CN117917983A

CN117917983A - Material for organic electroluminescent device

Info

Publication number: CN117917983A
Application number: CN202280060004.1A
Authority: CN
Inventors: 斯特凡·施拉姆; 伊洛娜·施滕格尔; 阿米尔·侯赛因·帕勒姆; 菲利普·许茨
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2021-09-13
Filing date: 2022-09-12
Publication date: 2024-04-23
Also published as: WO2023036976A1; EP4402141A1; KR20240058919A

Abstract

The present invention relates to heterocyclic compounds of formula (1) substituted with at least one cyano group, and compositions and devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as host materials.

Description

Material for organic electroluminescent device

Heterocyclic derivatives substituted with at least one cyano group are described, as well as compositions and devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as host materials.

Phosphorescent organometallic complexes are often used as light-emitting materials in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, in particular OLEDs exhibiting triplet emission (phosphorescence), for example in terms of efficiency, operating voltage and lifetime. The nature of phosphorescent OLEDs is determined not only by the triplet emitters used. Other materials used, such as host materials or charge transport materials, are also particularly important here. Thus, improving these materials may also lead to improved OLED properties.

There is also room for improvement in OLEDs which exhibit singlet luminescence (fluorescence and/or thermally activated delayed fluorescence), as well as in efficiency, operating voltage and lifetime. Here too, the properties of the fluorescent OLED are determined not only by the singlet emitters, but also by the other materials used, such as host materials and charge transport materials. Thus, improving these materials may also lead to improved OLED properties.

A light-emitting compound is herein considered to mean a compound that emits light during operation of an electronic device. In this case, the host compound is considered to mean a compound present in a mixture in a higher proportion than the emitter compound. The term matrix compound and the term host compound may be used synonymously. The host compound preferably does not emit light. Even if a plurality of different host compounds are present in the mixture of light-emitting layers, their respective proportions are typically greater than the proportions of the light-emitting compounds, or if a plurality of light-emitting compounds are present in the mixture of light-emitting layers, their respective proportions are typically greater than the proportions of the various light-emitting compounds.

If a mixture of compounds is present in the light-emitting layer, the light-emitting compound is generally a component present in a smaller amount, i.e. in a smaller proportion than the other compounds present in the mixture of light-emitting layers. In this case, the emitter compound is also referred to as a dopant.

Host materials for organic electronic devices are well known to those skilled in the art. The term "host material" is also often used in the art when referring to host materials for phosphorescent emitters. This use of the term is also applicable to the present invention. Meanwhile, many host materials have been developed for both fluorescent and phosphorescent electronic devices.

According to the prior art, carbazole derivatives, indenocarbazole derivatives, indolocarbazole derivatives and azacarbazole derivatives belong to host materials for phosphorescent emitters. Host compounds comprising azacarbazole groups and carbazole groups have been disclosed in the prior art (e.g. in JP 2006120689). There is generally still a need for improvements in these materials used as host materials. The problem addressed by the present invention is to provide compounds which are particularly suitable for use as host materials in phosphorescent or fluorescent OLEDs or as electron transport materials.

Another means of improving the performance data of electronic devices, especially organic electroluminescent devices, is to use a combination of two or more materials, especially a combination of two or more host materials. For example, US 6,392,250 B1 discloses the use of a mixture of an electron-transporting material, a hole-transporting material and a fluorescent emitter in the light-emitting layer of an OLED. US 6,803,720B1 discloses the use of a mixture comprising a phosphorescent emitter and a hole-transporting material and an electron-transporting material in the light-emitting layer of an OLED.

However, in the case of using the host material or in the case of using a mixture of the host materials, improvements are still needed, in particular with respect to improvements in efficiency, operating voltage and/or lifetime of the organic electronic device.

Unexpectedly, it has been found that the compounds and mixtures comprising said compounds described in more detail below solve this problem and are particularly suitable for use in OLEDs. In particular, the OLED has a long lifetime, high efficiency and low operating voltage. The object of the present invention is therefore these compounds, mixtures comprising these compounds and electronic devices, in particular organic electroluminescent devices, comprising these compounds.

Accordingly, the present invention provides a compound of formula (1):

the symbols and labels used therein are as follows:

ar ¹ is a group of formula (Ar 1),

Wherein the method comprises the steps of

The dotted bond indicates the bonding position to the biphenyl group in formula (1);

X is identical or different at each occurrence and is CR ^X or N, or two X groups together form a fused ring, and

Provided that at least one X in the group of formula (Ar 1) is N;

Ar ² is a group of formula (Ar 2-A) or (Ar 2-B):

Wherein the method comprises the steps of

The dotted bond indicates the bonding position to the biphenyl group in formula (1); and

Y is the same or different at each occurrence and is CR ^Y or N; and two Y groups may together form a fused ring,

R ¹、R²、R^X、R^Y, identically or differently on each occurrence, represents a linear alkyl, alkoxy or thioalkyl group having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms, which may each be substituted by one or more R groups, where in each case one or more non-adjacent CH ₂ groups may be replaced by rc=cr, c≡ C, si (R) ₂、Ge(R)₂、Sn(R)₂、C＝O、C＝S、C＝Se、P(＝O)(R)、SO、SO₂, O, S or CONR and where 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 be substituted by one or more R groups in each case, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R groups;

Wherein two R ¹ groups, two R ² groups, two R ^x groups, two R ^y groups may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more R groups;

R, identically or differently on each occurrence, represents ：H,D,F,Cl,Br,I,CHO,CN,C(＝O)Ar,P(＝O)(Ar)₂,S(＝O)Ar,S(＝O)₂Ar,N(R′)₂,N(Ar)₂,NO₂,Si(R^′)₃,B(OR′)₂,OSO₂R^′, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40C atoms, which may each be substituted by one or more R ^′ groups, where in each case one or more non-adjacent CH ₂ groups may be replaced by R^′C＝CR^′、C≡C、Si(R^′)₂、Ge(R^′)₂、Sn(R^′)₂、C＝O、C＝S、C＝Se、P(＝O)(R^′)、SO、SO₂、O、S or CONR ^′ and where 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 R ^′ groups, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ^′ groups; wherein two R groups may together form an aliphatic or aromatic ring system, which may be substituted with one or more R' groups;

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

R ^′, identically or differently, represents at each occurrence: h, D, F, cl, br, I, CN, a linear alkyl, alkoxy or thioalkyl group having from 1 to 20C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having from 3 to 20C atoms, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by SO, SO ₂, O, S and wherein one or more H atoms may be replaced by D, F, cl, br or I, or an aromatic or heteroaromatic ring system having from 5 to 24 aromatic ring atoms; and

N is the same or different at each occurrence and is 0, 1,2 or 3;

m is identical or different on each occurrence and is 0, 1,2, 3 or 4.

