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CN-122010882-A - Material for organic electroluminescent device

CN122010882ACN 122010882 ACN122010882 ACN 122010882ACN-122010882-A

Abstract

The present invention relates to materials for organic electroluminescent devices. In particular, the invention relates to amines having dibenzofuran, dibenzothiophene and fluorene groups for use as triplet matrix materials, in particular in organic electroluminescent devices. The invention also relates to a method for preparing the compounds of the invention and to electronic devices comprising said compounds.

Inventors

  • Emil Hussein Palem
  • Thomas Eberley
  • Anya Yatiski
  • Tobias grossman
  • Jonas Valentine Crobar
  • ELVIRA MONTENEGRO
  • Caroline Ville

Assignees

  • 默克专利有限公司

Dates

Publication Date
20260512
Application Date
20170206
Priority Date
20160303

Claims (20)

  1. 1. A compound of formula (1) for use in electron blocking and/or exciton blocking layers and/or hole transport layers and/or hole injection layers of organic electroluminescent devices, (1) The symbols used therein are as follows: X is O or S; Y is O, S or CR 2 ; Ar is selected from the structures of formulae (Ar-2) to (Ar-4), (Ar-8), (Ar-9), (Ar-11) and (Ar-13) to (Ar-16), wherein Ar comprises only an aryl or heteroaryl group having up to 15 aromatic ring atoms and does not comprise a carbazolyl group as heteroaryl group and does not comprise a 9,9' -spirobifluorenyl group, Wherein the method comprises the steps of Q is the same or different on each occurrence and is CR 4 or N, wherein no more than 3Q symbols in each ring are N; E is the same or different on each occurrence and is C (R 4 ) 2 , O, S or c=o, wherein two R 4 do not form an aromatic or heteroaromatic ring system; G is identical or different on each occurrence and is NR 4 、C(R 4 ) 2 , O, S or C=O, and Represents a bond to a nitrogen atom; R is identical or different on each occurrence and is selected from H,D,F,Cl,I,CN,NO 2 ,N(Ar 1 ) 2 ,N(R 4 ) 2 ,C(=O)Ar 1 ,C(=O)R 4 ,P(=O)(Ar 1 ) 2 ,P(Ar 1 ) 2 ,B(Ar 1 ) 2 , a straight-chain alkyl, alkoxy or thioalkyl having from 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl having from 3 to 20 carbon atoms or an alkenyl having from 2 to 20 carbon atoms, each of which radicals may be substituted by one or more R 4 radicals, wherein one or more non-adjacent CH 2 radicals may be replaced by R 4 C=CR 4 、C=O、C=S、C=NR 4 、P(=O)(R 4 )、SO、SO 2 、NR 4 , O, S or CONR 4 , and wherein one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO 2 an aromatic ring system having from 5 to 40 aromatic ring atoms and which may in each case be substituted by one or more R 4 radicals, an aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 1 radicals, or an aralkyl or heteroarylalkyl having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 radicals; R 1 is the same or different on each occurrence and is selected from the group consisting of linear, alkoxy or thioalkyl having from 1 to 20 carbon atoms, or branched or cyclic alkyl having from 3 to 20 carbon atoms, alkoxy or thioalkyl, or alkenyl having from 2 to 20 carbon atoms, each of which groups may be substituted with one or more R 4 groups, wherein one or more non-adjacent CH 2 groups may be replaced with R 4 C=CR 4 、C=O、C=S、C=NR 4 、P(=O)(R 4 )、SO、SO 2 、NR 4 , O, S or CONR 4 , and wherein one or more hydrogen atoms may be replaced with D, F, cl, br, I, CN or NO 2 , aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted with one or more R 4 groups, or aralkyl or heteroarylalkyl having from 5 to 40 aromatic ring atoms and which may be substituted with one or more R 4 groups; R 2 is identical or different on each occurrence and is selected from the group consisting of straight-chain alkyl, alkoxy or thioalkyl having from 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkyl having from 3 to 20 carbon atoms, or alkenyl having from 2 to 20 carbon atoms, each of which groups may be substituted by one or more R 4 groups, wherein one or more non-adjacent CH 2 groups may be replaced by R 4 C=CR 4 、C=O、C=S、C=NR 4 、P(=O)(R 