KR-20260065901-A - Materials for organic light-emitting devices

Abstract

The present invention relates to specific diazadibenzofuran and diazadibenzothiophen derivatives as OLEDs, mixtures and formulations comprising these, and electronic devices comprising these compounds, in particular organic light-emitting devices comprising these compounds as matrix materials, electron transport materials or hole blocking materials.

Inventors

• 파르함 아미르 호싸인
• 슈톨츠 세바슈티안
• 간쓰 슈테파니 마리
• 엥겔 미리암

Assignees

• 메르크 파텐트 게엠베하

Dates

Publication Date

20260511

Application Date

20240902

Priority Date

20230904

Claims (15)

1. Compound of Formula (1) below: The symbols and indices used in the expression are as follows: Y is bond, O, or S; o is 0 or 1; (D) a , (D) b , (D) c , (D) d indicate single substitution, disubstitution, trisubstitution, maximum allowable substitution, or no substitution by deuterium; R0 is an aromatic ring system having 5 to 40 ring atoms, which is the same or different in each case and can be substituted by CN, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, or one or more R1 radicals, wherein the two substituents R0 can together form a monocyclic or polycyclic, aliphatic, aromatic, or heteroaromatic ring system that can be substituted by one or more R1 radicals; a1 and a2 are the same or different in each case, and are 0, 1, 2, 3, or 4; n, m are 0 or 1, where n + m = 1; Rx is CN or Ar 2 ; L1 is a connector selected from L-1 to L-30, which is the same or different in each case, a single combination or: This can be partially or completely deuterinized; V 1 is O or S; The dashed line indicates the attachment to the corresponding remaining part of Equation (1); X is a C bonded to N, C-Ar 1 , or L 1 independently in each case, where exactly two Ys are Ns separated by the C bonded to C-Ar 1 or L 1 ; W is O or S; R# is a phenyl that can be independently substituted by D, F, CN, or one or more R2 radicals in each case; [R#] a3 indicates a single substitution, heterosubstitution, maximum allowable substitution, or no substitution by R#; R1 is the same or different in each case and is D, F, Cl, Br, I, CN, NO2 , C(=O) R2 , P(=O)(Ar) 2 , P(Ar) 2 , B(Ar) 2 , Si(Ar) 3 , Si( R2 ) 3 , a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms (each of these may be substituted by one or more R2 radicals, wherein one or more non-adjacent CH2 groups are R2 C= CR2 , Si( R2 ) 2 , C=O, C=S, C= NR2 , P(=O)( R2 ), SO, SO2 , NR2 Selected from the group consisting of: an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms that can be substituted by one or more R2 radicals in each case; an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms that can be substituted by one or more R2 radicals; or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms that can be substituted by one or more R2 radicals; Ar is an aromatic or heteroaromatic ring system that is the same or different in each case, has 5 to 40 ring atoms, and can be substituted by one or more R2 radicals; Ar1 is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms that can be substituted by one or more R1 radicals; Ar2 is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and capable of being substituted by one or more R1 radicals, except for heteroaromatic ring systems containing C=O bonds; R2 is the same or different in each case and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and one or more hydrogen atoms may be replaced by D, F or CN.
2. In paragraph 1, Y represents a bond, a compound where o = 1.
3. In Paragraph 1 or 2, Y represents O, a compound where o = 1.
4. In one or more of paragraphs 1 through 3, W is a compound of O.
5. A mixture comprising at least one compound described in one or more of claims 1 to 4, and at least one additional compound selected from the group consisting of a matrix material, a phosphorescent emitter, a fluorescent emitter and/or an emitter exhibiting TADF (thermally activated delayed fluorescence), and/or a solvent.
6. A mixture comprising at least one compound described in one or more of claims 1 to 4, at least one additional compound selected from the group consisting of electron transport materials, electron injection materials, hole blocking materials, and materials having a high dielectric constant, and/or a solvent.