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

Aryl groups in the sense of the present invention contain 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; heteroaryl groups in the sense of the present invention contain 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and S. This represents the basic definition. If other preferred matters are indicated in the description of the present invention, for example, with respect to the number of aromatic ring atoms or heteroatoms present, these matters are in control.

Aryl groups or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, for example pyridine, pyrimidine or thiophene, or fused (ring-extended) aromatic or heteroaromatic polycyclic rings, for example naphthalene, phenanthrene, quinoline or carbazole. A fused (added ring) aromatic or heteroaromatic polycyclic in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings fused to each other.

Aryl or heteroaryl groups which may in each case be substituted by the abovementioned groups and which may be linked to the aromatic or heteroaromatic ring system via any desired position are to be regarded as meaning in particular groups which originate from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene,Perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoOxazine, pyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole,Oxazole, benzoAzole, naphthoAzole, anthraceneAzole, phenanthroOxazole, isoOxazole, 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-Diazole, 1,2,4-Diazole, 1,2,5-Diazole, 1,3,4-Diazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizines, and benzothiadiazoles.

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

An aromatic ring system in the sense of the present invention contains 6 to 60C atoms, preferably 6 to 40C atoms, more preferably 6 to 20C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of the present invention is intended to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can also be linked by non-aromatic units (preferably less than 10% of the non-H atoms), for example sp ³ -hybridized C, si, N or O atoms, sp ² -hybridized C or N atoms or sp-hybridized C atoms. Thus, for example, systems such as 9,9 '-spirobifluorene, 9' -diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be considered aromatic ring systems in the sense of the present invention, and so are systems in which two or more aryl groups are linked, for example, by chain or cyclic alkyl, alkenyl or alkynyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to each other by single bonds, for example systems such as biphenyl, terphenyl or diphenyltriazine, are also considered aromatic or heteroaromatic ring systems in the sense of the invention.

An aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may also be substituted in each case by a group as defined above and which may be linked to the aromatic or heteroaromatic group by any desired position, is considered to mean in particular a group derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene,Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, tetrabiphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, trimeric indene, spirotetralin, spiro-isothianaphthene, 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, phenoOxazine, pyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole,Oxazole, benzoAzole, naphthoAzole, anthraceneAzole, phenanthroAzole, isoOxazole, 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, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoOxazine, phenothiazine, fluororuber, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2,3-Diazole, 1,2,4-Diazole, 1,2,5-Diazole, 1,3,4-Diazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizines, and benzothiadiazoles, or combinations of these groups.

For the purposes of the present invention, a linear alkyl group having from 1 to 40C atoms or a branched or cyclic alkyl group having from 3 to 40C atoms or an alkenyl or alkynyl group having from 2 to 40C atoms, where the individual H atoms or CH ₂ groups may also be substituted by the groups mentioned above under the definition of the groups, such groups preferably being considered to mean the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. Alkoxy or thioalkyl having 1 to 40C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctyloxy, 2-ethylhexoxy, pentafluoroethoxy, 2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio tert-butylthio, n-pentylthio, zhong Wuliu-yl, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, acetylenylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or Xin Guiliu-yl.

For the purposes of the present application, the expression that two groups can form a ring with each other is intended to be understood as meaning, in particular, that the two groups are linked to each other by chemical bonds. This is illustrated by the following scheme:

however, in addition, the above expression is also intended to be taken to mean that, in the case where one of the two groups represents hydrogen, the second group is bonded at the position where the hydrogen atom is bonded, and forms a ring. This is illustrated by the following scheme:

When two groups form a ring with each other, then preferably the two groups are adjacent groups. Adjacent groups in the sense of the present invention are groups bonded to atoms directly connected to each other or bonded to the same atom.

According to a preferred embodiment, the compound of formula (1) is selected from the group consisting of compounds of formulae (1-1) to (1-6),

Wherein the symbols have the definition as described above.

According to a very preferred embodiment, the compound of formula (1) is selected from the group consisting of compounds of formulae (1-1-1) to (1-6-2),

Wherein the symbols have the definition as described above.

Preferably the Ar ¹ group is selected from the group consisting of groups of formulae (Ar 1-1) to (Ar 1-14),

Wherein the dotted bond indicates a bond to a biphenyl group in formula (1) or formulae (1-1) to (1-5), wherein the symbol R ^X has the definition given above and wherein:

p is independently at each occurrence 0, 1,2, 3 or 4;

q is independently at each occurrence 0, 1, 2 or 3.

Among the formulae (Ar 1-1) to (Ar 1-14), the formulae (Ar 1-1), (Ar 1-3) and (Ar 1-5) are preferable, and the formula (Ar 1-1) is very preferable.

It is also preferred that the Ar ² groups are selected from the groups of formulae (Ar 2-A1) to (Ar 2-A15) and (Ar 2-B1),

Wherein the dashed bond indicates a bond to the biphenyl group in formula (1), wherein the symbol R ^Y has the definition given above and wherein:

s is independently at each occurrence 0, 1,2, 3 or 4;

t is independently at each occurrence 0, 1, 2 or 3.

Among the formulae (Ar 2-A1) to (Ar 2-A15) and (Ar 2-B1), the formulae (Ar 2-A1), (Ar 2-A5), (Ar 2-A7), (Ar 2-B1) are preferable, and the formulae (Ar 2-A1) and (Ar 2-B1) are very preferable.

Preferably, the Ar ¹ group is a group of formula (Ar 1-1) and the Ar ² group is a group of formula (Ar 2-A1) or (Ar 2-B1).

Preferably, R ¹、R²、R^X、R^Y, at each occurrence, is the same or different and represents: h, D, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms, which may each be substituted by one or more R groups, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by rc=cr, c≡ C, O or S and wherein one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more R groups.

More preferably, R ¹、R²、R^X、R^Y, at each occurrence, is the same or different and represents: h, D, F, a linear alkyl group having from 1 to 20, preferably from 1 to 10, more preferably from 1 to 6C atoms or a branched or cyclic alkyl group having from 3 to 20, preferably from 3 to 10, more preferably from 3 to 6C atoms, which alkyl groups may each be substituted by one or more R groups, an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, more preferably from 5 to 18, aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more R groups.

Particularly preferably, R ¹、R²、R^X、R^Y, at each occurrence, is identical or different and represents: h, D, a linear alkyl group having from 1 to 10, preferably from 1 to 6, C atoms or a branched or cyclic alkyl group having from 3to 10, preferably from 3to 6, C atoms, which may each be substituted by one or more R groups, or an aromatic or heteroaromatic ring system having from 5to 18, preferably from 6 to 12, aromatic ring atoms, which may in each case be substituted by one or more R groups.

