning as above.

According to a preferred embodiment, n = m = 0.

According to another preferred embodiment, n = m = 1.

According to a preferred embodiment, Ar ¹ and Ar ² are, on each occurrence, identically or differently, 5 to 40, more preferably 5 to 30, very preferred, which may on each occurrence be substituted by one or more radicals R represents an aromatic or heteroaromatic ring system having preferably 5 to 25, particularly preferably 6 to 18 aromatic ring atoms. According to a very preferred embodiment, Ar ¹ and Ar ² are in each case identical or different , phenyl, biphenyl, terphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, benzophenanthrene, benzanthracene, pyrene, perylene, triphenylene, benzopyrene, fluoran tene, dibenzofuran, dibenzothiophene, carbazole or a combination of two or three of these groups, each of which may be substituted with one or more radicals R. According to a particularly preferred embodiment, Ar ¹ and Ar ² are at each occurrence, identically or differently, phenyl, biphenyl, terphenyl, fluorene, spirobifluorene, dibenzofuran, dibenzothiophene, carbazole or represents a combination of two or three of these groups, each of which may be substituted with one or more radicals R.

Examples of suitable groups Ar ¹ and Ar ² are groups of formulas (Ar-1) to (Ar-9),

during the ceremony

- E ¹ in each case, identically or differently, represents C(R ⁰ ) ₂ , NR ^N , O or S,

- R ⁰ , R ^N are in each case, identically or differently, H, D, F, Cl, Br, I, CN, Si(R) ₃ , 1 to 40, preferably 1 to 20, more Preferably a straight chain alkyl, alkoxy or thioalkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms. , an alkoxy or thioalkyl group, each of which may be substituted with one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups are 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 one or more H atoms are D , F, Cl, Br, I, CN or NO ₂ ), 5 to 60, preferably 5 to 40, more preferably 5 to 40, which may in each case be substituted by one or more radicals R Aromatic or heteroaromatic ring systems having 30, particularly preferably 5 to 24, very particularly preferably 5 to 18 aromatic ring atoms, or 5 to 60, preferably 5 to 60, which may be substituted by one or more radicals R represents an aryloxy group having from 5 to 40, more preferably from 5 to 30, particularly preferably from 5 to 24 and very particularly preferably from 5 to 18 aromatic ring atoms, wherein two radicals R ⁰ are at least one radical R may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by;

- dotted lines indicate binding to adjacent anthracene moieties;

- The groups of formulas (Ar-1) to (Ar-9) may be substituted at each free position by a group R, wherein R has the same meaning as above.

Groups of the formulas (Ar-1) to (Ar-3) are particularly preferred.

Very suitable examples of groups Ar ¹ and Ar ² are groups of formulas (Ar1-1) to (Ar1-27):

during the ceremony

- E ¹ , R ⁰ , R ^N have the same meaning as above.

- dotted lines indicate binding to adjacent anthracene moieties;

- The groups of formulas (Ar-1) to (Ar-27) may be substituted at each free position by a group R, wherein R has the same meaning as above.

Preferably, the group Ar ^S is, identically or differently, in each case aromatic or heteroaromatic having 5 to 25, preferably 6 to 18, aromatic ring atoms which may in each case be substituted by one or more radicals R represents a ring system.

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

Examples of suitable groups Ar ^S are groups of formulas (ArS-1) to (ArS-27) as shown in the table below:

The dotted line bonds in formula (1) represent bonds to adjacent groups;

The groups of formulas (ArS-1) to (ArS-27) herein may be substituted at each free position by a group R, which has the same meaning as defined above.

Group E ³ in each case, identically or differently, is -BR ⁰ -, -C(R ⁰ ) ₂ -, -Si(R ⁰ ) ₂ -, -C(=0)-, -O-, -S-, -S(=0)-, -SO ₂ -, -N(R ⁰ )-, and -P(R ⁰ )-, where R ⁰ is as defined above. Preferably, E ³ is, identically or differently, selected from -C(R ⁰ ) ₂ -, -O-, -S- and -N(R ⁰ )-, where R ⁰ is as defined above.

Among the groups of formulas (ArS-1) to (ArS-27), formulas (ArS-1), (ArS-2), (ArS-3), (ArS-11), (ArS-12) and (ArS- 27) is preferred. Groups of the formulas (ArS-1), (ArS-2) and (ArS-3) are highly preferred. A group of the formula (ArS-1) is particularly preferred.

