阅读说明：本技术 用于电子器件的化合物 (Compounds for electronic devices ) 是由 阿米尔·帕勒姆 乔纳斯·克罗巴 多米尼克·约斯滕 奥雷莉·吕德曼 托比亚斯·格罗斯曼 于 2018-04-24 设计创作，主要内容包括：本申请涉及符合限定式的桥联三芳基胺。这些化合物适用于电子器件。本申请还涉及制备所述化合物的方法,以及包含所述化合物的电子器件。(The present application relates to bridged triarylamines according to defined formula (I). These compounds are suitable for use in electronic devices. The application also relates to methods of making the compounds, and electronic devices comprising the compounds.)

1. A compound of formula (I)

The variables appearing therein are as follows:

Y is identical or different on each occurrence and is selected from the group consisting of single bonds, O and S, wherein at least one Y group selected from the group consisting of O and S is present;

Z¹In each case identical or different and is CR¹n or C, wherein in the Y group and Z¹in the particular case of radical bonding Z¹The group is C;

Ar¹Are identical or different on each occurrence and are of 6 to 24 aromatic ring atoms and may be substituted by one or more R²an aromatic ring system substituted by radicals, or having 5 to 24 aromatic ring atoms and which may be substituted by one or more R²A group-substituted heteroaromatic ring system;

cbz is represented by R at each of its unoccupied positions³Divalent radicals substituted by radicals and containing one or more structural elements of the formula (Cbz)

Wherein one of the two bonds of the divalent group to the remainder of the compound is a dotted bond on the nitrogen atom of the formula (Cbz),

Wherein the second of the two bonds may be in any unoccupied position in the group, and wherein

Z²In each case identical or different and selected from C and N;

Ar²Is a compound having 5 to 30 aromatic ring atoms and may be substituted by one or more R⁴a group-substituted electron-deficient heteroaryl group;

R¹、R²、R³、R⁴In each case identical or different and selected from H, D, F, C (═ O) R⁵，CN，Si(R⁵)₃，N(R⁵)₂，P(＝O)(R⁵)₂，OR⁵，S(＝O)R⁵，S(＝O)₂R⁵A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³Or R⁴The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems may each be substituted by one or moreR⁵Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups₂the group may be represented by-R⁵C＝CR⁵-、-C≡C-、Si(R⁵)₂、C＝O、C＝NR⁵、-C(＝O)O-、-C(＝O)NR⁵-、NR⁵、P(＝O)(R⁵) -O-, -S-, SO or SO₂Replacing;

R⁵In each case identical or different and selected from H, D, F, C (═ O) R⁶，CN，Si(R⁶)₃，N(R⁶)₂，P(＝O)(R⁶)₂，OR⁶，S(＝O)R⁶，S(＝O)₂R⁶A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R⁵The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems may each be substituted by one or more R⁶Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups₂The group may be represented by-R⁶C＝CR⁶-、-C≡C-、Si(R⁶)₂、C＝O、C＝NR⁶、-C(＝O)O-、-C(＝O)NR⁶-、NR⁶、P(＝O)(R⁶) -O-, -S-, SO or SO₂Replacing;

R⁶Identical or different on each occurrence and selected from the group consisting of H, D, F, CN, alkyl or alkoxy radicals having from 1 to 20 carbon atoms, alkenyl or alkynyl radicals having from 2 to 20 carbon atoms, aromatic ring systems having from 6 to 40 aromatic ring atoms and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms; wherein two or more R⁶The groups may be linked to each other and may form a ring; and wherein the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F or CN;

I are identical or different on each occurrence and are 0 or 1, wherein at least two indices I in formula (I) are 1, and wherein the Y group in question is absent when the respective index I ═ 0;

n is 0, 1,2,3 or 4;

m is 0, 1,2,3 or 4.

2. The compound of claim 1, characterized by Ar²selected from those having 5 to 30 aromatic ring atoms and which may be substituted by one or more R⁴A group-substituted heteroaryl group, wherein the heteroaryl group contains at least one heteroaromatic five-membered ring having two or more heteroatoms selected from N, O and S or at least one heteroaromatic six-membered ring having one or more heteroatoms selected from N, O and S.