Very particularly preferably, R ¹、R²、R^X、R^Y represents H or D.

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

the present invention also provides a composition comprising a material selected from the group consisting of the compounds of formula (1) as defined above and a material selected from the group consisting of hole transporting host materials.

Preferably, the second host material in the composition is selected from: hole transporting host materials selected from carbazole derivatives and triarylamine derivatives, more particularly bicarbazole, bridged carbazole, triarylamine, dibenzofuran-carbazole derivatives or dibenzofuran-amine derivatives, and carbazole amines.

According to a preferred embodiment, the second host material is selected from hole transporting host materials selected from compounds of formula (h-1) or (h-2),

Wherein:

k is Ar ⁴ or-L ²-N(Ar)₂;

Z is C-R ^Z or C-R ^A, or two adjacent Z groups together form a fused ring;

R _A is-L ³-Ar⁵ or-L ¹-N(Ar)₂;

R ^Z is identical or different on each occurrence and is selected from ：H,D,F,Cl,Br,I,N(Ar)₂,N(R)₂,OAr,SAr,CN,NO₂,OR,SR,COOR,C(＝O)N(R)₂,Si(R)₃,B(OR)₂,C(＝O)R,P(＝O)(R)₂,S(＝O)R,S(＝O)₂R,OSO₂R, a linear alkyl group having from 1 to 20 carbon atoms or an alkenyl or alkynyl group having from 2 to 20 carbon atoms or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups may in each case be substituted by one or more R groups, where one or more non-adjacent CH ₂ groups may be replaced by Si (R) ₂, c= O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, preferably from 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R groups;

L ¹、L² is identical or different on each occurrence and is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which may be substituted by one or more R groups;

L ³ is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which may be substituted with one or more R groups, wherein one R group on L ³ may form a ring with an R ^Z group on carbazole;

Ar ⁴ is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted with one or more R groups;

Ar ⁵ is identical or different at each occurrence and is an unsubstituted or substituted heteroaromatic ring system having from 5 to 40 aromatic ring atoms, which heteroaromatic ring system may be substituted by one or more R;

r ^Z is identical or different on each occurrence and is ：H,D,F,Cl,Br,I,N(Ar)₂,N(R)₂,OAr,SAr,CN,NO₂,OR,SR,COOR,C(＝O)N(R)₂,Si(R)₃,B(OR)₂,C(＝O)R,P(＝O)(R)₂,S(＝O)R,S(＝O)₂R,OSO₂R, a linear alkyl group having from 1 to 20 carbon atoms or an alkenyl or alkynyl group having from 2 to 20 carbon atoms or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups may in each case be substituted by one or more R groups, where one or more non-adjacent CH ₂ groups may be replaced by Si (R) ₂, c= O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, preferably from 5 to 40 aromatic ring atoms, and which may in each case be substituted by one or more R groups; at the same time, two R ^Z groups together may also form a ring system;

E is independently at each occurrence a single bond or C (R ⁰)₂ group;

R ⁰ is independently selected at each occurrence from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, which alkyl group may be substituted in each case with one or more R' groups;

x, y are independently selected from 0 or 1, wherein when x or y is 0 then the corresponding E group is absent; and x+y=1 or 2;

Provided that the compounds of formulae (h-1) and (h-2) comprise at least one Z group representing R ^A;

And wherein R, R' and Ar have the same definition as above.

Preferably, L ¹、L² is the same or different at each occurrence and is a single bond or an aromatic or heteroaromatic ring system having 5 to 25, more preferably 5 to 20, even more preferably 6 to 18 aromatic ring atoms and which may be substituted with one or more R groups.

Preferably, L ³ is a single bond or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, more preferably 5 to 20, still more preferably 6 to 18 aromatic ring atoms and which may be substituted with one or more R groups, wherein one R group on L ³ may form a ring with an R ^Z group on carbazole.

Preferably, the Ar ⁵ group is an unsubstituted or substituted heteroaromatic ring system selected from the group consisting of the formulae (Ar 5-1) to (Ar 5-6),

Wherein the dashed bond indicates a bond to L ³ or Z;

V is C-R ^V, provided that when V is bonded to a group of formula (h-1) or (h-2), V represents C; or two adjacent V groups together form a fused ring;

t is C-R ^T, provided that when T is bonded to a group of formula (h-1) or (h-2), T represents C, or two adjacent T groups together form a fused ring;

M is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted with one or more R groups;

E ¹ is independently a single bond or C (R ⁰)₂ group; wherein R ⁰ has the same definition as above;

R ^T、R^V is identical or different on each occurrence and is selected from ：H,D,F,Cl,Br,I,N(Ar)₂,N(R)₂,OAr,SAr,CN,NO₂,OR,SR,COOR,C(＝O)N(R)₂,Si(R)₃,B(OR)₂,C(＝O)R,P(＝O)(R)₂,S(＝O)R,S(＝O)₂R,OSO₂R, a linear alkyl group having from 1 to 20 carbon atoms or an alkenyl or alkynyl group having from 2 to 20 carbon atoms or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups may in each case be substituted by one or more R groups, where one or more non-adjacent CH ₂ groups may be replaced by Si (R) ₂, c= O, NR, O, S or CONR, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, preferably from 5 to 40 aromatic ring atoms, and in each case may be substituted by one or more R groups; at the same time, two R ^T groups together may form a ring system and two R ^V groups together may form a ring system;

x ¹、y¹ is independently selected from 0 or 1, wherein when x ¹ or y ¹ is 0 then the corresponding E ¹ group is absent; provided that x ¹+y¹ = 1 or 2;

and wherein R and Ar have the same definition as above.

According to a very preferred embodiment, the second host material is selected from hole transporting host materials selected from compounds of formulae (h-1-1) to (h-1-3) and (h-2-1) to (h-2-2),

Wherein the symbols and labels x, y, x ¹ and y ¹ have the same definition as above, and wherein the other labels have the following meanings:

c. f independently represents 0, 1, 2, 3 or 4;

d. e independently represents 0, 1, 2 or 3;

g: if x ¹ = 0, g represents 0,1, 2 or 3; or if x ¹ = 1, g represents 0,1 or 2;

h: if y ¹ = 0, h represents 0, 1,2, 3 or 4; or if y ¹ =1, h represents 0, 1,2 or 3;

k: if x=0, k represents 0, 1, 2,3 or 4; or if x=1, k represents 0, 1, 2 or 3; and

L: if y=0, l represents 0, 1,2 or 3; or if y=1, l represents 0, 1 or 2.