Preferably, R ^X , R ^Y are each, identically or differently, H, D, F, CN, N(Ar) ₂ , 1 to 40, preferably 1 to 20, more preferably 1 to 10 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms. Alkyl groups, each of which may be substituted by one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by RC=CR, C≡C, O or S and one or more H atoms are D or F), or 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 6 to 18, which may in each case be substituted by one or more radicals R represents an aromatic or heteroaromatic ring system having two aromatic ring atoms; wherein two adjacent radicals R ^X may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; wherein two adjacent radicals R ^Y may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R. More preferably, R ^X , R ^Y are at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms. groups, each of which may be substituted by one or more radicals R, wherein in each case one or more H atoms may be replaced by D or F, or in each case 5 to 5, which may be substituted by one or more radicals R represents an aromatic or heteroaromatic ring system having 30, particularly preferably 6 to 18 aromatic ring atoms, wherein two adjacent radicals R ^X may be substituted by one or more radicals R may form together; wherein two adjacent radicals R ^Y may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R.

Preferably, R is at each occurrence, identically or differently, H, D, F, CN, N(Ar) ₂ , 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. A straight-chain alkyl, alkoxy or thioalkyl group having 3 to 40 atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms (these Each may be substituted by one or more radicals R', wherein in each case one or more non-adjacent CH ₂ groups may be replaced by R'C=CR', C≡C, O or S and one or more H atoms are D or F), in each case from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, particularly preferably from 6 to 18, which may in each case be substituted by one or more radicals R' represents an aromatic or heteroaromatic ring system having two aromatic ring atoms.

Preferably, Ar is on each occurrence, identically or differently, from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18 aromatics, which may on each occurrence be substituted by one or more radicals R'. represents an aromatic or heteroaromatic ring system having ring atoms.

Preferably, R ^´ is at each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a moiety having 3 to 10 carbon atoms organic or cyclic alkyl groups, wherein in each case one or more H atoms may be replaced by D or F, or aromatic or heteroaromatic ring systems having from 5 to 18 carbon atoms.

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

Compounds according to the present invention may be prepared by synthetic steps known to those skilled in the art, such as, for example, bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling and the like. can Examples of suitable synthetic processes are shown in general terms in Schemes 1 and 6 below.

Schematic 1

In Scheme 1 here:

X ¹ and X ² are the same or different leaving groups, and are preferably selected from the group consisting of halogen atoms, triflates and boronic acid derivatives.

Anth corresponds to an anthracene group;

Ar ¹ and Ar ² have the same definition as above.

Schematic 2

In Scheme 2 here:

X ¹ and X ² are different leaving groups, and are preferably selected from the group consisting of halogen atoms, triflates and boronic acid derivatives. More preferably, X ¹ is triflate and X ² is halogen;

Anth corresponds to an anthracene group;

Ar ¹ and Ar ² have the same definition as above.

The structures shown in Schemes 1 and 2 may be further substituted at any free position.

A further subject matter of the present application is therefore a process for the preparation of a compound according to formula (1), characterized in that it comprises a coupling reaction, preferably a Suzuki coupling reaction, of an anthracene derivative with a dibenzofuran having two reactive groups.

In order to process the compounds according to the invention from the liquid phase, for example by spin coating or by means of a printing process, a formulation of the compounds according to the invention is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be desirable to use a mixture of two or more solvents. The solvent is preferably selected from organic and inorganic solvents, more preferably organic solvents. The solvent is very preferably selected from hydrocarbons, alcohols, esters, ethers, ketones and amines. Suitable and preferred solvents are for example toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, di Oxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-Penchon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphtharene, 1 -Ethylnaphthalene, decylbenzene, phenyl naphthalene, menthyl isovalerate, para tolyl isobutyrate, cyclohexal hexanoate, ethyl para toluate, ethyl ortho toluate, ethyl meta toluate, decahydronaphthalene, ethyl 2-methoxy Benzoate, dibutylaniline, dicyclohexyl ketone, 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-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene , ethyl benzoate, indan, NMP, p-cymene, phenethol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3 ,4-dimethylphenyl)ethane or a mixture of these solvents.

