KR20240075872A - Materials for Electronic Devices - Google Patents

Abstract

The present invention relates to compounds suitable for use in electronic devices, and electronic devices containing these compounds, more particularly organic electroluminescent devices.

Description

Materials for Electronic Devices

The present invention relates to materials for use in electronic devices, especially organic electroluminescent devices, and to electronic devices comprising these materials, especially organic electroluminescent devices.

Electronic devices containing organic, organometallic and/or polymeric semiconductors are increasing in importance and are used in many commercial products for their performance and for cost reasons. Examples herein include organic-based charge transport materials (e.g., triarylamine-based hole transporters) in copiers, organic or polymeric light-emitting diodes (OLEDs or PLEDs) in read-out and display devices, or organic light emitting diodes in copiers. Contains receptors. Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic integrated circuits (O-IC), organic optical amplifiers and organic laser diodes (O-lasers) are It is in an advanced stage of development and may have great importance in the future.

Electronic devices in the context of the present invention are understood to mean organic electronic devices containing organic semiconductor materials as functional materials. In particular, electronic devices refer to electroluminescent devices such as OLED.

The construction of OLEDs in which organic compounds are used as functional materials is known to those skilled in the art from the prior art. In general, OLED is understood to mean an electronic device having one or more layers containing organic compounds and emitting light upon application of voltage.

In electronic devices, especially OLEDs, there is a great need to improve performance data, especially lifetime, efficiency and operating voltage. For these aspects, it has not been possible to find a satisfactory solution to date.

Electronic devices typically include a cathode, an anode and at least one functional, preferably emitting, layer. In addition to these layers, it also comprises 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. It may also be included.

The hole transport layer and electron transport layer have a significant impact on the performance data of electronic devices.

The object of the present invention is to provide compounds that are suitable for use in electronic devices, in particular OLEDs, in particular as materials of the hole transport layer or as materials of the electron transport layer, and which lead to excellent properties.

Surprisingly, it has been found that this aim is achieved by certain triptycenes, described in detail below, which are well suited for use in electronic devices, especially OLEDs. These OLEDs have particularly long lifetime, high efficiency and relatively low operating voltage. Accordingly, the present invention provides these compounds and electronic devices comprising these compounds, particularly organic electroluminescent devices.

The present invention provides compounds of the formula (1):

The symbols used in the formula are as follows:

X is the same or different at each occurrence and is CR or N, provided that not more than two X groups per ring are N;

R' is the same or different in each case and is D, F, Cl, Br, I, N(Ar ² ) ₂ , OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S( =O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case is substituted by one or more R ¹ radicals an aromatic or heteroaromatic ring system, which may be an aromatic or heteroaromatic ring system, provided that at least one or both R' comprises at least 1 nitrogen atom bonded to 3 carbon atoms, and at most 1 R' is N(Ar ² ) ₂ and any two groups bonded to Ar ² or at least one nitrogen atom in N(Ar ² ) ₂ are not connected or are connected via a single bond;

Ar ² is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R ¹ radicals;

R is the same or different in each case, H, D, F, Cl, Br, I, OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C (R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S(=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or A branched or cyclic alkyl group having 3 to 20 carbon atoms (said alkyl, alkenyl or alkynyl groups may in each case be substituted by one or more R ¹ radicals, and one or more non-adjacent CH ₂ groups may be -R ¹ C= CR ¹ -, -C≡C-, Si(R ¹ ) ₂ , NR ¹ , CONR ¹ , C=O, C=S, -C(=O)O-, P(=O)(R ¹ ), -O-, -S-, SO or SO ₂ ), or has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case with one or more R ¹ radicals an aromatic or heteroaromatic ring system which may be substituted, wherein two or more R radicals, preferably bonded to the same ring, together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring which may be substituted by one or more R ¹ radicals. Two R radicals bonded to the same carbon, silicon, germanium or tin atom together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ¹ radicals. You may;

Ar' is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R ¹ radicals;

R ¹ is the same or different in each case, H, D, F, I, B(OR ² ) ₂ , N(R ² ) ₂ , CHO, C(=O)R ² , CR ² =C(R ² ) ₂ , CN, C(=O)OR ² , Si(R ² ) ₃ , NO ₂ , P(= O)(R ² ) ₂ , OSO ₂ R ² , SR ² , OR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 carbon atoms or 2 to an alkenyl or alkynyl group having 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R ² radicals and one or more CH ₂ groups in the above-mentioned groups are -R ² C=CR ² -, -C≡C-, Si(R ² ) ₂ , C=O, C=S, -C(=O)O-, NR ² , CONR ² , P(=O)(R ² ), -O-, -S-, SO or SO ₂ and one or more hydrogen atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which in each case may be substituted by one or more R ² radicals, wherein two The above R ¹ radicals may be taken together to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

R ² is the same or different at each occurrence and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are also replaced by D or F may be; At the same time, two or more R ² substituents may be connected to each other or may form a ring.

A nitrogen atom bonded to three carbon atoms is understood to mean a nitrogen atom that has a covalent bond to three carbon atoms. For example, this is the nitrogen atom of the -NR ₂ group, where the radicals bonded to the nitrogen atom may also bridge with each other. The bridge preferably forms a five-membered ring via single bonds, as for example in the case of carbazole.

Aryl groups in the context of the present invention contain from 6 to 40 carbon atoms; Heteroaryl groups in the context of the present invention contain 5 to 40 carbon atoms and at least one heteroatom, provided that the total of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. Aryl or heteroaryl groups may herein be simple aromatic rings, such as benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused (annelated) aryl or heteroaryl groups, It is understood to mean, for example, naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked together by single bonds, for example biphenyls, are, in contrast, referred to as aromatic ring systems rather than aryl or heteroaryl groups.

Aromatic ring systems in the context of the present invention contain from 6 to 60 carbon atoms, preferably from 6 to 40 carbon atoms, in the ring system. A heteroaromatic ring system in the context of the present invention contains in the ring system 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and at least one heteroatom, provided that the total of the carbon atoms and heteroatoms is It's at least 5. The heteroatoms are preferably selected from N, O and/or S. Aromatic or heteroaromatic ring systems in the context of the present invention do not necessarily contain aryl or heteroaryl groups, but also include two or more aryl or heteroaryl groups containing non-aromatic units (preferably less than 10% of atoms other than H), e.g. It should be understood to mean a system that can be linked, for example, by carbon, nitrogen or oxygen atoms or carbonyl groups. These will likewise be understood to mean systems in which two or more aryl or heteroaryl groups are directly linked to each other, for example biphenyl, terphenyl, bipyridine or phenylpyridine. Therefore, systems such as, for example, fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. can also be used as aromatic rings in the context of the present invention. Systems will also be considered, as will systems in which two or more aryl groups are linked, for example by a linear or cyclic alkyl group or a silyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups and groups in which two or more aryl or heteroaryl groups are directly linked to each other, for example biphenyl, terphenyl, quarterphenyl or bipyridine, and also fluorene or spiro It is bifluorene.

Electron-rich heteroaromatic ring systems are characterized as being heteroaromatic ring systems that do not contain electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a 6-membered heteroaryl group having at least one nitrogen atom or a 5-membered heteroaryl group having at least two heteroatoms, one of which is a nitrogen atom and the other is an oxygen, sulfur or substituted nitrogen atom. original heteroaryl groups, where additional aryl or heteroaryl groups may also be fused to these groups in each case. In contrast, an electron-rich heteroaryl group is a 5-membered heteroaryl group having exactly one heteroatom selected from oxygen, sulfur, and substituted nitrogen, to which additional aryl groups and/or additional electron-rich 5-membered heteroaryl groups may be fused. . Thus, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. Electron-rich heteroaryl groups are also called electron-rich heteroaromatic radicals.