Examples of hole transporting host materials suitable as the second host material in the composition are depicted in the following table:

preferably, the composition comprises a first host material selected from the group of compounds of formula (1) as defined above, a second host material selected from the group of hole transporting host materials, and a third compound selected from the group of phosphorescent emitters, fluorescent emitters and emitters exhibiting TADF (thermally activated delayed fluorescence).

According to a preferred embodiment, the third compound is selected from phosphorescent emitters. Phosphorescence in the context of the present application is understood to mean luminescence from an excited state with a higher spin severity, i.e. a spin state >1, in particular from an excited triplet state. In the context of the present application, all luminescent complexes with transition metals or lanthanides, in particular all complexes of iridium, platinum and copper, should be regarded as phosphorescent emitters.

Examples of the above-mentioned luminophores can be found in ：WO 00/70655、WO 2001/41512、WO 2002/02714、WO 2002/15645、EP 1191613、EP 1191612、EP 1191614、WO 05/033244、WO 05/019373、US 2005/0258742、WO 2009/146770、WO 2010/015307、WO 2010/031485、WO 2010/054731、WO 2010/054728、WO 2010/086089、WO 2010/099852、WO 2010/102709、WO 2011/032626、WO 2011/066898、WO 2011/157339、WO 2012/007086、WO 2014/008982、WO 2014/023377、WO 2014/094961、WO 2014/094960、WO 2015/036074、WO 2015/104045、WO 2015/117718、WO 2016/015815、WO 2016/124304、WO 2017/032439、WO 2018/011186 and WO 2018/04769, WO 2019/020538, WO 2018/178001, WO 2019/115423 or WO 2019/158453 in the following applications. In general, all phosphorescent complexes which are used in phosphorescent OLEDs according to the prior art and are 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 other phosphorescent complexes without inventiveness.

Examples of phosphorescent dopants are depicted below:

According to another preferred embodiment, the third compound is selected from luminophores exhibiting thermally activated delayed fluorescence (TADF luminophores) (e.g. h. Uoyama et al, nature (Nature) 2012, volume 492, 234). These emitters are organic materials in which the energy gap between the lowest triplet state T ₁ and the first excited singlet state S ₁ is sufficiently small that the S ₁ state can be reached by heat from the T ₁ state. The TADF luminophore is preferably an aromatic compound having both donor and acceptor substituents with only slight spatial overlap between LUMO and HOMO of the compound. The understanding of donor substituents and acceptor substituents is known in principle to the person skilled in the art. Suitable donor substituents are in particular diaryl-or-heteroarylamino groups and carbazole groups or carbazole derivatives, each of which is preferably bonded to the aromatic compound via an N. These groups may also have further substitutions. Suitable acceptor substituents are in particular cyano groups, but also, for example, electron-deficient heteroaryl groups, which may also have further substitutions, for example substituted or unsubstituted triazine groups.

The general technical knowledge of the person skilled in the art includes knowledge of which materials are generally suitable as TADF compounds. For example, the following references disclose materials potentially suitable as TADF compounds:

Tanaka et al, materials chemistry (CHEMISTRY OF MATERIALS) 25 (18), 3766 (2013).

Lee et al, journal C (Journal of MATERIALS CHEMISTRY C) 1 (30), 4599 (2013).

Zhang et al, nature Photonics, 1 (2014), doi:10.1038/nphoton.2014.12.

Serevicius et al, physicochemical physical (PHYSICAL CHEMISTRY CHEMICAL PHYSICS) 15 (38), 15850 (2013).

-Li, etc., advanced materials (ADVANCED MATERIALS) 25 (24), 3319 (2013).

You Lee et al, application physical flash (APPLIED PHYSICS LETTERS) 101 (9), 093306 (2012).

Nishimoto et al, material View (MATERIALS HORIZONS) 1, 264 (2014), doi:10.1039/C3MH00079F.

Valchanov, etc., electronics (Organic Electronics), 14 (11), 2727 (2013).

Nasu et al, chemical communication (ChemComm), 49, 10385 (2013).

In addition, the following patent applications disclose potential TADF compounds ：WO2013/154064、WO 2013/133359、WO 2013/161437、WO 2013/081088、WO 2013/081088、WO 2013/011954、JP 2013/116975 and US 2012/024192.

Furthermore, the design principle of TADF compounds can be deduced from these publications by a person skilled in the art. For example Valchanov et al demonstrate how the color of TADF compounds can be adjusted.

Examples of suitable molecules exhibiting TADF are the structures shown in the following table:

According to yet another preferred embodiment, the third compound is selected from the group consisting of fluorescent emitters. Preferred fluorescent emitters are aromatic anthracamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic Amines or aromaticsA diamine. Aromatic anthraceneamines are understood to mean compounds in which one diarylamino group is directly bonded to an anthracene group, preferably directly bonded in the 9-position. Aromatic anthracenediamine is considered to mean a compound in which two diarylamino groups are directly bonded to the anthracene group, preferably directly bonded in the 9,10 position. Aromatic pyrenamines,Amine andThe definition of diamine is similar, with diarylamino groups preferably bonded to pyrene in the 1-position or in the 1, 6-positions. Other preferred fluorescent emitters are indenofluorene amines or indenofluorene diamines, for example according to WO 2006/108497 or WO 2006/122630, benzoindenofluorene amines or benzoindenofluorene diamines, for example according to WO 2008/006449, and dibenzoindenofluorene amines or dibenzoindenofluorene diamines, for example indenofluorene derivatives containing fused aryl groups, as disclosed in WO 2007/140847, and in WO 2010/012328. Still other preferred luminophores are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers linked through heteroaryl groups as in WO 2016/150244 or pheno/>, as disclosed in WO 2017/028940 and WO 2017/028941An oxazine derivative. Also preferred are pyrene aryl amines disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are benzoindenofluorene disclosed in WO 2014/037077, benzofluorenamine disclosed in WO 2014/106522, and indenofluorene disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421. Luminophores comprising dibenzofuran or indenodibenzofuran moieties as disclosed in WO 2018/095888, WO 2018/095940, WO 2019/076789, WO 2019/170572 and in WO2020/043657, WO2020/043646 and WO/2020/043640 are also preferred. Also preferred are, for example, boron derivatives as disclosed in WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 and in WO 2020/208051, WO2021/058406 and WO 2021/094269.

According to another preferred embodiment, the composition comprises a first host material selected from the compounds of formula (1) as defined above, a second host material selected from hole transporting host materials, a third compound selected from phosphorescent emitters and emitters exhibiting TADF (thermally activated delayed fluorescence), and a fourth compound selected from phosphorescent emitters and fluorescent emitters.