3. The compound of claim 1 or 2, characterized by Ar²Selected from the following formulae

The variables appearing therein are defined as follows:

V is identical or different on each occurrence and is N or CR⁴Wherein formula (Ar)²-A)、(Ar²-C)、(Ar²-D) and (Ar)²-at least one V group in each of E) is N;

W is identical or different on each occurrence and is N or CR⁴；

U is NR⁴；

Wherein the formula (Ar)²At least one group selected from the group consisting of W and V in B) is N; and is

Wherein each formula has one R⁴Radical is reacted with Ar¹A group or a Cbz-linked bond.

4. compound according to one or more of claims 1 to 3, characterized in that Ar²Selected from triazines and quinazolines, each of which may be substituted with one or more R⁴And (4) substituting the group.

5. Compound as claimed in one or more of claims 1 to 4, characterized in that the Cbz groups are identical or different on each occurrence and are selected from carbazole, azacarbazole, benzocarbazole, dibenzocarbazole, indenocarbazole, indolocarbazole, carbazole fused to benzofuran and carbazole fused to benzothiophene, where the radicals may each be substituted by one or more R³And (4) substituting the group.

6. Compound according to one or more of claims 1 to 5, characterized in that the Cbz group is selected from the following formulae

Wherein:

T is C (R)³)₂O, S or NR³；

Wherein the dotted bond represents a bond to the remainder of the compound, and

Wherein the groups in the above formula may each be substituted by R at any position shown as unsubstituted³And (4) substituting the group.

7. Compound according to one or more of claims 1 to 6, characterized in that Y is identical or different on each occurrence and is selected from O and S.

8. Compound according to one or more of claims 1 to 7, characterized in that Z¹Is CR¹Or C, wherein in the Y group with Z¹When radicals are bound to each other Z¹The radical is C.

9. Compound according to one or more of claims 1 to 8, characterized in that Ar¹In each case identical or different and are divalent radicals which originate from the basic skeleton of benzene, biphenyl, terphenyl, naphthalene, dibenzofuran, dibenzothiophene, carbazole and fluorene, where the divalent radicals may be substituted by one or more R²And (4) substituting the group.

10. Compound according to one or more of claims 1 to 9, characterized in that R¹、R²、R³And R⁴In each case identical or different and selected from H, D, F, CN, Si (R)⁵)₃，N(R⁵)₂A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl or alkoxy group, said aromatic ring system and said heteroaromatic ring system may each be substituted by one or more R⁵Substituted by groups; and wherein one or more CH in the alkyl or alkoxy group₂The radicals being optionally substituted by-C.ident.C-, -R⁵C＝CR⁵-、Si(R⁵)₂、C＝O、C＝NR⁵、-NR⁵-, -O-, -S-, -C (═ O) O-or-C (═ O) NR⁵-substitution.

11. compound according to one or more of claims 1 to 10, characterized in that R⁵in each caseAre identical or different and are selected from H, D, F, CN, Si (R)⁶)₃，N(R⁶)₂A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein said alkyl and alkoxy groups, said aromatic ring system and said heteroaromatic ring system may each be substituted by one or more R⁶Substituted by groups; and wherein one or more CH in the alkyl or alkoxy group₂The radicals being optionally substituted by-C.ident.C-, -R⁶C＝CR⁶-、Si(R⁶)₂、C＝O、C＝NR⁶、-NR⁶-, -O-, -S-, -C (═ O) O-or-C (═ O) NR⁶-substitution.

12. Compound according to one or more of claims 1 to 11, characterized in that R⁶Is H.

13. Compound according to one or more of claims 1 to 12, characterized in that m and n are in each case 0.

14. Compound according to one or more of claims 1 to 13, characterized in that formula (I) corresponds to one of the following formulae

Wherein the variables appearing are as defined in one or more of claims 1 to 13 and the formula may be shown unsubstituted in each position on an aromatic six-membered ring by R¹and (4) substituting the group.

15. A method for the preparation of a compound according to one or more of claims 1 to 14, characterized in that in a first step a triphenylamine compound substituted on one of the phenyl groups by a reactive group is prepared, wherein the bridging groups between the phenyl groups are selected from single bonds, O and S, and wherein at least 2 bridging groups are present, and in that in a further step a carbazole group is introduced into the compound via a transition metal catalyzed coupling reaction.

16. Oligomer, polymer or dendrimer containing one or more compounds of the formula (I) according to one or more of claims 1 to 14, wherein one or more bonds to the polymer, oligomer or dendrimer may be located in formula (I) by R¹、R²、R³Or R⁴Any desired position of substitution.