Electron-deficient heteroaromatic ring systems are characterized by containing at least one electron-deficient heteroaryl group and particularly preferably by containing no electron-rich heteroaryl groups.

In the context of the present invention, the term “alkyl group” is used as an umbrella term for both linear and branched alkyl groups and cyclic alkyl groups. Similarly, the terms “alkenyl group” and “alkynyl group” are used as umbrella terms for both linear or branched alkenyl or alkynyl groups and for cyclic alkenyl or alkynyl groups.

Cyclic alkyl, alkoxy or thioalkoxy groups in the context of the present invention are understood to mean monocyclic, bicyclic or polycyclic groups.

In the context of the present invention, an aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group, which may contain 1 to 40 carbon atoms and where individual hydrogen atoms or CH ₂ groups may also be replaced by the above-mentioned groups. Preferably it is understood to mean the following radicals: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s- Pentyl, t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2- Methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1-bicyclo[2.2.2]octyl , 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2, 2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl , 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl -n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept -1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl , 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1 -(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex -1-yl and 1-(n-decyl)cyclohex-1-yl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, jade thenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, fentinyl, hexynyl, heptynyl or octynyl. The alkoxy group OR ¹ having 1 to 40 carbon atoms is 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, cyclooctyloxy , 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl groups SR ¹ having 1 to 40 carbon atoms are in particular 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, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, Pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenyl It is understood to mean thio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, the alkyl, alkoxy or thioalkyl groups according to the invention may be straight-chain, branched or cyclic, where one or more non-adjacent CH ₂ groups may be replaced by the groups described above; Additionally, one or more hydrogen atoms may also be replaced by D, F, Cl, Br, I, CN or NO ₂ , preferably by F, Cl or CN, more preferably by F or CN.

has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may also be substituted in each case by the above-mentioned radicals or hydrocarbyl radicals and may be connected to an aromatic or heteroaromatic system via any desired position. Possible aromatic or heteroaromatic ring systems include, in particular, benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, Terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxen, isotruxen, spirotruxen, spiroisotruxen, furan, benzo. Furan, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthri Dean, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphtimidazole , phenanthroimidazole, pyridimidazole, pyrazinimidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, 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-tetraazaperylene, Pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotria Sol, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadia Sol, 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 , is understood to mean groups derived from indolizine and benzothiadiazole or groups derived from a combination of these systems.

The phrase that two or more radicals may together form a ring system should be understood, in the context of this detailed description, to mean, inter alia, that two radicals are linked to each other by a chemical bond with the formal removal of two hydrogen atoms. . This is illustrated by the following diagram:

.

.

However, in addition, the above-mentioned phrase should also be understood to mean that in the case where one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom was bonded, forming a ring. This will be illustrated by the following diagram:

.

.

Further preferred embodiments are represented by the following formulas (2), (3) and (4):

The symbols used here have the definitions given above for equation (1), and the following definitions are additionally applicable:

Ar ¹ is the same or different in each case and is a divalent aromatic or hetero group having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R ¹ radicals. It is an aromatic ring system;

R' is the same or different in each case and is D, F, Cl, Br, I, OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C(R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P( =O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S(=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , 5 to 60 aromatic ring atoms, preferably 5 to 60 aromatic ring atoms. It is an aromatic or heteroaromatic ring system having 40 aromatic ring atoms, which in each case may be substituted by one or more R1 radicals;

s is the same or different in each case and is 0 or 1, where 0 means that N is directly bonded to the basic skeleton and at least one s in equation (1) is 1.

Here it is possible for any two Ar ² and/or Ar ¹ and Ar ² groups to be linked to each other via a single bond, preferably forming a five-membered ring, as in the carbazole structure.

In a preferred embodiment of the invention, at most two symbols X per ring are N, more preferably at most one symbol X per ring is N.

In a preferred embodiment, all X's are CR.

In a preferred embodiment, all X's are CR, where R is H, D, F or CN.

In a preferred embodiment of the invention, the compound does not have a ring system fused to tryptycene.

Therefore, preferred embodiments of compounds of formulas (2), (3) and (4) are compounds of formulas (2-1), (3-1) and (4-1):

In the formulas, the symbols, if present, have the definitions given for formulas (2), (3) and (4).

Here it is possible for both Ar ² and/or Ar ¹ and Ar ² groups to be linked to each other, preferably via a single bond, to form a carbazole structure.

Compounds of formulas (2) and (3) or preferred embodiments thereof may form a pair of enantiomers depending on substitution. The compounds of the present invention preferably take the form of racemates, but may also take the form of pure enantiomers.

In a preferred embodiment of the invention, up to 5 R groups in formulas (2), (3) and (4), preferably in formulas (2-1), (3-1) and (4-1), are: Preferably no more than two R groups are H, F, CN or D.

Compounds of formulas (2) and (3), more preferably (2-1) and (3-1), are particularly preferred.

A description of the preferred substituents R, Ar', R ¹ and R ² follows. In a particularly preferred embodiment of the invention, the preferences specified below for R, Ar', R ¹ and R ² occur simultaneously and are applicable to the structure of formula (1) and to all the preferred embodiments detailed above.

In a preferred embodiment of the invention, R is the same or different at each occurrence and is H, D, F, CN, OR ¹ , a straight chain alkyl group having 1 to 10 carbon atoms or a straight chain alkyl group having 2 to 10 carbon atoms An alkenyl group or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may each be substituted by one or more R ¹ radicals, but is preferably unsubstituted and has one or more non-adjacent CH radicals. ₂ groups may be replaced by O), or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which in each case may be substituted by one or more R ¹ radicals; At the same time, the two R radicals together may also form an aliphatic, aromatic or heteroaromatic ring system. More preferably, R is the same or different at each occurrence and is H, F, CN, a straight-chain alkyl group having 1 to 6 carbon atoms, especially 1, 2, 3 or 4 carbon atoms, or 3 a branched or cyclic alkyl group having from 6 to 6 carbon atoms (wherein in each case the alkyl group may be substituted by one or more R ¹ radicals, but is preferably unsubstituted), or has from 6 to 24 aromatic ring atoms is selected from the group consisting of aromatic or heteroaromatic ring systems which may in each case be substituted by one or more R ¹ radicals, preferably non-aromatic R ¹ radicals. Most preferably ^, R is ^at each occurrence identical or different and is H, or an aromatic or It is selected from the group consisting of heteroaromatic ring systems.

Suitable aromatic or heteroaromatic ring systems R are phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quarterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quarterphenyl, fluorene which may be linked through the 1, 2, 3 or 4 position, spirobifluorene which may be linked via the 1, 2, 3 or 4 position, Naphthalene, indole, benzofuran, which may be linked via the 1 or 2 position; benzothiophene, dibenzofuran, which may be linked via the 1, 2, 3 or 4 position; Carbazole, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benz which may be linked through the 1, 2, 3 or 4 positions. is selected from imidazole, phenanthrene, triphenylene or combinations of two or three of these groups, each of which may be substituted by one or more R ¹ radicals. When R is a heteroaryl group, especially a triazine, pyrimidine or quinazoline, an aromatic or heteroaromatic R ¹ radical on this heteroaryl group may also be preferred.