Particularly preferred examples of such compositions are the following compositions comprising:

-a first host material selected from the group of compounds of formula (1) as defined above, a second host material selected from the group of hole transporting host materials, a third compound selected from the group of phosphorescent emitters and a fourth compound selected from the group of phosphorescent emitters, wherein the selection of the third and fourth compounds is different;

-a first host material selected from the group of compounds of formula (1) as defined above, a second host material selected from the group of hole transporting host materials, a third compound selected from the group of phosphorescent emitters and a fourth compound selected from the group of fluorescent emitters;

-a first host material selected from the group of compounds of formula (1) as defined above, a second host material selected from the group of hole transporting host materials, a third compound selected from the group of emitters exhibiting TADF (thermally activated delayed fluorescence) and a fourth compound selected from the group of fluorescent emitters;

preferred host materials, phosphorescent emitters, TADF emitters and fluorescent emitters are described above.

The composition may also comprise other organic or inorganic compounds as well used in electronic devices, such as other luminophores or other host materials.

The compound of formula (1) or the composition comprising the compound of formula (1) may be processed by vapor deposition or from solution. If the composition is applied from a solution, a formulation of the composition of the invention comprising at least one other solvent is required. For example, these formulations may be solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents.

The invention therefore also provides a formulation comprising a compound of formula (1) or a composition comprising a compound of formula (1) and at least one solvent.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, di-An alkane, phenoxytoluene, especially 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylindane), or mixtures of these solvents.

The invention also provides the use of the compound of formula (1) or a composition comprising the compound of formula (1) in an organic electronic device, preferably in a light-emitting layer and/or in an electron transport layer.

The organic electronic device is preferably selected from the group consisting of Organic Integrated Circuits (OIC), organic Field Effect Transistors (OFET), organic Thin Film Transistors (OTFT), organic electroluminescent devices, organic Solar Cells (OSC), organic optical detectors and organic photoreceptors, particularly preferred are organic electroluminescent devices.

Particularly preferred organic electroluminescent devices containing at least one compound of the formula (1) as described above or as described as preferred are Organic Light Emitting Transistors (OLET), organic Field Quench Devices (OFQDs), organic light emitting electrochemical cells (OLEC, LEC, LEEC), organic laser diodes (O-lasers) and Organic Light Emitting Diodes (OLEDs); particularly preferred are OLECs and OLEDs, most preferred are OLEDs.

Preferably, the compounds of formula (1) as described above or as preferably described are used in layers with electron transport functions in electronic devices. The layer is preferably an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL) and/or an emitting layer (EML), more preferably an ETL, EIL and/or an EML. Most preferably, the compound of formula (1) or the composition is used in EML as an electron transporting host material in combination with a hole transporting host material.

The invention therefore also provides an organic electronic device, which is in particular selected from one of the aforementioned electronic devices and comprises a compound of formula (1) or a composition comprising said compound of formula (1) as described above or as preferred, preferably in the light emitting layer (EML), in the Electron Transporting Layer (ETL), in the Electron Injecting Layer (EIL) and/or in the Hole Blocking Layer (HBL), very preferably in the EML, EIL and/or ETL, most preferably in the EML comprising said compound of formula (1) or said composition.

In a particularly preferred embodiment of the invention, the electronic device is an organic electroluminescent device, most preferably an Organic Light Emitting Diode (OLED), which contains the compound of formula (1) or a composition comprising the compound of formula (1) in a light emitting layer (EML).

Thus, in a particularly preferred embodiment of the invention, the organic electroluminescent device is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer comprising at least one light emitting layer, wherein the at least one light emitting layer comprises: at least one of said compounds of formula (1) or a composition comprising a compound of formula (1) as described above.

The light-emitting layer in the device of the invention as described above contains, based on the total composition of the light-emitting body and the host material, preferably between 99.9 and 1% by volume, further preferably between 99 and 10% by volume, particularly preferably between 98 and 60% by volume, very particularly preferably between 97 and 80% by volume, of a host material consisting of at least one compound of the formula (1) or of at least one first host material selected from the compounds of the formula (1) and of a second host material selected from the hole-transporting host materials as described above. Accordingly, the light-emitting layer in the device of the invention preferably contains between 0.1 and 99% by volume, further preferably between 1 and 90% by volume, more preferably between 2 and 40% by volume, most preferably between 3 and 20% by volume of said light-emitting body, based on the total composition of the light-emitting layer consisting of light-emitting body and host material. If the compounds are processed from solution, it is preferred to use the corresponding amounts in% by weight rather than the amounts specified above in% by volume.

The light emitting layer in the device of the invention as described above preferably contains the host material of formula (1), preferably in combination with a host material selected from hole transporting host materials in a volume percentage ratio between 3:1 and 1:3, preferably between 1:2.5 and 1:1, more preferably between 1:2 and 1:1. If the compounds are processed from solution, the corresponding ratios in% by weight are preferably used instead of the ratios specified above in% by volume.

In addition to the cathode, anode and layers comprising the composition of the invention, the electronic device may comprise other layers. These layers are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, light-emitting layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge Generation layers (IDMC 2003, taiwan; session 21OLED (5), T.Matsumoto, T.Nakada, J.Endo, K.Mori, N.Kawamura, A.Yokoi, J.Kido, multiphoton organic EL devices with charge Generation layers (Multiphoton Organic EL DEVICE HAVING CHARGE Generation layers)) and/or organic or inorganic p/n junctions in each case. However, it should be noted that each of these layers need not necessarily be present.

The sequence of layers in the organic electroluminescent device is preferably as follows:

Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode.

The order of the layers is the preferred order.

Also, it should be noted again that not all of the mentioned layers need be present and/or that other layers may also be present.

The organic electroluminescent device of the present invention may contain two or more light emitting layers. According to the present invention, at least one of the light emitting layers contains at least one of the compounds of formula (1) and a composition comprising the compound of formula (1) as described above. More preferably, in this case, the light emitting layers generally have a plurality of light emission peaks between 380nm and 750nm, so that the overall result is white light emission; in other words, a plurality of light-emitting compounds which can emit fluorescence or phosphorescence and blue or yellow or orange or red light are used in the light-emitting layer. Particularly preferred are three-layer systems, i.e. systems with three light-emitting layers, wherein the three layers display blue, green and orange or red light emission (see for example WO 2005/01013 for basic structure). It should be noted that, in order to generate white light, instead of a plurality of light-emitting body compounds that emit light in a wide wavelength range, it may also be appropriate to use one light-emitting body compound alone.

Suitable charge transport materials that can be used in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the organic electroluminescent device of the present invention are, for example, compounds disclosed in y.shirooa et al, chemical reviews (chem. Rev.) 2007, 107 (4), 953-1010, or other materials used in these layers according to the prior art.