7. An organic electronic device comprising an anode, a cathode, and at least one organic layer comprising at least one compound described in one or more of claims 1 to 4.
8. In Paragraph 7, The above electronic device is an organic electronic device that is an electroluminescent device.
9. In Article 7 or Article 8, An organic electronic device comprising at least one light-emitting layer in which the organic layer comprises a compound described in any one of claims 1 to 4.
10. In one or more of paragraphs 7 through 9, An organic electronic device characterized in that the light-emitting layer comprises an additional matrix material.
11. In Paragraph 10, An organic electroluminescent device characterized in that the above additional matrix material corresponds to a compound of formula (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6). The symbols and indices used in the expression are as follows: A 1 is C(R 7 ) 2 , NR 7 , O or S; L is bonded, O, S, C( R7 ) 2 , or NR7 ; A is the basis of equation (HH-4-1) or (HH-4-2) independently in each case, X 2 is the same or different in each case, CH, CR 6 or N, where two or fewer symbols X 2 may be N; * indicates the binding site for formula (HH-4); U1 and U2 are, in each case, bonded, O, S, C( R7 ) 2 or NR7 ; R6 is, in each case, the same or different and is D, F, CN, 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 (wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R7 radicals in each case and one or more non-adjacent CH2 groups may be replaced by Si( R7 ) 2 , C=O, NR7 , O, S or CONR7 ) or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may be substituted by one or more R7 radicals in each case; it is also possible for two R6 radicals to together form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system; Ar 5 is an aromatic or heteroaromatic ring system that, in each case, is identical or different and independently has 5 to 40 ring atoms and can be substituted with one or more R 7 radicals; R7 is the same or different in each case, and D, F, Cl, Br, I, N( R8 ) 2 , CN, NO2 , OR8 , SR8 , Si( R8 ) 3 , B( OR8 ) 2 , C(=O) R8 , P(=O)( R8 ) 2 , S(=O) R8 , S(=O) 2R8 , OSO2R8 , 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 (wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R8 radicals in each case, and one or more non-adjacent CH2 groups are Si( R8 ) 2 , It is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms (which may be replaced by C=O, NR8 , O, S, or CONR8 ) or which may be substituted by one or more R8 radicals in each case; simultaneously, two or more R7 radicals may together form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system; preferably, the R7 radicals do not form any such ring system; R 8 is, in each case, the same or different, an aliphatic, aromatic, or heteroaromatic organic radical having H, D, F, or 1 to 20 carbon atoms, particularly a hydrocarbyl radical, wherein one or more hydrogen atoms may also be replaced by F; c, c1, and c2 are each independently 0 or 1 in each case, where the sum of the indices in each case is c+c1+c2 = 1; d, d1, and d2 are independently 0 or 1 in each case, where the sum of the indices in each case is d+d1+d2 = 1; In each case, q, q1, and q2 are independently 0, 1, 2, 3, or 4; s is the same or different in each case, and is 0, 1, 2, 3, or 4; t is the same or different in each case, and is 0, 1, 2, or 3; u is the same or different in each case, and is 0, 1, or 2; u1 and u2 are independently 0 or 1 in each case, where the sum u1 + u2 = 1; v is 0, 1, 2, or 3.
12. In one or more of paragraphs 7 through 11, An organic electronic device characterized in that the light-emitting layer comprises a phosphorescent emitter.
13. In Article 7 or Article 8, An organic electronic device comprising at least one electron transport layer, electron injection layer, or hole blocking layer comprising a compound described in any one of claims 1 to 4.
14. In one or more of paragraphs 7 through 13, The organic electronic device is characterized by being an electroluminescent device selected from an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser), and an organic light-emitting diode (OLED).
15. A method for manufacturing a device described in one or more of claims 7 through 14, A method for manufacturing a device characterized in that the above organic layer is applied by vapor deposition or from a solution.