4 )、SO、SO 2 、NR 4 , O, S or CONR 4 , and wherein one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO 2 , an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R 4 groups, an aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 groups, or an aralkyl or heteroarylalkyl having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 groups, and wherein two or more adjacent R 4 may be optionally substituted by a single ring or multiple ring carbon atoms; R 3 is identical or different on each occurrence and is selected from the group consisting of linear, alkoxy or thioalkyl groups having from 1 to 20 carbon atoms or branched or cyclic alkyl groups having from 3 to 20 carbon atoms, alkoxy or thioalkyl groups or alkenyl groups having from 2 to 20 carbon atoms, each of which groups may be substituted by one or more R 4 groups, wherein one or more non-adjacent CH 2 groups may be replaced by R 4 C=CR 4 、C=O、C=S、C=NR 4 、P(=O)(R 4 )、SO、SO 2 、NR 4 , O, S or CONR 4 , and wherein one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO 2 , an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms and which may in each case be substituted by one or more R 4 groups, an aryloxy or heteroaryloxy group having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 groups, or an aralkyl or heteroarylalkyl group having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 groups, and wherein two or more adjacent R 1 groups may be bonded to one or more ring systems optionally with R 3 ; Ar 1 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system which has from 5 to 30 aromatic ring atoms and which may be substituted by one or more non-aromatic R 4 groups, while two Ar 1 groups bonded to the same phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridging group selected from N (R 4 )、C(R 4 ) 2 , O and S; R 4 is identical or different in each case and is selected from H, D, F, cl, br, I, CN, NO 2 ,N(R 5 ) 2 ,C(=O)R 5 , a linear alkyl, alkoxy or thioalkyl having from 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl having from 3 to 20 carbon atoms or an alkenyl having from 2 to 20 carbon atoms, each of which groups may be substituted by one or more R 5 groups, wherein one or more non-adjacent CH 2 groups may be replaced by R 5 C=CR 5 、C=O、C=S、C=NR 5 、P(=O)(R 5 )、SO、SO 2 、NR 5 , O, S or CONR 5 , and wherein one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO 2 , an aromatic ring system having from 5 to 40 aromatic ring atoms and which may be substituted in each case by one or more R 5 groups, an aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 5 groups, or an aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 5 groups, wherein one or more hydrogen atoms may be substituted by one or more R D, F, cl, br, I, CN groups, and wherein one or more hydrogen atoms may be substituted by two or more R 5 groups may be simultaneously substituted by one or more aromatic ring systems; R 5 is identical or different on each occurrence and is selected from H, D, F, CN, an aliphatic hydrocarbon radical having from 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, cl, br, I or CN and the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals each having from 1 to 4 carbon atoms, while two or more adjacent R 5 substituents may together form a mono-or polycyclic aliphatic ring system; Wherein in one instance a nitrogen atom is bonded to the corresponding carbon atom in place of R 1 or R 3 , wherein in the case of R 3 Y cannot be CR 2 ; Wherein the following compounds are excluded: 。
  2. 2. a compound according to claim 1, characterized in that X is O.
  3. 3. Compound according to one or more of claims 1 and 2, characterized in that Y is O or S.
  4. 4. A compound according to claim 1 to 3, wherein the compound is a compound of formula (1-1) or formula (1-2), (1-1) (1-2) Wherein the symbols have the definition given in claim 1.
  5. 5. The compound according to claim 1 to 4, characterized in that it is a compound of formula (2), (2) Wherein the symbols have the definition given in claim 1 and wherein one R 2 and one R 4 bonded to a carbon atom are replaced by single bonds.