Accordingly, the invention also relates to formulations comprising a compound according to the invention and at least one further compound. The further compound may be, for example, a solvent, in particular one of the solvents mentioned above, or a mixture of such solvents. However, the further compound may also be at least one further organic or inorganic compound which is likewise used in electronic devices, for example a phosphorescent dopant, a fluorescent dopant, a TADF dopant and/or a host material. Suitable compounds are shown below in relation to organic electroluminescent devices. These additional compounds may also be polymeric. Preferably, the formulation comprises a compound of formula (1) and at least one solvent. More preferably, the formulation comprises a compound of formula (1), an emitting material selected from fluorescent emitters, TADF emitters and phosphorescent emitters and at least one solvent. Even more preferably, the formulation comprises a compound of formula (1), an emitting material selected from fluorescent emitters, TADF emitters and phosphorescent emitters, an additional host material and at least one solvent.

The compounds and mixtures according to the present invention are suitable for use in electronic devices. An electronic device is taken here to mean a device comprising at least one layer comprising at least one organic compound. However, the component here can also comprise an inorganic material or a layer built entirely from also an inorganic material.

Accordingly, the invention also relates to the use of a compound or mixture according to the invention in an electronic device, in particular an organic electroluminescent device.

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

The electronic device is preferably an organic electroluminescent device (OLED, PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic Solar cells (OSCs), organic dye-sensitized solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and "organic Plasmon emitting devices" (DM Koller et al. , Nature Photonics 2008 , 14), preferably organic electroluminescent devices (OLED, PLED), in particular phosphorescent OLEDs.

An organic electroluminescent device includes a cathode, an anode and at least one emissive layer. In addition to these layers, it may also comprise further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and/or charge generating layers in each case. can include It is likewise possible for an intermediate layer, for example with an exciton blocking function, to be introduced between the two emitting layers. However, it should be noted that each of these layers need not necessarily be present. The organic electroluminescent device here may comprise one emissive layer or a plurality of emissive layers. If a plurality of emission layers are present, they preferably have a plurality of emission maxima between 380 nm and 750 nm as a whole, which collectively result in white emission, i.e. various emission compounds capable of fluorescence or phosphorescence are used in the emission layer. . Systems with three emitting layers are particularly preferred, where the three layers exhibit blue, green and orange or red emission (for basic structure, see eg WO 2005/011013). These may be fluorescent or phosphorescent emitting layers or hybrid systems in which fluorescent and phosphorescent emitting layers are combined with each other.

The compounds according to the present invention according to the embodiments shown above can be used in various layers depending on their exact structure and depending on the substitution. An organic electroluminescent device comprising the compound of formula (1) or a preferred embodiment as a fluorescent emitter, an emitter exhibiting TADF (Thermally Activated Delayed Fluorescence), or as a host material for a dopant selected from an emitting material is preferred.

Particularly preferred are organic electroluminescent devices comprising the compound of formula (1) or a preferred embodiment as a host material for fluorescent emitters, more particularly for blue-emitting fluorescent emitters. The compound of formula (1) can also be used in the electron transport layer and/or the electron blocking or exciton blocking layer and/or the hole transport layer depending on the precise substitution. The preferred embodiments indicated above also apply to the use of the material in organic electronic devices.

The compounds according to the present invention are particularly suitable for use as host materials for fluorescence-emitting compounds. The terms host material and matrix material may be used synonymously.

A host material is taken here to mean a material, preferably as a main component, which is present in the emissive layer and which does not emit light during operation of the device.

The proportion of the emitting compound in the mixture of the emitting layer is 0.1 to 50.0%, preferably 0.5 to 20.0%, particularly preferably 1.0 to 10.0%. Correspondingly, the proportion of the host material or host materials is 50.0 to 99.9%, preferably 80.0 to 99.5%, particularly preferably 90.0 to 99.0%.

Specifications of percentages are, for the purposes of this application, taken to mean percent by volume when the compound is applied from a gas phase, and percent by weight when the compound is applied from a solution.

When the compound according to the present invention is used as a host material for a fluorescence-emitting compound in an emission layer, it may be used in combination with one or more fluorescence-emitting compounds.