The R groups here, if they are aromatic or heteroaromatic ring systems, are preferably selected from groups of the formulas R-1 to R-163:

In the formula, R ¹ has the definition given above, the dotted line bond represents the bond to equation (1), and the following definitions are additionally applicable:

Ar ³ is the same or different at each instance and is a divalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms and which at each instance may be substituted by one or more R ¹ radicals;

A ¹ is the same or different at each occurrence and is BR ¹ , C(R ¹ ) ₂ , NR ¹ , O or S, preferably C(R ¹ ) ₂ , NR ¹ , O or S;

A ² is the same or different at each occurrence and is C(R ¹ ) ₂ , NR ¹ , O or S;

p is 0 or 1, where p = 0 means that the Ar ³ group is absent and the corresponding aromatic or heteroaromatic group is bonded directly to a carbon atom or to a heteroatom such as nitrogen, formula R-44, R- For bonding to heteroatoms for 49, R-53, R-57, R-58, R-62, R-66, R-70, R-71, R-112 and R-152 to R-160 , p = 1;

r is 0 or 1, where r = 0 means that the A ¹ group is not bonded at this position, and instead the R ¹ radical is bonded to the corresponding carbon atom.

In a preferred embodiment, Ar ³ comprises a divalent aromatic or heteroaromatic ring system based on groups R-1 to R-163, where p = 0 and a dotted bond and R ¹ is a ring system based on R-1 to R-163. Indicates a bond to an aromatic or heteroaromatic group.

If the groups R-1 to R-163 mentioned above have two or more A ¹ groups, possible choices for them include all combinations from the definition of A ¹ . In that case a preferred embodiment is that one A ¹ group is C(R ¹ ) ₂ , NR ¹ , O or S and the other A ¹ group is C(R ¹ ) ₂ or both A ¹ groups are S or O. Or, both A ¹ groups are O or S.

When A ¹ is NR ¹ , the substituent R ¹ bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and which may also be substituted by one or more R ² radicals. . In a particularly preferred embodiment, these R ¹ substituents are in each case identical or different and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, which are at least two The aromatic or heteroaromatic 6-membered ring groups do not have fused aryl or heteroaryl groups that are directly fused to each other, and may also be substituted in each case by one or more R ² radicals. Particular preference is given to phenyl, biphenyl, terphenyl and quarterphenyl having bonding patterns as listed above for R-1 to R-35, although these structures may also be substituted by one or more R ¹ radicals. It is not replaced.

When A ¹ is C(R ¹ ) ₂ , the substituent R ¹ bonded to this carbon atom is preferably the same or different in each case and is a linear alkyl group having 1 to 10 carbon atoms or 3 to 10 carbon atoms. It is a branched or cyclic alkyl group having atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more R ² radicals. Most preferably, R ¹ is a methyl group or a phenyl group. In this case, the R ¹ radicals together may also form a ring system, which leads to a spiro system.

In a further preferred embodiment of the invention, R ¹ is at each occurrence the same or different and is H, D, F, CN, OR ² , a straight-chain alkyl group having 1 to 10 carbon atoms or 2 to 10 carbon atoms. an alkenyl group having or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may in each case be substituted by one or more R ² radicals and one or more non-adjacent CH ₂ groups are ), or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which in each case may be substituted by one or more R ² radicals; At the same time, two or more R ¹ radicals may together form an aliphatic ring system. In a particularly preferred embodiment of the invention, R ¹ is at each occurrence the same or different and is H, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular 1, 2, 3 or 4 carbon atoms, or 3 a branched or cyclic alkyl group having from to 6 carbon atoms, wherein the alkyl group may be substituted by one or more R ² radicals, but is preferably unsubstituted, or having from 6 to 24 aromatic ring atoms in each case It is selected from the group consisting of aromatic or heteroaromatic ring systems, which may be substituted with one or more R ² radicals, but are preferably unsubstituted.

In a further preferred embodiment of the invention, R ² is in each case the same or different and is H, F, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which is 1 It may be substituted with an alkyl group having from 1 to 4 carbon atoms, but is preferably not substituted.

In a further preferred embodiment of the invention, all R ¹ radicals (if they are aromatic or heteroaromatic ring systems), or R ² radicals (if they are aromatic or heteroaromatic groups) are selected from the groups R-1 to R-163. However, in this case they are correspondingly substituted by R ² or by the groups mentioned for R ² .

In a preferred embodiment, the R radical does not form any additional aromatic or heteroaromatic group fused to the basic skeleton of formula (1).

In a preferred embodiment of the invention, one R' is selected from N(Ar ² ) ₂ or the groups R-44 to R-74, R-143, R-146 to R-148 and R-153 to R-163. However, R-45 to R-48, R-50 to R-52, R-54 to R-56, R-59 to R-61, R-63 to R-65, R-67 to R- In groups 69, R-143, R-146 and R-161 to R-163, at least A ¹ is NR ¹ . In a preferred embodiment of the invention, the Ar ² group is then also a group R-1 to R-163, preferably R-1 to R-149 and R-153 to R-163, more preferably R-2 to R. -149 and R-153 to R-163.

In a preferred embodiment of the invention, one R' is selected from N(Ar ² ) ₂ or the groups R-44 to R-74, R-143 and R-146 to R-148, provided that R-45 to R-48, R-50 to R-52, R-54 to R-56, R-59 to R-61, R-63 to R-65, R-67 to R-69, R-143 and R- In group 146, at least A ¹ is NR ¹ , in which case R ¹ is the same or different at each occurrence and is H, D, F or CN. In a preferred embodiment of the invention, the Ar ² group is then also a group R-1 to R-163, preferably R-1 to R-149 and R-153 to R-163, more preferably R-2 to R. -149 and R-153 to R-163, where R ¹ is the same or different at each occurrence and is more preferably H, D, F or CN.

In a preferred embodiment, one R' is as defined in one of the previous two paragraphs and the other R' is selected from groups R-1 to R-163, provided that the other R' is N( When Ar ² ) ₂ , R-44, R-49, R-53, R-57, R-58, R-62, R-66, R-70, R-71 and R-152 to R-160 In group p is 1.

In a preferred embodiment, one R' does not comprise an electron-deficient heteroaryl group; Preferably neither R' contains an electron-deficient heteroaryl group. Examples of electron-deficient heteroaryl groups are R-79 to R-113, R-144 and R-145.

In a preferred embodiment, none of the R comprises an electron-deficient heteroaryl group, more preferably none of R and at least one R', more preferably none of R or R'.

At the same time, in the compounds of the invention treated by vacuum evaporation, the alkyl group preferably has at most 5 carbon atoms, more preferably at most 4 carbon atoms, and most preferably at most 1 carbon atom. For compounds to be processed from solution, suitable compounds also include alkyl groups, especially those substituted by branched alkyl groups, having up to 10 carbon atoms or oligoarylene groups, for example ortho-, meta-, para. -those substituted by terphenyl or branched terphenyl or quarterphenyl groups.

The preferred embodiments mentioned above may be combined with each other as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages appear simultaneously.

Examples of preferred compounds according to the embodiments detailed above are those detailed in the table below:

The compounds of the present invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling, etc. It can be manufactured by.

The invention therefore also provides a process for preparing the compounds of the invention, characterized by the following steps:

(A) synthesizing the basic skeleton of formula (1);

(B) Coupling the R' radical.