  6. 6. The compound according to claim 1 to 5, characterized in that it is a compound of formulae (2-1) and (2-2), (2-1) (2-2) Wherein the symbols have the definition given in claim 1, and wherein one R 2 in formula (2-2) and one R 4 in formula (2-1) bonded to a carbon atom are replaced by single bonds.
  7. 7. The compound according to claim 6, wherein R 2 substituted by a single bond in the formula (2-2) is not disposed on a 6-membered ring bonded to a nitrogen atom.
  8. 8. Compound according to one or more of claims 1 to 7, characterized in that Ar is selected from the group of formulae (Ar-2-1) to (Ar-16-6): Wherein the symbols correspond to those in the formulae (Ar-2) to (Ar-16), and the above formulae may be substituted at the free position by R 4 .
  9. 9. Compound according to one or more of claims 1 to 8, characterized in that Ar is a group of formula (Ar-14), wherein G is identical or different on each occasion and is NR 4 、C(R 4 ) 2 or O.
  10. 10. Compound according to claim 9, characterized in that G is identical or different in each case and is C (R 4 ) 2 or O.
  11. 11. Compound according to one or more of claims 1 to 10, characterized in that the following applies to the symbols used: x, Y and Ar have the definitions in claim 1; R is the same or different on each occurrence and is selected from H, D, a linear alkyl group having from 1 to 8 carbon atoms or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, each of which groups may be substituted by one or more R 4 groups, wherein one or more hydrogen atoms may be replaced by D, or an aromatic ring system having from 6 to 18 aromatic ring atoms and in each case may be substituted by one or more R 4 groups; R 1 is identical or different on each occurrence and is selected from H, D, F, CN, N (Ar 1 ) 2 , straight-chain alkyl having 1 to 8 carbon atoms or branched or cyclic alkyl having 3 to 8 carbon atoms, each of which groups may be substituted by one or more R 4 groups, in which one or more hydrogen atoms may be replaced by D; R 2 is identical or different on each occurrence and is selected from H, D, F, CN, N (Ar 1 ) 2 , straight-chain alkyl having 1 to 8 carbon atoms or branched or cyclic alkyl having 3 to 8 carbon atoms, each of which groups may be substituted by one or more R 4 groups, wherein one or more hydrogen atoms may be replaced by D, or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms and which may be substituted in each case by one or more R 4 groups; R 3 is identical or different on each occurrence and is selected from H, D, F, CN, N (Ar 1 ) 2 , straight-chain alkyl having 1 to 8 carbon atoms or branched or cyclic alkyl having 3 to 8 carbon atoms, each of which groups may be substituted by one or more R 4 groups, wherein one or more hydrogen atoms may be replaced by D, or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms and which may be substituted in each case by one or more R 4 groups; ar 1 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system which has from 5 to 30 aromatic ring atoms and which may be substituted by one or more non-aromatic R 4 groups; R 4 is identical or different on each occurrence and is selected from H, D, F, CN, straight-chain alkyl having 1 to 8 carbon atoms or branched or cyclic alkyl having 3 to 8 carbon atoms, in which one or more hydrogen atoms may be replaced by D, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms; Wherein in one instance a nitrogen atom is bonded to the corresponding carbon atom in place of R 1 or R 3 .