Preferred fluorescent emitters are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrendiamine, aromatic chrysenamine or aromatic chrysendiamine. Aromatic anthraceneamines are taken to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably at the 9-position. Aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups bond directly to an anthracene group, preferably at the 9,10-position. Aromatic pyreneamines, pyrendiamines, chryseneamines and chryssendiamines are similarly defined, wherein the diarylamino group is bonded to the pyrene, preferably at the 1- or 1,6-position. Further preferred emitters are indenofluorenamines or indenofluorenediamines (e.g. according to WO 2006/108497 or WO 2006/122630), benzoindenofluorenamines or benzoindenofluorenediamines (e.g. eg according to WO 2008/006449), and dibenzoindenofluorenamine or dibenzoindenofluorenediamine (eg according to WO 2007/140847), and condensed aryl groups disclosed in WO 2010/012328 It is an indenofluorene derivative containing Still further preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers linked via a heteroaryl group as in WO 2016/150544 or WO 2017/028940 and phenoxazine derivatives as disclosed in WO 2017/028941. The pyrenearylamines disclosed in WO 2012/048780 and WO 2013/185871 are likewise preferred. Likewise preferred are the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorenamines disclosed in WO 2014/106522 and the indenofluorenes disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421. dibenzofuran or indenodyne as also 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/EP2019/072662 Emitters comprising a benzofuran moiety are preferred. Likewise, preference is given to boron derivatives as disclosed for example in WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 and unpublished applications EP 19168728.4, EP 19199326.0 and EP 19208643.7.

Examples of fluorescent emitting compounds suitable for use in combination for compounds of formula (1) are depicted in the table below:

A related electronic device may comprise a single emissive layer comprising a compound according to the invention or may comprise two or more emissive layers. The further release layer here may comprise one or more compounds according to the invention or alternatively other compounds.

When the compound according to the present invention is used as a host material for a fluorescence emitting compound in an emission layer, it may be used in combination with one or more additional host materials.

Preferred host materials for use in combination with the compounds of formula (1) or preferred embodiments thereof are oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes (eg DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (eg WO 2004/081017), hole conducting compounds (eg according to WO 2004/058911), electron conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (eg WO 2005/084081 and WO 2005/ 084082), atropisomers (eg according to WO 2006/048268), boronic acid derivatives (eg according to WO 2006/117052), benzanthracenes (eg according to WO 2008/145239) ) or phenanthrenes (eg according to WO2009/100925). Particularly preferred host materials are selected from the classes of oligoarylenes, including naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred host materials are selected from the class of oligoarylenes comprising anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. An oligoarylene in the meaning of the present invention is taken to mean a compound in which at least three aryl or arylene groups are bonded to one another.

Particularly preferred host materials for use in combination with compounds of formula (1) in the emissive layer are shown in the table below:

On the other hand, the compound according to the present invention can also be used as a fluorescence-emitting compound. In this case, a suitable host material for the compound of formula (1) used as the fluorescence-emitting compound corresponds to the additional compound of formula (1) or the preferred host materials described above.

The compounds according to the invention can also be used as hole transport materials in other layers, for example hole injection or hole transport layers or electron blocking layers, or as host materials in emissive layers, preferably as host materials for phosphorescent emitters. .

When the compound of formula (1) is used as a hole transport material in a hole transport layer, hole injection layer or electron blocking layer, the compound can be used as a pure material, i.e. in a proportion of 100%, in the hole transport layer, or one or more additional It may be used in combination with a compound. According to a preferred embodiment, the organic layer containing the compound of formula (I) then additionally comprises at least one p-dopant. The p-dopants used according to the present invention are preferably organic electron acceptor compounds capable of oxidizing one or more of the other compounds of the mixture.

Particularly preferred embodiments of p-dopants are disclosed in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/0034070, WO 2045848 /120709, US 2010/0096600 and WO 2012/095143.

The compound of formula (1) is preferably used as a host material in combination with a fluorescent material. However, the compound of formula (1) may also be used as a host material in combination with a phosphorescent emitter in an emissive layer. In this case, the phosphorescent emitter is preferably selected from the classes and embodiments of phosphorescent emitters indicated below. Also in this case at least one additional host material is preferably present in the release layer. A so-called mixed matrix system or mixed host system of this type preferably comprises two or three different host materials, particularly preferably two different host materials. Here, it is preferable that one of the two materials is a material having hole transport properties and the other material is a material having electron transport properties. The compound of formula (1) is preferably a material having hole transport properties. However, the desired electron transport and hole transport properties of the mixed host component may also be primarily or completely combined in a single mixed host component in which additional mixed host components or components fulfill different functions. The two different host materials here are 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, and very particularly preferably 1:4 to 1: may exist in a ratio of 1. Further details on mixed host systems are contained, inter alia, in the application WO 2010/ 108579.