The compound of the present invention is prepared from 9,10-dihydro-4-iodo-9,10[1',2']-benzenanthracen-1-yl trifluoromethanesulfonate [1370032-72-6]. It can be manufactured by proceeding:

1) Suzuki coupling using aryl-/heteroarylboronic acid or ester ((HO) ₂ B-Ar), followed by Y. Imazaki et al., J. Am. Chem. Soc., 2012 , 134, 14760 and another Suzuki coupling incorporating an arylamine:

2) Suzuki coupling using aryl-/heteroarylboronic acid or ester ((HO) ₂ B-Ar), followed by ruthenium catalyzed triflate-bromide exchange, and diaryl-/hetearylamine Ar1Ar2N-H Final Buchwald-Hartwig amination or Ullmann coupling used:

For processing of the compounds of the invention from the liquid phase, for example by spin-coating or printing methods, a formulation of the compounds of the invention is required. These formulations may be solutions, dispersions or emulsions, for example. For this purpose, it may be desirable to use mixtures of two or more solvents. Suitable and preferred solvents are for example toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, Dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-phenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 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, indane, NMP, p-cymene, phenetol, 1, 4-Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether , tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl phenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or a mixture of these solvents.

The invention therefore also provides formulations, especially solutions, dispersions or emulsions, comprising at least one compound of 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 mixtures of these solvents. The preparation of such solutions is known to the person skilled in the art and is described, for example, in WO 2002/072714, WO 2003/019694 and the literature cited therein. The further compound may alternatively be at least one further organic or inorganic compound, for example an emitting compound and/or a matrix material, which is likewise used in electronic devices. These additional compounds may also be polymeric.

The compounds of the invention are suitable for use in electronic devices, especially organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds may be used in different functions and layers.

Accordingly, the present invention also provides the use of the compounds of the present invention in electronic devices.

The invention still also provides an electronic device comprising at least one compound of the invention.

The compounds of the invention may also be used in particular in the form of racemates or pure enantiomers.

An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also include an inorganic material, or a layer that is otherwise formed entirely from an inorganic material.

The electronic device is preferably an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET). , organic solar cell (O-SC), dye-sensitized organic solar cell (DSSC), organic photodetector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC), organic laser It is selected from the group consisting of diodes (O-lasers) and organic plasmon emitting devices, but is preferably an organic electroluminescent device (OLED).

The device is more preferably an organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, which may be an emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, an electron blocking layer or another functional layer. The organic layer contains at least one compound of the invention. The layer depends on the substitution of the compound.

In addition to these layers, the organic electroluminescent device may still have additional 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, charge generation, in each case one or more It may also include layers and/or organic or inorganic p/n junctions. It is likewise possible for an intermediate layer with an exciton blocking function to be introduced, for example, between the two emitting layers. However, it should be mentioned that not all of these layers necessarily need to be present.

In this case, the organic electroluminescent device may comprise one emitting layer, or may comprise multiple emitting layers. If there are multiple emitting layers, these preferably have several emission maxima overall between 380 nm and 750 mm so that the overall result is white emission; In other words, various emitting compounds that may cause fluorescence or phosphorescence are used in the emitting layers. Particularly preferred are systems with three emitting layers, where the three layers exhibit blue, green and orange or red emissions (the basic structure is described for example in WO 2005/011013). The organic electroluminescent device of the invention may also be a tandem OLED, especially for white-emitting OLED.

Compounds of formula (1) are preferably used in organic electroluminescent devices comprising at least one phosphorescent emitter. The compounds of the invention according to the embodiments detailed above may also be used in different layers, depending on their exact structure.

In this case, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers, where at least one layer contains at least one compound of the invention. In addition, the compounds of the invention can also be used in electron transport layers and/or in hole blocking layers and/or in hole transport layers and/or in exciton blocking layers.

The expression "phosphorescent compound" usually refers to a compound that emits light via a spin-banned transition, e.g. a transition from an excited triplet state or a state with a higher spin quantum number, e.g. a quintet state. refers to compounds that are

Suitable phosphorescent compounds (=triplet emitters) emit light, in particular, when suitably excited, preferably in the visible region, and also have a density greater than 20, preferably greater than 38, and less than 84, more preferably 56 It is a compound containing at least one atom with an atomic number greater than and less than 80. Preferred phosphorescent compounds contain transition metals or lanthanides, in particular copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially if the compounds contain iridium, platinum or copper. If it contains, it is all luminescent complexes. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent-emitting compounds.

Examples of the emitters described above are in applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2 005/ 0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/1 02709, WO 2011/032626, WO 2011/ 066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/10 4045, WO 2015/117718, WO 2016/ 015815, WO 2016/124304, WO 2017/032439, WO 2018/011186, WO 2018/041769, WO 2019/020538, WO 2018/178001, WO 2019/115423 and WO 2019/15 It can be found at 8453. In general, all phosphorescent complexes as used in phosphorescent OLEDs according to the prior art and as known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive steps. Furthermore, the person skilled in the art can use additional phosphorescent complexes in combination with the compounds of formula (1) in organic electroluminescent devices without incurring inventive step capabilities. Additional examples are provided in the following table.

According to the invention, it is also possible to use the compounds of formula (1) in electronic devices containing one or more fluorescent emitting compounds.

In a preferred embodiment of the invention, compounds of formula (1) are used as hole transport materials. In this case, the compound is preferably present in the hole transport layer, electron blocking layer or hole injection layer. It is particularly preferred for use in electron blocking layers.

A hole transport layer in the context of the present application is a layer that has a hole transport function between the anode and the emission layer.

Hole injection layer and electron blocking layer in the context of the present application are understood to mean specific embodiments of a hole transport layer. The hole injection layer is a hole transport layer that is either immediately adjacent to the anode, in the case where there are multiple hole transport layers between the anode and the emission layer, or is separated from it only by a single coating of the anode. The electron blocking layer is the hole transport layer immediately adjacent to the emitting layer on the anode side, in the case of a plurality of hole transport layers between the anode and the emitting layer. The OLED of the invention preferably comprises, between the anode and the emitting layer, 2, 3 or 4 hole transport layers, preferably at least 1, more preferably exactly 1 or 2, of the formula ( Contains the compounds of 1).

If the compound of formula (1) is used as a hole transport material in the hole transport layer, hole injection layer or electron blocking layer, the compound may be used in the hole transport layer as a pure material, i.e. in a 100% proportion, or it may be used in combination with one or more additional compounds. It can also be used. Next, in a preferred embodiment, the organic layer containing the compound of formula (1) additionally contains at least one p-dopant. It is preferred that the p-dopant used according to the invention is an organic electron acceptor compound such that it is capable of oxidizing one or more other compounds in the mixture.

Particularly preferred embodiments of p-dopants are those described in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/00. 3455, WO 2010/094378, WO 2011 /120709, US 2010/0096600, WO 2012/095143 and DE 102012209523.

Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenedione, azaphenalene, azatriphenylene, I ₂ , metal halides, preferably transition metal halides, metal oxides, preferably at least one transition. It is a complex of a metal or a metal oxide containing a metal of the main group 3, and a transition metal complex, preferably Cu, Co, Ni, Pd and Pt, and a ligand containing at least one oxygen atom as a binding site. Additionally, transition metal oxides are preferred as dopants, oxides of rhenium, molybdenum and tungsten are preferred, and Re ₂ O ₇ , MoO ₃ , WO ₃ and ReO ₃ are more preferred.