  12. 12. Compound according to one or more of claims 1 to 11, characterized in that the following applies to the symbols used: X is O; Y is O; ar has the definition in claim 1; R 1 is identical or different on each occurrence and is selected from H, D, N (Ar 1 ) 2 , straight-chain alkyl having 1, 2, 3 or 4 carbon atoms or branched or cyclic alkyl having 3, 4, 5 or 6 carbon atoms, where one or more hydrogen atoms may be replaced by D; R 2 is the same or different on each occurrence and is selected from H, D, N (Ar 1 ) 2 , straight-chain alkyl having 1, 2,3 or 4 carbon atoms or branched or cyclic alkyl having 3, 4, 5 or 6 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, or an aromatic ring system having 6 to 13 aromatic ring atoms and in each case may be substituted by one or more R 4 groups; r 3 is identical or different on each occurrence and is selected from H, D, a straight-chain alkyl radical having 1,2, 3 or 4 carbon atoms or a branched or cyclic alkyl radical having 3, 4, 5 or 6 carbon atoms, where one or more hydrogen atoms may be replaced by D, or an aromatic ring system having 6 to 13 aromatic ring atoms and in each case may be substituted by one or more R 4 radicals; Ar 1 is identical or different on each occurrence and is an aromatic ring system which has 5 to 30 aromatic ring atoms and which may be substituted by one or more non-aromatic R 4 groups; R 4 is identical or different on each occurrence and is selected from H, D, a straight-chain alkyl radical having 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl radical having 3, 4, 5 or 6 carbon atoms, in which one or more hydrogen atoms may be replaced by D, or an aromatic ring system having 6 to 13 aromatic ring atoms; Wherein in one instance a nitrogen atom is bonded to the corresponding carbon atom in place of R 1 or R 3 .
  13. 13. Compound according to one or more of claims 1 to 12, characterized in that the following applies to the symbols used: X is O; Y is O; ar has the definition in claim 1; R 1 are the same or different on each occurrence and are selected from H, D or N (Ar 1 ) 2 ; R 2 are identical or different on each occurrence and are selected from H or D; r 3 are identical or different on each occurrence and are selected from H or D; Ar 1 is identical or different on each occurrence and is an aromatic ring system having from 5 to 30 aromatic ring atoms; R 4 is identical or different on each occurrence and is selected from H, D or an aromatic ring system having from 6 to 13 aromatic ring atoms, while, optionally, two R 4 substituents bonded to the same carbon atom may form a mono-or polycyclic aliphatic or aromatic ring system; Wherein in one instance a nitrogen atom is bonded to the corresponding carbon atom in place of R 1 or R 3 .
  14. 14. Compound according to one or more of claims 1 to 13, characterized in that the following applies to the symbols used: X is O; Y is O; ar is a group of the formula (Ar-14) in which G is identical or different on each occurrence and is C (R 4 ) 2 or O; R 1 are the same or different on each occurrence and are selected from H, D or N (Ar 1 ) 2 ; R 2 are identical or different on each occurrence and are selected from H or D; r 3 are identical or different on each occurrence and are selected from H or D; r 4 is identical or different on each occurrence and is selected from H, D or an aromatic ring system having 6 aromatic ring atoms, while, optionally, two R 4 substituents bonded to the same carbon atom may form a mono-or polycyclic aliphatic or aromatic ring system; Wherein in one instance a nitrogen atom is bonded to the corresponding carbon atom in place of R 1 or R 3 .
  15. 15. A mixture comprising at least one compound according to one or more of claims 1 to 14 and at least one further compound and/or at least one solvent.
  16. 16. Use of a compound according to one or more of claims 1 to 14 or a mixture according to claim 15 in an electronic device.
  17. 17. An electronic device comprising at least one compound according to one or more of claims 1 to 14 or a mixture according to claim 15.
  18. 18. Electronic device according to claim 17, characterized in that it is an organic electroluminescent device.
  19. 19. Electronic device according to claim 18, characterized in that the compound according to one or more of claims 1 to 14 or the mixture according to claim 15 is used in a light-emitting layer or in a hole-transporting layer or an electron-blocking layer.
  20. 20. Electronic device according to claim 18 or 19, characterized in that the compound according to one or more of claims 1 to 14 is used in a hole transport layer or an electron blocking layer.