Particularly suitable host materials that can be used as host components of mixed host systems in combination with the compounds according to the present invention are the preferred host materials for phosphorescent emitters shown below, depending on which type of emitter compound is used in the mixed host system, or selected from preferred host materials for fluorescent emitters.

Suitable phosphorescent emitters are in particular at least one which emits light upon suitable excitation, preferably in the visible region, and has an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. A compound containing one atom. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper .

For the purposes of this invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds.

Examples of the aforementioned phosphorescent emitters are disclosed in applications WO 2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 2005/ 033244, WO 2005/019373 and US 2005 It is revealed by /0258742. In general, all phosphorescent complexes used according to the prior art for phosphorescent OLEDs and known to the person skilled in the art of organic electroluminescent devices are suitable for use in the device according to the invention. A person skilled in the art will also be able to employ further phosphorescent complexes without inventiveness in combination with the compounds according to the invention in OLEDs.

Preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triaryls, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680 amines, carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives (WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, or WO 2008/ 086851), for example indolocarbazole derivatives according to WO 2007/063754 or WO 2008/056746, for example indenocarbazole according to WO 2010/136109, WO 2011/000455, or WO 2013/041176 Derivatives, for example azacarbazole derivatives according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, dipolar matrix materials, for example according to WO 2007/137725, silanes according to WO 2005/111172, azabolol or boronic esters, for example according to WO 2006/117052, for example triazine derivatives according to WO 2010/015306, WO 2007/063754 or WO 2008/056746, for example EP 652273 or WO 2009 Zinc complexes according to /062578, eg diazasilol or tetraazacylol derivatives according to WO 2010/054729, eg diazaphosphole derivatives according to WO 2010/054730, eg US 2009/0136779, WO 2010/ 050778, WO 2011/042107, WO 2011/088877 or WO2012/143080 bridged carbazole derivatives, for example triphenylene derivatives according to WO 2012/048781, or for example WO 2011/116865 or WO It is a lactam according to 2011/137951.

In addition to the compounds according to the present invention, suitable charge transport materials as may be used in the electron transport layer or in the hole injection or hole transport layer or electron blocking layer of the electronic device according to the present invention are, for example, Y. Shirota et al. Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

Materials that can be used for the electron transport layer are all materials used according to the prior art as electron transport materials in the electron transport layer. In particular, 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, diazaphosphole derivatives and phosphine oxide derivatives are suitable. Also 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 in the hole transport, hole injection or electron blocking layer in the electroluminescent device according to the present invention are indenofluorenamine derivatives (eg according to WO 06/122630 or WO 06/100896) , amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (eg according to WO 01/049806), amine derivatives containing fused aromatic rings (eg according to US 5,061,569), WO 95 /09147, monobenzoindenofluorenamine (eg according to WO 08/006449), dibenzoindenofluorenamine (eg according to WO 07/140847), spiro bifluorenamine (eg according to WO 2012/034627 or WO 2013/120577), fluorenamine (eg according to applications EP 2875092, EP 2875699 and EP 2875004), spirodibenzopyranamine (eg according to applications EP 2875092, EP 2875699 and EP 2875004) eg according to WO 2013/083216) and dihydroacridine derivatives (eg according to WO 2012/150001). The compounds according to the invention can also be used as hole transport materials.

The cathode of the organic electroluminescent device is preferably a metal having a low work function, such as an alkaline earth metal, an alkali metal, a main group metal, or a lanthanoid (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) or metal alloys containing various metals or multilayer structures. Also suitable are alloys comprising an alkali or alkaline earth metal and silver, for example an alloy comprising magnesium and silver. In the case of multi-layer structures, further metals with a relatively high work function, such as for example Ag or Al, can also be used in addition to the above metals, in which case for example Ca/Ag, Mg/Ag or Ag/ Combinations of metals such as Ag are commonly used. It may also be desirable to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. For this purpose, for example, alkali metal fluorides or alkaline earth metal fluorides, as well as corresponding oxides or carbonates (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ , etc.) also suitable Lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

The anode preferably includes a material with a high work function. The anode preferably has a work function greater than 4.5 eV versus vacuum. On the other hand, for this purpose, metals having a high redox potential, such as Ag, Pt or Au, for example, are suitable. On the other hand, metal/metal oxide electrodes (eg Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. For some applications, in order to facilitate irradiation of organic materials (organic solar cells) or coupling-out of light (OLED, O-lasers), at least one of the electrodes must be transparent or partially transparent. do. Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductively doped organic materials, in particular conductive doped polymers, are also preferred.