The p-dopant is preferably distributed essentially uniformly in the p-doped layer. These can be achieved, for example, by simultaneous evaporation of the p-dopant and the hole transport material matrix.

Preferred p-dopants are in particular the following compounds:

In a further preferred embodiment of the invention, the compounds of formula (1) are used as hole transport materials in combination with hexaazatriphenylene derivatives as described in US 2007/0092755. Particular preference is given to using the hexaazatriphenylene derivative in a separate layer.

In a further embodiment of the invention, the compounds of formula (1) are used in the emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds.

In this case, the proportion of matrix material in the emitting layer is between 50.0 vol.% and 99.9 vol.%, preferably between 80.0 vol.% and 99.5 vol.%, more preferably between 92.0 vol.% and 99.5 vol.% for the fluorescent emitting layer. , for the phosphorescent emitting layer is between 85.0% and 97.0% by volume.

Correspondingly, the proportion of the emitting compound is between 0.1 vol.% and 50.0 vol.% for the fluorescent emitting layer, preferably between 0.5 vol.% and 20.0 vol.%, more preferably between 0.5 vol.% and 8.0 vol.%, and the phosphorescence emission For the layer it is between 3.0% and 15.0% by volume.

The emitting layer of an organic electroluminescent device may also comprise systems containing multiple matrix materials (mixed matrix systems) and/or multiple emitting compounds. Even in this case, generally, the emitting compounds are those with a smaller proportion in the system and the matrix materials are those with a larger proportion in the system. However, in individual cases, the proportion of single matrix materials in the system may be less than the proportion of single emitting compounds.

Compounds of formula (1) are preferably used as components of mixed matrix systems. The mixed matrix system preferably consists of two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties and the other material is a material with electron transport properties. The compound of formula (1) is preferably a matrix material with hole transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components can also be combined primarily or completely in a single mixed matrix component, in which case the additional mixed matrix component(s) fulfill other functions. The two different matrix materials are mixed in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. It can exist as rain. It is desirable to use mixed matrix systems in phosphorescent organic electroluminescent devices. A source of more detailed information on mixed matrix systems is application WO 2010/108579.

The mixed matrix system may contain one or more emitting compounds, preferably one or more phosphorescent compounds. In general, it is desirable to use mixed matrix systems in phosphorescent organic electroluminescent devices.

Particularly suitable matrix materials that can be used in combination with the compounds of the present invention as matrix components of mixed matrix systems include the preferred matrix materials specified below for phosphorescent compounds or the preferred matrix materials for fluorescent compounds, depending on the type of emitting compound used in the mixed matrix system. is selected from

Preferred phosphorescent compounds for use in mixed matrix systems are generally the same as those further described as preferred phosphorescent emitter materials.

Preferred embodiments of different functional materials in electronic devices are presented below.

Examples of phosphorescent compounds are given below.

Preferred fluorescent emitting compounds are selected from the class of arylamines. Arylamine or aromatic amine is understood in the context of the present invention to mean a compound containing a system of three substituted or unsubstituted aromatic or heteroaromatic rings directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine or aromatic chrysendiamine. Aromatic anthraceneamines are understood to mean compounds in which the diarylamino group is bonded directly to the anthracene group, preferably in position 9. Aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at positions 9 and 10. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined similarly, wherein the diarylamino group is preferably attached to the pyrene at the 1-position or at the 1,6-position. Further preferred releasing compounds are indenofluorenamine or fluorenediamine (for example according to WO 2006/108497 or WO 2006/122630), benzoindenofluoreneamine or -fluorenediamine (for example according to WO 2008/ 006449), and dibenzoindenofluoreneamines or -diamines (e.g. according to WO 2007/140847), and indenofluorene derivatives with fused aryl groups disclosed in WO 2010/012328. Likewise, pyrenearylamines disclosed in WO 2012/048780 and WO 2013/185871 are preferred. Similarly, benzoindenofluorene amine disclosed in WO 2014/037077, benzofluorenamine disclosed in WO 2014/106522, extended benzoindenofluorene disclosed in WO 2014/111269 and WO 2017/036574, WO 2017/ Preference is given to the phenoxazines disclosed in 028940 and WO 2017/028941, and the fluorine derivatives bonded to furan units or to thiophene units disclosed in WO 2016/150544. It is also possible to use boron compounds according to WO2020208051, WO2015102118, WO2016152418, WO2018095397, WO2019004248, WO2019132040, US20200161552, and WO2021089450.

Useful matrix materials, preferably for fluorescent compounds, include materials from a variety of material classes. Preferred matrix materials are oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), especially oligoaryls with fused aromatic groups, oligoarylenevinyl ren (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g. according to WO 2004/081017), hole-conducting compounds (e.g. according to WO 2004/058911) , electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), selected from the class of boronic acid derivatives (e.g. according to WO 2006/117052) or benzanthracenes (e.g. according to WO 2008/145239). Particularly preferred matrix materials are selected from the class of oligoarylenes, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides with naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds. Very particularly preferred matrix materials are selected from the class of oligoarylenes, including anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. Oligoaryl in the context of the present invention is understood to mean compounds in which at least three aryl or arylene groups are bonded to each other. WO 2006/097208, WO 2006/131192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO 2008/145239, WO 2009/100925, WO 2011/054442 and EP 1 Anthracene derivatives disclosed in 553154, EP 1749809, Further preferred are the pyrene compounds disclosed in EP 1905754 and US 2012/0187826, the benzanthracenylanthracene compounds disclosed in WO 2015/158409, the indenobenzofurans disclosed in WO 2017/025165, and the phenanthrylanthracenes disclosed in WO 2017/036573. .

Like the compounds of formula (1), preferred matrix materials for phosphorescent compounds are aromatic ketones, aromatic phosphine oxides or aromatic oxides, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680. Sulfoxides or sulfones, triarylamines, carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl) or WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008 /086851 or WO 2013/041176, for example according to WO 2007/063754 or WO 2008/056746, for example WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/ 056776 Indenocarbazole derivatives according to, e.g. EP 1617710, EP 1617711, EP 1731584, azacarbazole derivatives according to JP 2005/347160, e.g. bipolar matrix materials according to WO 2007/137725, e.g. WO 2005/ Silane according to 111172, for example azaborole or boronic ester according to WO 2006/117052, for example WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or W O Triazine derivatives according to 2011/060877, e.g. zinc complexes according to EP 652273 or WO 2009/062578, e.g. diazacylol or tetraazacylol derivatives according to WO 2010/054729, e.g. in WO 2010/054730 Diazaphosphole derivatives according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, bridged carbazole derivatives, e.g. triphenylene derivatives according to WO 2012/048781 , a lactam, for example according to WO 2011/116865 or WO 2011/137951, or a dibenzo, for example according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565 Puran It is a derivative. Likewise, additional phosphorescent emitters with a shorter wavelength emission than the actual emitter may be co-hosts in the mixture, or compounds that, if any, do not participate in charge transport to a significant extent, as described for example in WO 2010/108579. It is possible to exist as

Suitable charge transport materials that can be used in the hole injection or hole transport layer or in the electron blocking layer or in the electron transport layer of the electronic component of the invention include, for example, the compounds of formula (1), as well as those of Y. Shirota et al. Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