17. A formulation comprising at least one compound according to one or more of claims 1 to 14, or a polymer, oligomer or dendrimer according to claim 16, and at least one solvent.

18. An electronic device comprising at least one compound according to one or more of claims 1 to 14, or a polymer, oligomer or dendrimer according to claim 16.

19. Electronic device according to claim 18, characterized in that the electronic device is an organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, wherein the light-emitting layer is at least one organic layer of the device, which organic layer is a light-emitting layer, an electron transport layer or a hole blocking layer, which organic layer comprises the at least one compound.

20. Use of a compound according to one or more of claims 1 to 14 in an electronic device.

Examples

A) Synthetic examples

stage a) 7-bromo [1,4] benzothiazino [2,3,4-kl ] phenothiazine

To a solution of [1,4] benzothiazino [2,3,4-kl ] phenothiazine (CAS1050521-47, 48.5g, 154mmol) in chloroform (1000ml) was added N-bromosuccinimide (24.7g, 139mmol) in portions at 0 ℃ under exclusion of light and the mixture was stirred at that temperature for 2 hours. The reaction was stopped by adding sodium sulfite solution and the mixture was stirred at room temperature for a further 30 minutes. After phase separation, the organic phase is washed with water and the aqueous phase is extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. The residue was dissolved in ethyl acetate and filtered through silica gel. Subsequently, the crude product was recrystallized from heptane.

Yield: 42g (110mmol), 64% of theory, of colorless solid.

In a similar manner, the following compounds are obtained:

In a similar manner, two equivalents of NBS can be used to obtain the following compounds:

Stage b) dithio-13 b-azanaphtho [3,2,1-de ] anthracene-7-boronic acid

28g (73mmol) of 7-bromo- [1,4] benzothiazino [2,3,4-kl ] phenothiazine are dissolved in 150ml of anhydrous THF and cooled to-78 ℃. At this temperature, 30ml (76mmol/2.5M hexane solution) of n-butyllithium were added over about 5 minutes, and the mixture was stirred at-78 ℃ for a further 2.5 hours. At this temperature, 15g (145mmol) of trimethyl borate are added very rapidly and the reaction is allowed to gradually reach room temperature (about 18 hours). The reaction solution was washed with water, and the precipitated solid and organic phase were azeotropically dried with toluene. The crude product was extracted from toluene/dichloromethane with stirring and filtered off with suction at about 40 ℃. Yield: 22g (63mmol), 90% of theory.

The following compounds were prepared in a similar manner:

stage c): 3, 7-bis (dibenzofuran-1-yl) -5, 9-dioxa-13 b-azanaphtho [3,2,1de ] anthracene

To 116g (470mmol) of 1-bromodibenzofuran, 169g (470.0mmol) of 5, 9-dioxa-13 b-azanaphtho [3,2,1-de]Anthracene-3, 7-bisboronic acid 149.02g (702.0mmol) of K₃PO₄1000ml of twoTo a degassed mixture of alkane and 1000ml water was added 13.52g (11.7mmol) Pd (PPh)₃)₄. After heating the mixture to 80 ℃ for 7 hours, 4.58g (93.6mmol) of NaCN were added. After cooling to room temperature, the aqueous phase was removed. H for organic phase₂O washed twice and then Na₂SO₄And (5) drying. Removing the solvent and separating the dark red solid from the secondAfter two recrystallizations from alkane, the product was obtained in the form of red needles.

Yield: 184g (304mmol), 66% of theory; purity: according to HPLC 97%.

The following compounds can be prepared in a similar manner:

Stage d) 3-bromo-7, 11-bis (dibenzofuran-1-yl) -5, 9-dioxa-13 b-azanaphtho [3,2,1-de ] anthracene

First, 45.1g (74.6mmol) of 3, 7-bis (dibenzofuran-1-yl) -5, 9-dioxa-13 b-azanaphtho [3,2,1de]Anthracene was charged in 80ml DMF. Subsequently, 13.3g (74.6mmol) of NBS were added in portions and stirring was continued at this temperature for 4 hours. Subsequently, 15ml of water and CH were added to the mixture₂Cl₂extraction is realized. The organic phase is over MgSO₄Dried and the solvent removed under reduced pressure. The product was extracted with hot hexane with stirring and filtered off with suction. Yield: 39g (58mmol), 78% of theory, according to¹The H NMR purity was about 96%.