Description

Material for organic electroluminescent device The invention relates to a patent application with international application number of PCT/EP2017/000154, international application date of 2017, 2 months and 6 days, application number of 201780014250.2 entering China national stage, and divisional application of the patent application with the name of material for organic electroluminescent devices. Technical Field The present invention relates to materials for organic electroluminescent devices. In particular, amines having dibenzofuran, dibenzothiophene and fluorene groups are described for use as triplet host materials, particularly in organic electroluminescent devices. The invention also relates to methods of preparing the compounds of the invention and to electronic devices comprising these compounds. Background The structure of organic electroluminescent devices (OLEDs), in which organic semiconductors are used as functional materials, is described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. The luminescent materials used are typically organometallic complexes that exhibit phosphorescence. For quantum mechanical reasons, up to 4 times higher energy and power efficiencies can be obtained using organometallic compounds as phosphorescent emitters. In general, in OLEDs, in particular OLEDs exhibiting phosphorescence, there is still a need for improvements in terms of, for example, efficiency, operating voltage and lifetime. The performance of phosphorescent OLEDs is not determined solely by the triplet emitters used. More specifically, other materials used, such as matrix materials, are also of particular importance. Thus, improvements in these materials also result in significant improvements in OLED performance. Amines having fluorene and dibenzofuran groups are known from US 2014/0284978 according to the prior art. Compounds with carbazole are also known from EP 2421064. US 2013/023418 discloses amines with fused aromatic groups such as pyrene. In general, where these materials are used as host materials, there remains a need for improvements in particular in terms of lifetime and oxidation sensitivity, as well as in terms of efficiency and operating voltage of the device. Disclosure of Invention It is an object of the present invention to provide compounds suitable for use in phosphorescent or fluorescent OLEDs, in particular as matrix materials. More specifically, it is an object of the present invention to provide matrix materials which are suitable for OLEDs which emit red, yellow and green phosphorescence and which may also be suitable for OLEDs which emit blue phosphorescence and lead to a long lifetime, good efficiency and low operating voltage. In particular, the properties of the host material also have an important influence on the lifetime and efficiency of the organic electroluminescent device. It has been found that, surprisingly, electroluminescent devices comprising compounds of the formula (1) below have an improvement over the prior art, in particular when used as host materials for phosphorescent dopants. Accordingly, the present invention provides a compound of formula (1): (1) The symbols used therein are as follows: X is O or S; Y is O, S or CR 2; Ar is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R groups, wherein Ar comprises only aryl or heteroaryl groups having up to 15 aromatic ring atoms and does not comprise a carbazolyl group as heteroaryl group and does not comprise a 9,9' -spirobifluorenyl group; R is identical or different on each occurrence and is selected from H,D,F,Cl,Br,I,CN,NO2,N(Ar1)2,N(R4)2,C(=O)Ar1,C(=O)R4,P(=O)(Ar1)2,P(Ar1)2,B(Ar1)2, a linear alkyl, alkoxy or thioalkyl having from 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl having from 3 to 20 carbon atoms or an alkenyl having from 2 to 20 carbon atoms (each of said groups may be substituted by one or more R 4 groups, wherein one or more non-adjacent CH 2 groups may be replaced by R 4C=CR4、C=O、C=S、C=NR4、P(=O)(R4)、SO、SO2、NR4, O, S or CONR 4, and wherein one or more hydrogen atoms may be replaced by R5384 or NO 2), an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms and which may in each case be substituted by one or more R 4 groups, an aryloxy or heteroaryloxy having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 1 groups, or an aralkyl or heteroarylalkyl having from 5 to 40 aromatic ring atoms and which may be substituted by one or more R 4 groups, and wherein one or more hydrogen atoms may be substituted by one or more R 4 groups, and two of the same carbon atoms may optionally be bonded to one or more adjacent carbon atoms, may form an aliphatic ring or a ring system; R 1 is identical or different on each occurrence and is selected from H,D,F,Cl,Br,I,CN,NO2,N(Ar1)2,N(R4)