The OLED of the invention preferably comprises at least two different hole transport layers. Compounds of formula (1) may be used herein in one or more hole transport layers or in all hole transport layers. In a preferred embodiment, the compounds of formula (1) are used in exactly one or exactly two hole transport layers and other compounds, preferably aromatic amine compounds, are used in the additional hole transport layers present. Additional compounds preferably used together with the compounds of formula (1) in the hole transport layer of the OLED of the invention are in particular indenofluorenamine derivatives (for example according to WO 06/122630 or WO 06/100896), EP 1661888 Amine derivatives disclosed in, hexaazatriphenylene derivatives (e.g. according to WO 01/049806), amine derivatives with fused aromatics (e.g. according to US 5,061,569), amine derivatives disclosed in WO 95/09147, mono Benzoindenofluorenamines (e.g. according to WO 08/006449), dibenzoindenofluorenamines (e.g. according to WO 07/140847), spirobifluoreneamines (e.g. according to WO 2012/ 034627 or WO 2013/120577), fluoreneamines (e.g. according to WO 2014/015937, WO 2014/015938, WO 2014/015935 and WO 2015/082056), spirodibenzopyranamines (e.g. according to WO 2013/083216), dihydroacridine derivatives (e.g. according to WO 2012/150001), spirodibenzofurans and spirodibenzothiophenes (e.g. according to WO 2015/022051, WO 2016/102048 and according to WO 2016/131521), phenanthrenediarylamine (e.g. according to WO 2015/131976), spirotribenzotropolone (e.g. according to WO 2016/087017), spirobiflu with meta-phenyldiamine group orene (e.g. according to WO 2016/078738), spirobisacridine (e.g. according to WO 2015/158411), xanthenedialylamine (e.g. according to WO 2014/072017), and diarylamino groups It is a 9,10-dihydroanthracene spiro compound (according to WO 2015/086108).

The use of spirobifluorene substituted by a diarylamino group in the 4-position as hole transport compounds, in particular the use of such compounds as claimed and disclosed in WO 2013/120577, and spiro substituted by a diarylamino group in the 2-position as hole transport compounds. Very particular preference is given to the use of bifluorenes, especially those compounds claimed and disclosed in WO 2012/034627.

The material used in the electron transport layer may be any material used as an electron transport material in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes, such as Alq3, zirconium complexes, such as Zrq4, lithium complexes, such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, These are quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, borane, diazaphosphole derivatives and phosphine oxide derivatives. Further 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 cathodes for electronic components are metals with low work function, various metals such as alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm etc.) is a metal alloy or multi-layer structure. Additionally, alloys of alkali metals or alkaline earth metals and silver are suitable, for example alloys of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use additional metals with a relatively high work function, for example Ag or Al, for example Ca/Ag, Mg/Ag or Ba/ Combinations of metals such as Ag are commonly used. It may also be advantageous to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of suitable materials are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

Preferred anodes are materials with a high work function. The anode preferably has a work function greater than 4.5 eV relative to vacuum. Firstly suitable for this purpose are metals with a high redox potential, for example Ag, Pt or Au. Second preferred may also be metal/metal oxide electrodes (eg Al/Ni/NiOx, Al/PtOx). For some applications, at least one of the electrodes must be transparent or partially transparent to enable irradiation of organic materials (organic solar cells) or emission of light (OLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Additionally conductively doped organic materials are preferred, especially conductively doped polymers. Additionally, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

The device is suitably structured (depending on the application), contact-connected and finally sealed to exclude the harmful effects of water and air.

In the further layers of the organic electroluminescent device of the invention, any materials typically used according to the prior art can be used. It will therefore be possible for a person skilled in the art to use any material known for organic electroluminescent devices in combination with the compounds of the invention of formula (1) or of the preferred embodiments mentioned above, without inventive thinking.

Additional preference is given to organic electroluminescent devices, characterized in that at least one layer is coated by a sublimation method. In this case, the material is applied by vapor deposition in a vacuum sublimation system at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, the initial pressure can also be much lower, for example below 10 ^-7 mbar.

Likewise, preference is given to organic electroluminescent devices, characterized in that one or more layers are coated by the organic vapor phase deposition (OVPD) method or with the aid of carrier gas sublimation. In this case, the materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, where the material is applied directly by a nozzle and structured accordingly.

Additionally, one or more layers may be prepared from solution, for example by spin coating, or by any printing method, for example screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging, thermal transfer printing). , organic electroluminescent devices are preferred, characterized in that they are manufactured by inkjet printing or nozzle printing. For this purpose, soluble compounds are needed, which can be obtained, for example, through suitable substitutions.

Hybrid methods are also possible, for example in which one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

Those skilled in the art are generally aware of these methods and can apply them without inventive capabilities to organic electroluminescent devices comprising the compounds of the invention.

According to the invention, electronic devices containing one or more compounds of formula (1) can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (e.g. light therapy).

The compounds of the present invention and the organic electroluminescent devices of the present invention are notable for one or more of the following surprising properties:

1. The compound of the present invention has a long life span.

2. The compounds of the present invention reach high efficiency, especially high EQE.

3. The compounds of the present invention reach low operating voltages.

The invention is illustrated in detail by the following examples, which are not intended to limit the invention. A person skilled in the art, using the information given, will be able to practice the invention to its full extent disclosed, to prepare further compounds of the invention and to use them in electronic devices or to use the methods of the invention without inventive inventive capabilities. will be.

Examples:

Unless otherwise stated, the following syntheses are performed under a protective gas atmosphere in a dry solvent. Metal complexes are further treated with light exclusion or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. Each number in brackets or cited for an individual compound refers to the CAS number of the compound as known from the literature. For compounds that may have multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown in a representative manner.

Synthons LS known from the literature:

A) Synthesis of synthon S:

Example S1:

52.8 g (100 mmol) of LS2, 12.8 g (105 mmol) of phenylboronic acid [98-80-6], 48.9 g (150 mmol) of cesium carbonate, anhydrous, 1.43 g (2 mmol) of bis(triphenyl) A well-stirred mixture of phosphino)palladium dichloride, 100 g of glass beads (diameter 3 mmol) and 400 ml of THF is stirred at 60° C. for 24 hours. Once conversion is complete, the mixture, while still hot, is filtered through a bed of Celite in the form of a THF slurry, the filtrate is concentrated to dryness, and the residue is taken up in 500 ml of dichloromethane (DCM), 200 ml each time. Washed twice with water and once with 100 ml of saturated sodium chloride solution and dried over sodium sulfate. Filter the desiccant using a silica gel bed in the form of a DCM slurry, gradually concentrate the filtrate, gradually replace the DCM with about 200 ml of methanol, filter the crystallized product with suction, and wash with a small amount of methanol. Washed and dried under reduced pressure. Yield: 44.5 g (93 mmol) 93%; Purity: approx. 97% by ^1H NMR.

The following compounds can be prepared similarly:

Example S200:

Y. Imazaki et al., J. Am. Chem. Similar procedure to Soc., 2012 , 134, 14760.

47.9 g (100 mmol) of S1, 130.4 g (150 mmol) of lithium bromide, 2.54 g (5 mmol) of Cp*Ru(MeCN) ₃ OTf [113860-02-9], 100 g of glass beads (diameter 3 mm) and 400 ml of NMP are stirred at 100° C. for 40 hours. Upon completion of conversion, the glass beads are decanted, the NMP is removed under reduced pressure and the residue is taken up in 500 ml of ethyl acetate (EA), twice with 300 ml of water each time and once with 200 ml of saturated sodium chloride solution. Washed twice and dried over magnesium sulfate. The desiccant was filtered using a silica gel bed in the form of EA slurry, the filtrate was concentrated to dryness, the residue was stirred and extracted with 200 ml of hot methanol, the product was suction filtered, washed with a small amount of methanol and dried under reduced pressure. I ordered it. Yield: 36.9 g (90 mmol), 90%; Purity: Approximately 97% based on ¹ H NMR.