The following compounds can be prepared in a similar manner:

Stage e)7- [9- (4, 6-diphenyl- [1,3,5] triazin-2-yl) -9H-carbazol-3-yl ] -5, 9-dithia-13 b-azanaphtho [3,2,1-de ] anthracene

11g (32mmol) of dithia-13 b-azanaphtho [3,2,1-de]Anthracene-7-boronic acid, 14g (31.6mmol) of 3-bromo-9- (4, 6-diphenyl- [1,3, 5)]Triazin-2-yl) -9H-carbazole and 31ml (63mmol) of Na₂CO₃(2M solution) was suspended in 120ml of toluene, 120ml of ethanol. To the suspension was added 0.73g (0.63mmol) of Pd (PPh)₃)₄And the reaction mixture was heated to reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200ml of water and then concentrated to dryness. The residue was recrystallized from toluene and purified twice by sublimation under reduced pressure (p ═ 5 × 10)^-5Mbar, T329 ℃). The yield was 16.7g (24mmol), corresponding to 76% of theory.

In a similar manner, the following compounds were obtained:

B) Device embodiments

The subsequent examples E1 to E12 (see table 1) show the use of the compounds according to the invention in OLEDs. Examples V1 to V4 (see table 1) are reference examples.

1) General description of the manufacture and analysis of OLEDs:

Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50nm were treated with oxygen plasma followed by argon plasma prior to coating. These plasma treated glass plates form the substrate to which the OLED is applied.

the OLED has essentially the following layer structure: substrate/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/Electron Blocking Layer (EBL)/emissive layer (EML)/optional Hole Blocking Layer (HBL)/Electron Transport Layer (ETL) and finally a cathode. The cathode is formed from a 100nm thick layer of aluminum. The HIL used was a 5nm thick layer of the material HATCN. The HTL used was a 125nm thick layer of the material SpMA 1. The EBL used was a 10nm thick layer of the material SpMA 3. Other configurations of OLEDs can be inferred from table 1. The materials used to make the OLEDs are shown in table 2.

All materials were applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one host material (host material) and a light-emitting dopant (emitter) which is added to the host material or materials in a specific volume proportion by co-evaporation. Details given here in the form of, for example, IC5: IC3: TEG2 (55%: 35%: 10%) mean that the material IC5 is present in the layer in a proportion by volume of 55%, IC3 is present in the layer in a proportion by volume of 35% and TEG2 is present in the layer in a proportion by volume of 10%, in each case by volume. Similarly, the electron transport layer may also be composed of a mixture of two materials.

The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum and the current-voltage-luminescence density characteristic (IUL characteristic) were measured. At 1000cd/m²The electroluminescence spectrum is measured at the luminescence density of (a), and the CIE 1931x and y color coordinates are calculated therefrom.

2) Comparison of the Compounds of the invention EG1-EG4 with the Prior Art Compounds SdT1 to SdT4

The materials of the present invention can be used in the light emitting layer in red phosphorescent OLEDs. By using the molecules of the invention as matrix material in the light-emitting layer, in comparison with the prior art (compounds SdT1-4 of examples V1-V4 in Table 1), it was found to be 1000cd/m in each case²The voltage drop at the luminous density of (example E1 and V1, E2 and V2, E3 and V3 and E4 and V4) was 10%. This constitutes a significant improvement of OLEDs.

3) The use of the compounds of the invention in the light-emitting layer, hole-blocking layer and electron-transport layer of an OLED.

the compounds EG1 to EG9 and EG13 to EG15 according to the invention are used in the light-emitting layer as matrix materials in combination with phosphorescent emitters in examples E1 to E12. The color coordinates of the electroluminescence spectra of the OLEDs from these experiments are CIEx 0.67 and CIEy 0.33. Therefore, the material is suitable for use in the light emitting layer of a red OLED.

Furthermore, the materials of the present invention can be successfully used in Electron Transport Layers (ETL) or Hole Blocking Layers (HBL). This is shown in experiments E13-E15. Here, the color coordinates of the OLED spectrum are also CIEx 0.67 and CIEy 0.33.

Table 1: structure of OLED

Table 2: structural formula of material for OLED