Description

Materials for organic light-emitting devices The present invention relates to specific diazadibenzofurans and diazadibenzothiophen derivatives, mixtures and formulations comprising these, and electronic devices comprising these compounds, particularly organic electroluminescent devices comprising these compounds as matrix materials, electron transport materials or hole blocking materials. Phosphorescent organometallic complexes are frequently used in organic electroluminescent devices (OLEDs). From a general perspective, improvements are still needed in OLEDs, for example, in terms of efficiency, operating voltage, and lifetime. The characteristics of phosphorescent OLEDs are not determined solely by the triplet emitter used. More specifically, other materials used, such as the matrix material, are also particularly important here. Therefore, improvements in these materials can also lead to significant improvements in OLED characteristics. WO2018060307 A1, WO2018074881 A1, WO2021112303 A1, US2021036244 A, KR20210144979 A, WO22173203 A1, KR2022042658 A, WO2019027189 A1, WO2019013526 A1, CN102786508 A and CN113861171 A describe the suitability of certain diazadibenzofuran derivatives or diazadibenzothiophen derivatives and their organic electronic devices. In general, these materials, particularly for use as matrix materials, still require improvement. The problem addressed by the present invention is to provide a compound particularly suitable for use as a matrix material, electron transport material, electron injection material, or hole blocking material in phosphorescent OLEDs. More specifically, the object of the present invention is to provide a matrix material leading to an improved lifetime. This corresponds particularly to the use of low emitter concentrations to intermediate emitter concentrations, namely 3% to 20%, particularly 3% to 15%, because the device lifetime is particularly limited therein. Examples Synthetic example The following synthesis is carried out in a dry solvent under a protective gaseous atmosphere unless otherwise noted. The compounds of the present invention may be prepared by synthesis methods known to those skilled in the art. a) 2-chloro-4,8-diphenylbenzofuro[3,2-d]pyrimidine 31.4 g (100 mmol) of 2,4-dichloro-8-phenylbenzofuro[3,2-d]pyrimidine, 12.2 g (100 mmol) of phenylboronic acid, and 11.8 g (111 mmol) of sodium carbonate were dissolved in 800 ml of 1,4-dioxane, 800 ml of water, and 250 ml of toluene, and stirred under an argon atmosphere. 1.2 g (1 mmol) of tetrakis(triphenylphosphine)palladium was added to the flask. The reaction mixture was stirred overnight under reflux. After cooling, the mixture was quenched. The organic phase was separated, washed three times with 300 ml of water, dried over MgSO₄ , filtered, and the solvent removed under reduced pressure. The residue was purified by column chromatography using silica gel (eluent: DCM/heptane (1:10)). The yield is 28 g (80 mmol), which corresponds to 80% of the theoretical value. The following compounds are prepared in a similar manner: b) 4,8-diphenyl-2-(9,9'-spirobi[fluorene]-2'-yl)benzofuro[3,2-d]pyrimidine 35.6 g (100 mmol) of 2-chloro-4,8-diphenylbenzofuro[3,2-d]pyrimidine, 36 g (100 mmol) of 9,9'-spirobi[fluorene]-2'-voronic acid, and 11.8 g (111 mmol) of sodium carbonate were dissolved in 800 ml of 1,4-dioxane, 800 ml of water, and 250 ml of toluene, and stirred under an argon atmosphere. 1.2 g (1 mmol) of tetrakis(triphenylphosphine)palladium was added. The reaction mixture was stirred overnight under reflux. After cooling, the mixture was quenched. The organic phase was separated, washed three times with 300 ml of water, dried over MgSO₄ , filtered, and the solvent removed under reduced pressure. The residue is purified by column chromatography using silica gel (eluent: DCM/heptane (1:10)) and finally sublimated under high vacuum. The yield is 51 g (79 mmol), corresponding to 79% of the theoretical value. The following compounds are manufactured in a similar manner: c) B-[4-(9,9′-spirobi[9H-fluorene-9,9′-[9H]xanthen-2-yl)phenyl]boronic acid 46 g (95 mmol) of 2-(4-bromophenyl)spiro[ 9H -fluorene-9,9′-[ 9H ]xanthen was dissolved in 500 ml of THF under an argon atmosphere and cooled to -78°C. 10 ml of butyllithium (104 mmol/2.5 M in hexane) was added dropwise at -78°C, and the mixture was stirred at -78°C for 2 hours. Subsequently, 15 g (144 mmol) of trimethylborate was added dropwise at -78°C, and the mixture was stirred overnight at room temperature. 200 ml of 2 N hydrochloric acid was added, and the mixture was stirred for 1 hour. The organic phase was separated, washed three times with 300 ml of water, dried over MgSO₄ , filtered, and the solvent removed under reduced pressure. The residue was washed with 500 ml of heptane, filtered, and dried. The yield is 32.6 g (72 mmol), which corresponds to 76% of the theoretical value. OLED manufacturing Example A) In the following Examples V1 to V12 and B1 to B34 (s