The material for the electron transport layer may be any material that is used as an electron transport material in an electron transport layer according to the prior art. Particularly suitable are: aluminum complexes, such as Alq ₃, zirconium complexes, such as Zrq ₄, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives,Diazole derivatives, aromatic ketones, lactams, boranes, diazaphospha-cyclopentadiene derivatives and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred hole transporting materials are in particular materials which can be used in the hole transporting layer, the hole injecting layer or the electron blocking layer, for example indenofluorene derivatives (for example according to WO 06/122630 or WO 06/100896), amine derivatives disclosed in EP 1661888, hexaazapolytrimethylene derivatives (for example according to WO 01/049806), amine derivatives with fused aromatic systems (for example according to US 5,061,569), amine derivatives disclosed in WO 95/09147, mono-benzoindenofluorene derivatives (for example according to WO 08/006449), dibenzoindenofluorene derivatives (for example according to WO 07/140847), spirobifluorene derivatives (for example according to WO 2012/034627 or EP 12000929.5 not yet published), fluorenamines (for example according to WO 2014/015937, WO 2014/015938 and WO 2014/015935), spirodibenzopyranamines (for example according to WO 2013/083216) and dihydro-acridine derivatives (for example according to WO 2012012/150001).

Preferred cathodes for electronic devices are metals, metal alloys or multilayer structures with low work functions, which are composed of various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, ba, mg, al, in, mg, yb, sm, etc.). Also suitable are alloys of alkali metals or alkaline earth metals with silver, for example alloys of magnesium and silver. In the case of multilayer structures, other metals with a relatively high work function, such as Ag or Al, can be used in addition to the metals mentioned, in which case combinations of the metals, such as Ca/Ag, mg/Ag or Ba/Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are fluorides of alkali metals or alkaline earth metals, and the corresponding oxides or carbonates (e.g. LiF, li ₂O、BaF₂、MgO、NaF、CsF、Cs₂CO₃, etc.). Lithium hydroxyquinoline (Liq) may also be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5eV relative to vacuum. First, metals with a high redox potential, such as Ag, pt or Au, are suitable for this. Second, metal/metal oxide electrodes (e.g., al/Ni/NiO _x、Al/PtO_x) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to irradiate organic materials (organic solar cells) or emit light (OLED, O-laser). The preferred anode material herein is a conductive mixed metal oxide. Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) is particularly preferred. Furthermore, preference is given to conductively doped organic materials, in particular conductively doped polymers. In addition, 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.

Since the lifetime of the device of the invention is reduced in the presence of water and/or air, the organic electronic device is properly structured during production (depending on the application), the contacts are connected and finally sealed.

In another preferred embodiment, an organic electronic device comprising the composition of the invention is characterized in that one or more organic layers comprising the composition of the invention are coated by sublimation. 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. In this case, however, the initial pressure may also be even lower, for example less than 10 ^-7 mbar.

Also preferred are organic electroluminescent devices as described below, characterized in that the layer or layers are applied by the OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, the material is applied at a pressure of between 10 ^-5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and is structured thereby (e.g. m.s. arnold et al, applied physical fast report (appl. Phys. Lett.) 2008, 92, 053301).

Also preferred are organic electroluminescent devices as described below, characterized in that one or more organic layers comprising the composition of the invention are produced from a solution, for example by spin coating or by any printing method, for example screen printing, flexography, nozzle printing or offset printing, but more preferably LITI (photoinitiated thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble compounds of the components of the compositions of the invention are required. High solubility can be obtained by appropriate substitution of the corresponding compounds. The advantage of processing from solution is that the layer comprising the composition according to the invention can be applied in a very simple and inexpensive manner. This technique is particularly suitable for mass production of organic electronic devices.

In addition, a hybrid process is possible, for example, in which one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

The invention therefore also provides a method for manufacturing an organic electronic device comprising the composition of the invention as described above or as preferably described, characterized in that at least one organic layer comprising the composition of the invention is applied by vapor deposition, in particular by sublimation and/or by OVPD (organic vapor deposition) method and/or sublimation by means of a carrier gas, or from solution, in particular by spin coating or by printing methods.

In the manufacture of organic electronic devices by vapor deposition, there are in principle two methods by which an organic layer to be comprised of the composition of the present invention and which may comprise a variety of different components can be applied to any substrate, or by vapor deposition. First, the materials used may each be initially supported in a material source and ultimately vaporized ("co-vaporized") from a different material source. Second, the various materials may be pre-mixed (a premix system), and the mixture may be initially supported in a single material source, ultimately being vaporized from the material source ("premix vaporization"). In this way, vapor deposition of a layer of uniformly distributed composition can be achieved in a simple and rapid manner without precisely driving the various material sources.

The present invention therefore also provides a process characterized in that the at least one compound of formula (1) as described above or as described preferably and a composition comprising a compound of formula (1) as described above or as described preferably are deposited from the vapor phase, from at least two material sources, optionally together with other materials as described above or as described preferably, sequentially or simultaneously, and an organic layer is formed.

The present invention therefore also provides a process characterized in that the composition of the invention as described above or as preferably described is used as a source of material for the vapour deposition of a host system, optionally together with other materials, to form an organic layer.

The invention also provides a method of manufacturing an organic electronic device comprising the composition of the invention as described above or as preferably described, characterized in that the formulation of the invention as described above is used for applying the organic layer.

It should be noted that the scope of the present invention covers variations of the embodiments described in the present invention. Any feature disclosed in this application may be replaced by an alternative feature serving the same, equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise indicated, any feature disclosed in this specification should be considered as an example of a generic series or equivalent or similar feature.

All features of the invention may be combined with each other in any way, unless the specific features and/or steps are mutually exclusive. This is especially true for the preferred features of the invention. Also, features in unnecessary combinations may be used separately (without combination).

The technical teachings of the present disclosure may be refined and combined with other examples. The following examples illustrate the invention in more detail, but are not intended to limit the invention in any way.

Synthesis example

The synthesis scheme is as follows:

Synthesis of 3-bromo-5-gamma-carboline benzonitrile

A 1000mL three-necked flask was flushed three times with vacuum and nitrogen. To the flask was added 3.56g (0.148 mol,2.0 eq.) of 60% NaH (suspension in paraffin oil) and 100mL of dry DMF under nitrogen atmosphere. The reaction mixture was cooled to 0-5℃with an ice bath, and then a solution of 12.5g (1.0 eq,0.074 mol) of 5H-pyrido [4,3-b ] indole in 150mL of dry DMF was added at 0-5 ℃. The reaction mixture was stirred at 0-5 ℃ for 30 minutes. A solution of 15.6g (1.05 eq,0.078 mol) of 3-bromo-5-fluorobenzonitrile in 120mL of dry DMF is then added at 0-5 ℃. Stirring of the reaction mixture was continued overnight at 150 ℃.