The device is structured appropriately (according to the application), contacts are provided 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 present invention is produced by a sublimation process in which the material is applied by vapor deposition in a vacuum sublimation unit at an initial pressure of less than 10 ⁻⁵ mbar, preferably less than 10 ⁻⁶ mbar. Characterized in that one or more layers are coated. However, it is also possible here that the initial pressure is much lower, for example less than 10 ⁻⁷ mbar.

Equally preferred are organic electroluminescent devices, characterized in that at least one layer is coated by means of an OVPD (organic vapor deposition) process or with the aid of carrier gas sublimation, wherein the material is applied at a pressure of between 10 ⁻⁵ mbar and 1 bar. . A special case of this process is the OVJP (organic vapor jet printing) process, where materials are applied directly through a nozzle and thus structured (e.g. MS Arnold et al. , Appl. Phys. Lett. 2008 , 92 , 053301). .

One or more layers may be applied, for example by spin coating, or by, for example, screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, Also preferred are organic electroluminescent devices characterized in that they are produced from a solution, such as by any desired printing method, such as thermal transfer printing) or inkjet printing. A soluble compound of formula (I) is needed for this purpose. High solubility can be achieved through suitable substitution of compounds.

Hybrid processes are also possible, for example in which one or more layers are applied from solution and one or more additional layers are applied by vapor deposition. Thus, for example, it is possible to apply the release layer from solution and to apply the electron transport layer by vapor deposition.

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

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

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

A) Synthesis example

Synthesis of Compound A1:

15 g (38 mmol) trifluoro-methanesulfonic acid 8-bromo-dibenzofuran-1-yl ester, 43.3 g (114 mmol) 4,4,5,5-tetramethyl-2-(10-phenyl-anthracene-9 -day)-[1,3,2]dioxaborolane, 35.5 g (167 mmol) potassium phosphate and 1.6 g (1,9 mmol) XPhos Palladacycle Gen. 3 is dissolved in 450 ml THF/water (2:1). The mixture is stirred at 90° C. for 16 hours. After cooling to room temperature, 300 ml of ethanol is added and the mixture is stirred for 1 hour. The precipitate is filtered off and washed with ethanol. The raw material was dissolved in toluene and filtered through a filter plug (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). The remaining solvent is removed by sublimation (10 ⁻⁵ bar at 300° C.).

Yield: 15.2 g (22.6 mmol; 60%)

The following compounds can be synthesized in a similar manner:

Synthesis of Compound B1:

Step 1 - Synthesis of Intermediates

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

Yield: 6.3 g (11 mmol; 43%)

The following compounds can be synthesized in a similar manner:

Step 2 - Synthesis of Product

10 g (17.4 mmol) compound I1, 8.3 g (18.5 mmol) 952604-31-8, 8.1 g (38.3 mmol) potassium phosphate and 0.8 g (1 mmol) XPhos Palladacycle Gen. 3 was dissolved in 450 ml THF/water (2:1). The mixture is stirred at 90° C. for 16 hours. After cooling to room temperature, 300 ml of ethanol is added and the mixture is stirred for 1 hour. The precipitate is filtered off and washed with ethanol. The raw material was dissolved in toluene and filtered through a filter plug (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). The remaining solvent is removed by sublimation (10 ⁻⁵ bar at 300° C.).

Yield: 8.2 g (9.1 mmol, 52%)

The following compounds can be synthesized in a similar manner:

B) Fabrication of OLED

The preparation of solution-based OLEDs has already been described a number of times in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is adapted to the circumstances described below (layer-thickness variations, materials).