The following compounds can be prepared similarly:

B) Synthesis of Compounds of the Invention

Example A1:

A. G. Martinez et al., J. Chem. Soc., Perkin Trans. Procedure similar to I, 1986 , 1595. Palladium-charcoal (5% by weight) in a solution of 51.2 g (100 mmol) of S50 in a mixture of 500 ml of THF, 200 ml of methanol-D1 (H ₃ C-OD) and 16.6 ml (120 mmol) of triethylamine. After adding 2 g, stir in an autoclave at 40°C under deuterium (D ₂ ) at 2 bar for 30 hours. The reaction mixture was filtered through a bed of Celite in the form of a THF slurry, the filtrate was concentrated to dryness, the residue was taken up in 500 ml of DCM, washed twice with 200 ml of water each time and with 200 ml of saturated sodium chloride solution, dried over sodium sulfate. I ordered it. Filter the desiccant using a silica gel bed in the form of a DCM slurry, gradually concentrate the filtrate, gradually replace the DCM with about 150 ml of methanol, filter the crystallized product with suction, and add a small amount of methanol. and dried under reduced pressure. Further purification is carried out by repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or heat treatment under high vacuum. . Yield: 35.2 g (71 mmol), 71%; Purity: approximately 99.9% by HPLC.

The following compounds can be prepared similarly:

Example A100:

47.9 g (100 mmol) of S1, 31.6 g (110 mmol) of 9-phenylcarbazol-3-ylboronic acid [854952-58-2], 25.5 g (110 mmol) of potassium phosphate monohydrate, 1.16 ( A well-stirred mixture of 1 mmol) of tetrakis(triphenylphosphino)palladium(0), 500 ml of DMSO and 100 g of glass beads (3 mm in diameter) is stirred at 80° C. for 16 hours. Once conversion is complete, the mixture is allowed to cool, the glass beads are decanted, most of the DMSO is removed under reduced pressure, 300 ml of methanol and 200 ml of water are added to the residue, the crude product is filtered with suction and washed with 200 ml of methanol each time. Washed twice and dried under reduced pressure. The crude product was taken up in 300 ml of DCM and filtered through a bed of silica gel in the form of DCM slurry, the filtrate was concentrated to dryness, the residue was stirred and extracted with 200 ml of hot methanol, the crude product was filtered, and 50 ml each time. Washed twice with ml of methanol and dried under reduced pressure. Further purification is carried out by repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or heat treatment under high vacuum. . Yield: 35.2 g (71 mmol), 71%; Purity: approximately 99.9% by HPLC.

The following compounds can be prepared similarly:

Example A300:

40.9 g (100 mmol) of S200, 27.0 g (110 mmol) of 4-biphenylphenylamine [32228-99-2], 19.2 g (200 mmol) of sodium tert-butoxide, 304 mg (1.5 mmol) of Tri-tert-butylphosphine [13716-12-6] (alternatively other phosphines, e.g. tricyclohexylphosphine, bis(tert-butyl)-2-biphenylphosphine, S-Phos, It is also possible to use Heat for an hour. Carbazole can be converted similarly; The base used is for example preferably Cs ₂ CO ₃ rather than Na-Ot-Bu; The solvent used is o-xylene at 135°C; The catalyst used is, for example, preferably 2 mol% XanthPhos:1 mol% palladium(II) acetate. On completion of conversion, the mixture is cooled to about 80° C., 300 ml of water are added and the organic phase is separated, washed twice with 300 ml of water each time and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. Let's do it. The desiccant was filtered using a silica gel bed in the form of toluene slurry and washed with a small amount of toluene, the filtrate was concentrated to dryness, the residue was stirred and extracted with 200 ml of hot methanol, the crude product was filtered, and each time 50 ml of Washed twice with methanol and dried under reduced pressure. Further purification is carried out by repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or heat treatment under high vacuum. . Yield: 34.8 g (70 mmol), 70%; Purity: approximately 99.9% by HPLC.

The following compounds can be prepared similarly:

Example A500:

Well stirred mixture of 36.5 g (50 mmol) of S305, 6.3 g (70 mmol) of copper cyanide [544-92-3], 100 g of glass beads (3 mm in diameter) and 300 ml of dimethylacetamide (DMAC). The resulting mixture is heated to 160°C for 24 hours. The mixture, while still hot, was filtered with suction through a Celite bed in the form of a DMAC (dimethylacetamide) slurry, washed with 100 ml of hot DMAC, and the filtrate was concentrated under reduced pressure. The residue was taken up in 500 ml of DCM, 300 ml of 10% ammonia solution was added, the mixture was stirred for 1 hour, the organic phase was separated, once with 100 ml of 10% ammonia solution, three times with 100 ml of water each time and saturated chloride. It was washed once with 300 ml of sodium solution and dried over magnesium sulfate. The desiccant was filtered off using a silica gel bed in the form of a DCM slurry, the filtrate was concentrated under reduced pressure, the distillate was replaced with ethanol and the mixture was concentrated to a volume of approximately 100 ml. The precipitated product is suction filtered, washed three times with 50 ml of ethanol each time, and dried under reduced pressure. Further purification is carried out by repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or heat treatment under high vacuum. . Yield: 22.9 g (33.5 mmol), 67%; Purity: approximately 99.9% by HPLC.

The following compounds can be prepared similarly:

Example: Manufacturing of OLED

1) Vacuum-processed device:

The OLEDs of the invention and OLEDs according to the prior art are produced by the general method according to WO 2004/058911, adapted to the circumstances described here (variation of layer thickness, materials used).

In the examples below, results for various OLEDs are presented. Cleaned glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm (Miele laboratory glass washer, cleaned in Merck Extran detergent) are pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). These coated glass plates form the substrate to which the OLED is applied.

1a) Blue fluorescent OLED component - BF:

The compounds of the present invention can be used in hole injection layers (HIL), hole transport layers (HTL), and electron blocking layers (EBL). All materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer (EML) herein always consists of an emitting dopant (dopant, emitter) D and at least one matrix material (host material) SMB, which are added to the matrix material(s) in a specific volume ratio by co-evaporation (see Table 1 ). Details given in such a form as SMB:D (97:3%) mean here that the material SMB is present in the layer in a volume fraction of 97% and the dopant D in a fraction of 3%. Similarly, the electron transport layer may also consist of a mixture of two materials; See Table 1. The materials used in the manufacture of OLED are shown in Table 5.

OLEDs are characterized in a standard way. For this purpose, the current efficiency (measured in cd/A), power efficiency (in lm/W) as a function of luminance, calculated from the electroluminescence spectrum, the current-voltage-luminance characteristic (IUL characteristic) assuming Lambertian emission characteristics. measured) and external quantum efficiency (EQE, measured in %), and also the lifetime is determined. EQE in (%) and voltage in (V) are reported at a luminance of 1000 cd/m ² . The lifetime is determined at a starting luminance of 10 000 cd/m ² . LT80, a value in (h) units, is the measurement time for the brightness to drop to 80% of the initial brightness.