For work-up, the reaction mixture was taken up in water (300 mL) and saturated aqueous NH4Cl solution (70 mL) in a further round-bottomed flask, cooled to 5-10 ℃, and the reaction mass was added dropwise via a dropping funnel. The product precipitated and was filtered and washed with water (100 mL).

For further purification, the crude product was dissolved in 100mL of 2-propanol at 90 ℃/1 h. It was then cooled to 25 ℃. The product was filtered off, washed with 15mL of 2-propanol and dried in vacuo. Further purification can be achieved by column chromatography in cyclohexane/ethyl acetate.

This gives 14.3g of pure (uHPLC > 95%) product in 55% yield.

The following compounds can be synthesized in a similar manner:

synthesis of gamma-carboline e-bodies

13,6G (39.058 mmol,1 eq) of 3-bromo-5-gamma-carboline-benzonitrile, 17.3g (46.87 mmol,1.2 eq) of 9- [3- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] carbazole and 1.35g (1.172 mmol,0.03 eq) Pd (PPh 3) 4 were suspended in 196mL of toluene in a dry 500mL flaskAlkane (4:1) mixture. The suspension was degassed by bubbling with nitrogen for 15 minutes. 39mL (2 eq) of an aqueous solution of 2MNA2CO3 (degassed with nitrogen for 15 minutes) was added thereto. The reaction mixture was then evacuated and nitrogen was purged 2 times. The reaction was stirred at 80 ℃ overnight. For work-up, the reaction mixture was diluted with toluene (200 mL), filtered through celite, the celite was washed with toluene (150 mL), no product was checked in the celite, and the aqueous layer was separated from toluene. The aqueous layer was then washed with toluene until there was no product in the aqueous layer. Finally, the toluene layer was evaporated.

To purify the crude product, acetonitrile (100 mL) was added and heated to 85 ℃ (bath temperature) for 1 hour. After this time, the reaction mixture was cooled to 10 ℃, the precipitated product was filtered off and washed with acetonitrile (30 mL). Finally, the product was recrystallized in ethanol (100 ml) by heating to 80℃for 1 hour. After which it was cooled to 25 ℃ and then to 10 ℃. The resulting solid was filtered, washed with ethanol (2X 10 mL) and dried in vacuo.

This gives 13.8g of pure (uHPLC > 95%) product in 69% yield.

The following compounds can be synthesized in a similar manner:

Examples of synthesis of alpha-carboline-n-BIMBIM (alpha-Carboline-Ortho-BIMBIM) host:

Synthesis of 3-bromo-5-alpha-carboline benzonitrile

A 1000mL three-necked flask was flushed three times with vacuum and nitrogen. To the flask was added 3.56g (0.148 mol,2.0 eq.) of 60% NaH (suspension in paraffin oil) and 100mL of dry DMF under nitrogen atmosphere. The reaction mixture was cooled to 0-5 ℃ with an ice bath. A solution of 12.4g (1.0 eq.0.074 mol) of the alpha-carboline in 150mL of dry DMF was then added at 0-5 ℃. The reaction mixture was stirred at 0-5 ℃ for 30 minutes. A solution of 15.6g (1.05 eq,0.078 mol) of 3-bromo-5-fluorobenzonitrile in 120mL of dry DMF was then added at 0-5 ℃. Stirring of the reaction mixture was continued overnight at 150 ℃.

For work-up, the reaction mixture was taken up in water (300 mL) and saturated aqueous NH ₄ Cl (70 mL) in another round bottom flask and cooled to 5-10 ℃. The product precipitated and was filtered and washed with water (100 mL).

This gives 12.1g of pure 3-bromo-5- α -carboline benzonitrile (uHPLC > 95%) in 44% yield.

Synthesis of alpha-carboline-n-BIMBIM main body

In a dry 500mL flask, 10,0g (28.72 mmol,1 eq) of 3-bromo-5- α -carboline-benzonitrile, 14.1g (34.46, 1.2 eq) of 9- [3- (4, 5-methyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] BIMBIM and 0.99g (0.86 mmol,0.03 eq) Pd (PPh ₃)₄) were suspended in 170mL of toluene: diAlkane (4:1) mixture. The suspension was degassed by bubbling with nitrogen for 15 minutes. To this was added 35mL (2 eq) of a 2m aqueous na2co3 solution (15 minutes deaerated with nitrogen). The reaction volume was then evacuated and purged with nitrogen 2 times. The reaction was stirred at 80 ℃ overnight.

For work-up, the reaction mixture was diluted with 175ml of toluene, filtered through celite, the celite was washed with 150ml of toluene, no product was checked in the celite, and the aqueous layer was separated from toluene. The aqueous layer was then washed with toluene until there was no product in the aqueous layer. Finally, the toluene layer was evaporated.

For purification, the crude product was taken up in 100ml of acetonitrile and heated to 85 ℃ (bath temperature) for 1 hour. After this time, the reaction mixture was cooled to 10 ℃, the precipitated product was filtered off and washed with 30ml of acetonitrile. Finally, the product was recrystallized in 75ml of ethanol by heating to 80 ℃ for 1 hour. After which it was gradually cooled to 25 ℃ and finally to 10 ℃. The resulting solid was filtered, washed twice with 10ml of ethanol and dried in vacuo.

11.8G of pure (uHPLC > 95%) product are thus obtained in 74% yield.

OLED fabrication

Fabrication of vapor-treated OLED devices

The OLED device was manufactured according to WO 04/058911 with modifications in film thickness and layer sequence. The following examples V1 and E1 show data for OLED devices.

Substrate pretreatment of examples V1, E1 to E2:

a glass plate with structured ITO (50 nm, indium tin oxide) was formed into a substrate on which an OLED device was fabricated.

The OLED device has in principle the following layer structure:

The substrate is a substrate having a surface,

-ITO(50nm)，

Hole Injection Layer (HIL)

A Hole Transport Layer (HTL),

An Electron Blocking Layer (EBL),

A light-emitting layer (EML),

A Hole Blocking Layer (HBL),

An Electron Transport Layer (ETL),

An Electron Injection Layer (EIL),

-A cathode.

The cathode was formed of an aluminum layer having a thickness of 100 nm. Table a shows the detailed stacking sequence. Table C shows the materials used for the OLED fabrication.

All materials were applied by thermal vapor deposition in a vacuum chamber. The light-emitting layer here always consists of at least one host material and one light-emitting dopant which is mixed with the host material by co-evaporation in a certain volume proportion. The expression h1:h2:d1 (50%: 45%: 5%) means here that material H1 is present in the layer in a proportion of 50% by volume, material H2 in a proportion of 45% by volume and material D1 in a proportion of 5% by volume. Similarly, the electron transport layer and the hole injection layer may also be composed of a mixture of two or more materials.