The material combination of the present invention is used in the following layer sequence:

- Board,

- ITO (50 nm),

- a hole injection layer (20 nm);

- a hole transport layer (25 nm);

- the emission layer (EML) (30 nm),

- electron blocking layer (HBL) (10 nm),

- electron transport layer (ETL) (40 nm),

- Cathode (Al) (100 nm).

A glass plate coated with structured ITO (indium tin oxide) to a thickness of 50 nm serves as the substrate. They are coated with buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen). Spin coating of the buffer is performed from water in air. Subsequently, the layer is dried by heating at 180° C. for 10 minutes. A hole transport layer and an emission layer are applied to the glass plate coated in this way.

The hole transport layer is either a polymer (HTM1) of the structure shown in Table 1 synthesized according to WO2013156130 or a polymer HTM2 (Table 1) synthesized according to WO2018/114882. Since the polymer is soluble in toluene, such a solution typically has a solids t content of the order of 6 g/l, if the layer thickness of 25 nm typical for devices as here is to be achieved by spin coating. The layer is applied by spin coating in an inert gas atmosphere, in this case argon, and dried by heating at 225° C. for 30 minutes.

The emissive layer consists of a matrix material (host material) H and an emissive dopant (emitter) D. Both materials are present in the release layer in a proportion of 98 wt % H and 2 wt % D. The mixture for the release layer is dissolved in toluene. If, as here, a layer thickness of 30 nm, typical for devices, is to be achieved by spin coating, the solids content of this solution is about 10 mg/ml. The layer was applied by spin coating in an inert gas atmosphere and dried by heating at 145 DEG C for 15 minutes. The materials used in this case are shown in Table 1.

Likewise the materials for the electron blocking layer and the electron transporting layer were applied by thermal evaporation in a vacuum chamber and are shown in Table 2. The electron blocking layer consists of the material ETM1 and the electron transport layer consists of the two materials ETM1 and ETM2, which are mixed with each other by co-evaporation in a volume ratio of 55% of ETM1 and 45% of ETM2. The cathode is a 100 nm thick aluminum layer formed by thermal evaporation. OLEDs are characterized by standard methods. For this purpose, electroluminescence spectra were recorded, and the current efficiency (measured in cd/A) and the external quantum efficiency (measured in EQE, %) as a function of luminous concentration, assuming Lambertian emission characteristics, were determined. It is calculated from the current/voltage/luminous concentration characteristic line (IUL characteristic line). An electroluminescence spectrum is recorded at a luminous concentration of 500 cd/m ² , and CIE 1931 x and y color coordinates are calculated from this data. Lifetime LT80 @ 500 cd/m² is defined as the time after which the initial luminous density of 500 cd/m² has decreased by 20%.

Use of the Compounds of the Invention as Emissive Materials in Fluorescent OLEDs

The compounds of the present invention are particularly suitable as hosts when blended with a fluorescent blue dopant to form the emissive layer of a fluorescent blue OLED device. Representative examples are H1, H2, H3 and H4. The characteristics of the various OLEDs are summarized in Table 3. Examples V1 and V2 represent the prior art, while Examples E1, E2, E3, E4 and E5 represent the properties of OLEDs containing the materials of the present invention.

Table 3 shows that the use of the host materials H1, H2, H3 and H4 according to the present invention, when used as matrix materials in fluorescent blue OLEDs, increases lifetime while maintaining similar efficiency and color compared to the prior art (HR). .

Claims (14)

A compound of formula (1) below.