OLED has the following layer structure:

Board

Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm, or ex. In BF15, A309 doped with 5% NDP-9, 20nm

Hole transport layer (HTL), see Table 1

Electronic blocking layer (EBL), see Table 1

Emissive layer (EML), see Table 1

Electron transport layer (ETL1) composed of ETM1:ETM2 (50%:50%), 30　nm

Electron injection layer (EIL) composed of ETM2, 1 nm

Cathode made of aluminum, 100 nm

Table 1: Structure of blue fluorescent OLED components

Table 2: Results for blue flTable 2: Results for blue fluorescent OLED components

1b) Phosphorescent OLED component:

Compound A of the present invention can be used as a matrix material (host material) M (see Table 5) or A (see Table 5) in the hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL) and emission layer (EML). (see materials)). For this purpose, all materials are applied by thermal evaporation in a vacuum chamber. The emitting layer here always consists of at least one matrix material M and the phosphorescent dopant Ir, which is added to the matrix material(s) by co-evaporation in a specific volume proportion. Details given in the form M1:M2:Ir (55%:35%:10%), where material M1 is present in a volume fraction of 55% in the layer, M2 is present in a volume fraction of 35%, and Ir This means that it exists at a volume ratio of 10%. Similarly, the electron transport layer may also consist of a mixture of two materials. The exact structure of OLED can be found in Table 3. The materials used in the manufacture of OLED are shown in Table 5.

OLEDs are characterized in a standard way. For this purpose, the current efficiency (measured in cd/A), power efficiency (in lm/W) as a function of luminance, calculated from the electroluminescence spectrum, the current-voltage-luminance characteristic (IUL characteristic) assuming Lambertian emission characteristics. measured) and external quantum efficiency (EQE, measured in %), and also the lifetime is determined. EQE in (%) and voltage in (V) are reported at a luminance of 1000 cd/m ² . The lifetime is determined at a starting luminance of 1000 cd/m ² for the blue and red emitting components and at 10 000 cd/m ² for the green and yellow emitting components. LT80, a value in (h) units, is the measurement time for the brightness to drop to 80% of the initial brightness.

OLED has the following layer structure:

Board

Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (available from Novaled), 20 nm, or ex. In GP3, A101 doped with 5% NDP-9, 20 nm

Hole transport layer (HTL), see Table 3

Electronic blocking layer (EBL), see Table 3

Emission Layer (EML), see Table 3

Hole blocking layer (HBL), see Table 3

Electron transport layer (ETL1) composed of ETM1:ETM2 (50%:50%), 30　nm

Electron injection layer (EIL) composed of ETM2, 1 nm

Cathode made of aluminum, 100 nm

Table 3: Structure of phosphorescent OLED components

Table 4: Results for phosphorescent OLED components

Table 5: Structural formulas of materials used

Claims (9)

A compound of the formula (1) below.

The symbols used in the formula are as follows:
X is the same or different at each occurrence and is CR or N, provided that not more than two X groups per ring are N;
R' is the same or different in each case and is represented by D, F, Cl, Br, I, N(Ar ² ) ₂ , OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S( =O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case is substituted by one or more R ¹ radicals an aromatic or heteroaromatic ring system, which may be an aromatic or heteroaromatic ring system, provided that at least one or both R' comprises at least 1 nitrogen atom bonded to 3 carbon atoms, and at most 1 R' is N(Ar ² ) ₂ and any two groups bonded to Ar ² or at least one nitrogen atom in N(Ar ² ) ₂ are not connected or are connected via a single bond;
Ar ² is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R ¹ radicals;
R is the same or different in each case, H, D, F, Cl, Br, I, OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C (R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S(=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or A branched or cyclic alkyl group having 3 to 20 carbon atoms (said alkyl, alkenyl or alkynyl groups may in each case be substituted by one or more R ¹ radicals, and one or more non-adjacent CH ₂ groups may be -R ¹ C= CR ¹ -, -C≡C-, Si(R ¹ ) ₂ , NR ¹ , CONR ¹ , C=O, C=S, -C(=O)O-, P(=O)(R ¹ ), -O-, -S-, SO or SO ₂ ), or has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case with one or more R ¹ radicals an aromatic or heteroaromatic ring system which may be substituted, wherein two or more R radicals, preferably bonded to the same ring, together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring which may be substituted by one or more R ¹ radicals. Two R radicals bonded to the same carbon, silicon, germanium or tin atom together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ¹ radicals. You may;
Ar' is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R ¹ radicals;
R ¹ is the same or different in each case, H, D, F, I, B(OR ² ) ₂ , N(R ² ) ₂ , CHO, C(=O)R ² , CR ² =C(R ² ) ₂ , CN, C(=O)OR ² , Si(R ² ) ₃ , NO ₂ , P(= O)(R ² ) ₂ , OSO ₂ R ² , SR ² , OR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 carbon atoms or 2 to an alkenyl or alkynyl group having 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R ² radicals and one or more CH ₂ groups in the above-mentioned groups are -R ² C=CR ² -, -C≡C-, Si(R ² ) ₂ , C=O, C=S, -C(=O)O-, NR ² , CONR ² , P(=O)(R ² ), -O-, -S-, SO or SO ₂ and one or more hydrogen atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which in each case may be substituted by one or more R ² radicals, wherein two The above R ¹ radicals may be taken together to form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;
R ² is the same or different at each occurrence and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are also replaced by D or F may be; At the same time, two or more R ² substituents may be connected to each other or may form a ring. According to claim 1,
A compound selected from compounds of the following formulas (2), (3) and (4).

The symbols used herein have the definitions given in paragraph 1, and the following definitions are additionally applicable:
Ar ¹ is the same or different in each case and is a divalent aromatic or hetero group having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R ¹ radicals. It is an aromatic ring system;
R' is the same or different in each case and is D, F, Cl, Br, I, OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C(R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO ₂ , P( =O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S(=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , 5 to 60 aromatic ring atoms, preferably 5 to 60 aromatic ring atoms. is an aromatic or heteroaromatic ring system having 40 aromatic ring atoms, which in each case may be substituted by one or more R ¹ radicals;
s is the same or different in each case and is 0 or 1, where 0 means that N is directly bonded to the basic skeleton and at least one s in equation (4) is 1. The method of claim 1 or 2,
A compound selected from compounds of the following formulas (2-1), (3-1) and (4-1).

The symbols used in the formula have the definitions given in paragraph 2. A method for preparing a compound according to one or more of claims 1 to 3, comprising the following steps:
(A) synthesizing the basic skeleton of formula (1);
(B) coupling the R' radical
A method of producing a compound characterized by: An oligomer, polymer or dendrimer comprising at least one compound of formula (1) according to one or more of claims 1 to 3, wherein the linkage(s) to said polymer, oligomer or dendrimer is in formula (1) Oligomers, polymers or dendrimers, which can be located at any desired position. A formulation comprising at least one compound according to one or more of claims 1 to 3 and at least one further compound and/or at least one solvent. Use of the compound according to one or more of claims 1 to 3 or the formulation according to claim 6 in an electronic device. An electronic device comprising at least one compound according to one or more of claims 1 to 3, and/or at least one oligomer, polymer or dendrimer according to claim 5. According to claim 8,
An organic electroluminescent device, the device comprising an anode, a cathode and at least one emitting layer, wherein the at least one organic layer, which may be an emitting layer, a hole transport layer, an electron transport layer, a hole blocking layer, an electron blocking layer or another functional layer, has the formula: An electronic device comprising at least one compound of (1).