The OLED device was characterized in a standard way. For this purpose, assuming lambertian emission characteristics, the electroluminescence spectrum, current efficiency (measured in cd/a), power efficiency (lm/W) and external quantum efficiency (EQE, measured in% at 1000cd/m ²) are determined from the current/voltage/luminance characteristic line (IUL characteristic line). The Electroluminescence (EL) spectrum was recorded at an emission density of 1000cd/m ², and then CIE 1931x and y coordinates were calculated from the EL spectrum. U1000 is defined as the voltage at an luminous density of 1000cd/m ². SE1000 represents the current efficiency at 1000cd/m ², LE1000 represents the power efficiency at 1000cd/m ². EQE1000 is defined as the external quantum efficiency at an emission density of 1000cd/m ².

Table B summarizes device data for various OLED devices. Example V1 represents a comparative example according to the prior art. Examples E1 and E2 show data for OLED devices of the present invention.

In the following sections, several embodiments are described in more detail to show the advantages of the OLED device of the present invention.

Use of the compounds according to the invention as host materials in fluorescent OLEDs

The compounds of the present invention are particularly suitable as hosts (hosts) when blended with phosphorescent blue dopants (emitters) to form the emissive layer of phosphorescent blue OLED devices. SdT represents a comparative compound of the prior art (structure see Table C). The use of the compounds of the present invention as hosts (hosts) in phosphorescent blue OLED devices yields superior device data, especially in terms of power efficiency (LE 1000), when compared to the prior art (E1 versus V1, see device data of table B).

Table a: device stack for vapor-processed OLED

Table B: device data for vapor processed OLEDs

Table C: structure of gas phase processed OLED material

Claims

1. A compound of formula (1),

The symbols and labels used therein are as follows:

ar ¹ is a group of formula (Ar 1),

Wherein the method comprises the steps of

Provided that at least one X in the group of formula (Ar 1) is N;

Ar ² is a group of formula (Ar 2-A) or (Ar 2-B):

Wherein the method comprises the steps of

N is the same or different at each occurrence and is 0, 1,2 or 3;

m is identical or different on each occurrence and is 0, 1,2, 3 or 4.

2. A compound according to claim 1, wherein the compound is selected from the group consisting of compounds of formulae (1-1) to (1-6),

Wherein the symbols have the definition given in claim 1.

3. A compound according to claim 1 or 2, characterized in that the Ar ¹ group is selected from the group of formulae (Ar 1-1) to (Ar 1-14),

Wherein the dashed bond indicates a bond to a biphenyl group in formula (1), wherein the symbol R ^X has the definition given in claim 1 and wherein:

p is independently at each occurrence 0, 1,2, 3 or 4;

q is independently at each occurrence 0, 1, 2 or 3.

4. The compound according to one or more of the preceding claims, characterized in that the group Ar ² is selected from the group of formulae (Ar 2-A1) to (Ar 2-A15) and (Ar 2-B1),

Wherein the dashed bond indicates a bond to a biphenyl group in formula (1), wherein the symbol R ^Y has the definition given in claim 1 and wherein:

s is independently at each occurrence 0, 1,2, 3 or 4;

t is independently at each occurrence 0, 1, 2 or 3.

5. Compound according to one or more of the preceding claims, characterized in that the Ar ¹ group is a group of formula (Ar 1-1) as defined in claim 3 and the Ar ² group is a group of formula (Ar 2-A1) or (Ar 2-B1) as defined in claim 4.

6. A composition, the composition comprising:

-a material selected from the group of compounds of formula (1) as defined in claim 1; and

-A material selected from hole transporting host materials.

7. A composition, the composition comprising:

-a first host material selected from the group of compounds of formula (1) as defined in claim 1;

-a second host material selected from hole transporting host materials; and

-A third compound selected from phosphorescent emitters, fluorescent emitters and emitters exhibiting TADF (thermally activated delayed fluorescence).

8. The composition according to claim 6 or 7, comprising:

-a second host material selected from hole transporting host materials;

-a third compound selected from phosphorescent emitters and emitters exhibiting TADF;

-a fourth compound selected from phosphorescent emitters and fluorescent emitters.

9. Composition according to one or more of claims 6 to 8, characterized in that the second host material is chosen from: hole transporting host materials selected from carbazole derivatives and triarylamine derivatives, more particularly bicarbazole, bridged carbazole, triarylamine, dibenzofuran-carbazole derivatives or dibenzofuran-amine derivatives, and carbazole amines.

10. Composition according to one or more of claims 6 to 9, characterized in that the second host material is selected from hole-transporting host materials selected from compounds of formula (h-1) or (h-2),

Wherein:

k is Ar ⁴ or-L ²-N(Ar)₂;

Z is C-R ^Z or C-R ^A; or two adjacent Z groups together form a fused ring;

R _A is-L ³-Ar⁵ or-L ¹-N(Ar)₂;

E is independently at each occurrence a single bond or C (R ⁰)₂ group;

and wherein R, R' and Ar have the definitions defined in detail in claim 1.

11. The composition according to claim 10, wherein Ar ⁵ is an unsubstituted or substituted heteroaromatic ring system selected from the group consisting of the formulae (Ar 5-1) to (Ar 5-6),

Wherein the dashed bond indicates a bond to L ³ or Z;

V is C-R ^V, provided that when V is bonded to a group of the formula (h-1) or (h-2), V represents C; or two adjacent V groups together form a fused ring;

E ¹ is independently at each occurrence a single bond or C (R ⁰)₂ group; wherein R ⁰ has the same meaning as in claim 10;

And wherein R and Ar have the same definition as in claim 1.

12. The composition according to claim 10 or 11, wherein the second host material is selected from hole transporting host materials selected from compounds of formulae (h-1-1) to (h-2-2),

Wherein the symbols have the same meaning as in claims 1, 10 and 11, and wherein the marks have the following meanings:

x, y have the same meaning as in claim 10;

x ¹、y¹ has the same meaning as in claim 11;

c. f independently represents 0, 1, 2, 3 or 4;

d. e independently represents 0, 1,2 or 3;

L: if y=0, l represents 0, 1,2 or 3; or if y=1, l represents 0, 1 or 2.

13. A formulation comprising a compound according to one or more of claims 1 to 5 or a composition according to one or more of claims 6 to 12 and at least one solvent.

14. An electronic device comprising at least one compound according to one or more of claims 1 to 5 or a composition according to one or more of claims 6 to 12.

15. The electronic device of claim 14, which is an organic electroluminescent device comprising:

-an anode;

-a cathode; and

-At least one light emitting layer, wherein the light emitting layer comprises at least one compound according to one or more of claims 1 to 5 or a composition according to one or more of claims 6 to 12.