The following applies to the symbols and indices used in expressions:
E represents O or S;
X at each occurrence, identically or differently, represents CR ^X or N;
Y at each occurrence, identically or differently, represents CR ^Y or N; or Y is Ar ^S , Ar ¹ or C when bonded to Ar ² or heterocycle represented in formula (1) when Ar ^S is absent;
Ar ¹ , Ar ² on each occurrence, identically or differently, represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which on each occurrence may be substituted by one or more radicals R;
Ar ^S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may on each occurrence be substituted by one or more radicals R;
R ^X , R ^Y are at each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, C(=0)Ar, P(=0)(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, 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups are RC=CR, C≡C, Si(R) ₂ , Ge(R) ₂ , Sn(R) ₂ , C=O, C=S, C=Se, P(=O)(R), may be replaced by SO, SO ₂ , O, S or CONR, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), in each case by one or more radicals R represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;
wherein the two radicals R ^X may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; Two radicals R ^Y may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R;
R is at each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, C(=0)Ar, P(=0)(Ar) ₂ , S(=0)Ar , S(=O) ₂ Ar, N(R´) ₂ , N(Ar) ₂ , NO ₂ , Si(R ^´ ) ₃ , B(OR´) ₂ , OSO ₂ ^R´ , 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R', wherein in each case one or more Nonadjacent CH ₂ groups are 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 one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R ^′ , or 5 to 60 ring systems, which may be substituted by one or more radicals R ^′ represents an aryloxy group having two aromatic ring atoms; wherein the two radicals R may together form an aliphatic or aromatic ring system, which may be substituted by one or more radicals R ^' ;
Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may also be substituted on each occurrence by one or more radicals R ^′ ;
R ^´ is at each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms a branched or cyclic alkyl, alkoxy or thioalkyl group having, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by SO, SO ₂ , O, S and one or more H atoms are D, F, Cl, Br or I), or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms.
n and m represent integers selected from 0, 1 and 2; provided that n = m;
p and q represent, in each case, identically or differently, an integer selected from 1, 2 or 3. According to claim 1,
A compound characterized in that it is selected from compounds of formula (2), (3), (4) or (5).

Symbols and indices in the formula have the same meaning as in claim 1. According to claim 1 or 2,
A compound characterized by being selected from compounds of the following formulas (2-1), (3-1), (4-1) or (5-1).

Symbols and indices in the formula have the same meaning as in claim 1. According to any one of claims 1 to 3,
A compound characterized in that n = m = 0 or n = m = 1. According to any one of claims 1 to 4,
Ar ¹ and Ar ² are, at each occurrence, identically or differently, phenyl, biphenyl, terphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, benzophenanthrene, benzanthracene , pyrene, perylene, triphenylene, benzopyrene, fluoranthene, dibenzofuran, dibenzothiophene, carbazole or a combination of two or three of these groups, each of which may be substituted with one or more radicals R ) A compound characterized in that it represents. According to any one of claims 1 to 5,
A compound characterized in that Ar ¹ and Ar ² each, identically or differently, represent a group of one of the following formulas (Ar-1) to (Ar-9).

during the ceremony
- E ¹ in each case, identically or differently, represents C(R ⁰ ) ₂ , NR ^N , O or S,
- R ⁰ , R ^N are in each case, identically or differently, H, D, F, Cl, Br, I, CN, Si(R) ₃ , 1 to 40, preferably 1 to 20, more Preferably a straight chain alkyl, alkoxy or thioalkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms. , an alkoxy or thioalkyl group, each of which may be substituted with one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups are 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 one or more H atoms are D , F, Cl, Br, I, CN or NO ₂ ), 5 to 60, preferably 5 to 40, more preferably 5 to 40, which may in each case be substituted by one or more radicals R Aromatic or heteroaromatic ring systems having 30, particularly preferably 5 to 24, very particularly preferably 5 to 18 aromatic ring atoms, or 5 to 60, preferably 5 to 60, which may be substituted by one or more radicals R represents an aryloxy group having from 5 to 40, more preferably from 5 to 30, particularly preferably from 5 to 24 and very particularly preferably from 5 to 18 aromatic ring atoms, wherein two radicals R ⁰ are at least one radical R may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by;
- dotted lines indicate binding to adjacent anthracene moieties; and
- The groups of formulas (Ar-1) to (Ar-9) may be substituted at each free position by a group R having the same meaning as in claim 1. A composition comprising as a host material a compound according to any one of claims 1 to 6 and a dopant selected from emissive materials. According to claim 7,
A composition comprising a second host material. A formulation comprising a compound according to any one of claims 1 to 6 and at least one solvent. According to claim 9,
A formulation characterized in that it comprises an additional compound selected from release materials. According to claim 9 or 10,
A formulation characterized in that it comprises an additional compound selected from the host material. An electronic device comprising at least one compound according to any one of claims 1 to 6, comprising an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, An electronic device selected from the group consisting of dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices. According to claim 12,
characterized in that the electronic device is an organic electroluminescent device, the compound according to any one of claims 1 to 6 is used as a host material in an emission layer, and the emission layer contains at least one fluorescent emitter. electronic device. 14. The organic electroluminescent device according to claim 13, characterized in that the emissive layer further comprises at least one additional component selected from a host material.