CN111635355A - Compound, hole transport material and organic electroluminescent device - Google Patents
Compound, hole transport material and organic electroluminescent device Download PDFInfo
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- CN111635355A CN111635355A CN202010518276.4A CN202010518276A CN111635355A CN 111635355 A CN111635355 A CN 111635355A CN 202010518276 A CN202010518276 A CN 202010518276A CN 111635355 A CN111635355 A CN 111635355A
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- Prior art keywords
- aryl
- substituted
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- heteroaryl
- reaction
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 230000005525 hole transport Effects 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- -1 heterocyclic arylamines Chemical class 0.000 claims abstract description 36
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 26
- 150000003254 radicals Chemical class 0.000 claims description 14
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 13
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 125000005549 heteroarylene group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000005580 triphenylene group Chemical group 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
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- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 7
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 6
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- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 6
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
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- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YEYHFKBVNARCNE-UHFFFAOYSA-N pyrido[2,3-b]pyrazine Chemical compound N1=CC=NC2=CC=CN=C21 YEYHFKBVNARCNE-UHFFFAOYSA-N 0.000 claims description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005556 thienylene group Chemical group 0.000 claims description 2
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- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 70
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 46
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 14
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- 239000002019 doping agent Substances 0.000 description 14
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 14
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
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Abstract
The embodiment of the invention provides a compound shown in a general formula (I), which can be used for a hole transport material. The compound has a parent structure connected by diversified fused heterocyclic arylamines, high bond energy among atoms, good thermal stability, contribution to solid-state accumulation among molecules and strong transition capability of a hole, and can be used as a hole transport layer material to effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device. The present application also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
Description
Technical Field
The invention relates to the technical field of organic light-emitting display, in particular to a hole transport material and an organic electroluminescent device containing the hole transport material.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical property, the electrical property, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. Currently, as an important functional material, a hole transport material has a direct influence on the mobility of holes, and ultimately influences the light emitting efficiency of the OLED. However, the hole transport materials currently used in OLEDs have low hole transport rates and poor energy level matching with adjacent layers, which severely limits the light emitting efficiency of the OLEDs and the display function of the OLED display devices.
Disclosure of Invention
The embodiment of the invention aims to provide a hole transport material to improve the luminous efficiency and prolong the service life of an organic electroluminescent device.
A first aspect of the invention provides a compound of general formula (I):
wherein,
Ar1and Ar2Each independently selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
l is selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
R1-R4each independently selected from hydrogen and C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl radical, C3-C30Heteroaryl, amine, the hydrogen atoms on the aryl, heteroaryl and amine each independentlyMay be substituted on its own by Ra, said R1-R4Wherein two adjacent groups can be connected to form a ring;
x and Y are each independently selected from O, S, CR5R6、NR7，R5And R6Each independently selected from C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl or C3-C30Heteroaryl radical, R7Is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
Z1-Z8each independently selected from CR8Or N, R8Selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl or C3-C30Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Ra, the Z1-Z8Any of which is linked to general formula (I) by a chemical bond;
the heteroatoms of the heteroaryl or heteroarylene groups are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
In a second aspect, the present application provides a hole transport material comprising at least one of the compounds provided herein.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the hole transport materials provided herein.
A fourth aspect of the present application provides a display apparatus comprising an organic electroluminescent device as provided herein.
The compound provided by the application has a parent structure connected by diversified fused heterocyclic arylamines, has high bond energy among atoms, good thermal stability, favorability for solid-state accumulation among molecules and strong transition capacity of holes. When the material is used as a hole transport material, the material has a proper energy level with the adjacent layers, so that the injection and the migration of holes are facilitated, the take-off and drop voltage can be effectively reduced, the hole migration rate is high, and the good luminous efficiency can be realized in an organic electroluminescent device. The organic electroluminescent device comprises the compound as a hole transport material, so that the take-off and landing voltage can be effectively reduced, the luminous efficiency is improved, and the service life of the organic electroluminescent device is prolonged. The display device provided by the application has an excellent display effect.
Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one embodiment of the present invention, and it is obvious for those skilled in the art that other embodiments can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first aspect of the invention provides a compound of general formula (I):
wherein,
ar1 and Ar2 are independently selected from aryl of C6-C30 or heteroaryl of C3-C30, and hydrogen atoms on the aryl and the heteroaryl can be independently substituted by Ra;
l is selected from a chemical bond, an arylene group of C6-C30, or a heteroarylene group of C3-C30, each independently hydrogen atom on the arylene and heteroarylene groups being substitutable with Ra;
R1-R4 are respectively and independently selected from hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl and amine, hydrogen atoms on the aryl, the heteroaryl and the amine can be independently substituted by Ra, and two adjacent groups in the R1-R4 can be connected to form a ring;
x and Y are each independently selected from O, S, CR5R6, NR7, R5 and R6 are each independently selected from C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl, R7 is selected from C6-C30 aryl or C3-C30 heteroaryl, and the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted by Ra;
Z1-Z8 are each independently selected from CR8 or N, R8 is selected from hydrogen, deuterium, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl, the hydrogen atoms on the aryl and heteroaryl can each independently be substituted by Ra, and any one of Z1-Z8 is connected with the general formula (I) through a chemical bond;
the heteroatoms of the heteroaryl or heteroarylene groups are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably, Ar1 and Ar2 are each independently selected from the group consisting of C6-C25 aryl and C3-C12 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently being substitutable by Ra;
preferably, L is selected from a bond, an arylene group of C6-C18, or a heteroarylene group of C3-C12, each independently of the hydrogen atoms on the arylene and heteroarylene groups being substitutable by Ra;
preferably, R1-R4 are each independently selected from hydrogen, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, C3-C12 heteroaryl, amine groups, the hydrogen atoms on the aryl, heteroaryl and amine groups each independently may be substituted with Ra;
preferably, R5 and R6 are each independently selected from C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl or C3-C12 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently being substitutable by Ra;
preferably, R7 is selected from C6-C18 aryl or C3-C18 heteroaryl, each of which independently hydrogen atoms may be substituted with Ra;
preferably, R8 is selected from hydrogen, deuterium, C1-C10 alkyl, C3-C6 cycloalkyl, C6-C12 aryl or C3-C12 heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently being substitutable by Ra.
More preferably, Ar1 and Ar2 are each independently selected from the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
More preferably, L is selected from the group consisting of a bond, a subunit of the following compound unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole.
More preferably, said R1-R4、R8Each independently selected from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, fluorenyl, phenanthryl, phenanthr,Benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, said R5And R6Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, said R7Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
For example, the compound of formula (I) is selected from the following compounds:
in a second aspect, the present application provides a hole transport material comprising at least one of the above compounds of the present application.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically shows the structure of a typical organic electroluminescent device, and the present application is not limited to this structure, and the hole transport material of the present application may be used in any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, and the like. In practice, these layers may be added or omitted as the case may be.
The compound adopted by the hole transport material has a parent structure connected by diversified fused heterocyclic arylamines, has high bond energy among atoms, good thermal stability, is beneficial to solid accumulation among molecules, has strong hole transition capability, can be used as a hole transport layer material, can effectively reduce the driving voltage of an organic electroluminescent device, improves the current efficiency of the organic electroluminescent device, and prolongs the service life of the organic electroluminescent device.
The derivative of diversified fused heterocycle is applied to a hole transport layer, has a proper energy level with adjacent layers, is favorable for injection and migration of holes, can effectively reduce the starting voltage, and can realize good luminous efficiency in a device due to high hole migration rate. The compound has a larger conjugate plane, is beneficial to molecular accumulation, shows good thermodynamic stability and shows long service life in an organic electroluminescent device.
Meanwhile, the preparation process of the derivative is simple and feasible, the raw materials are easy to obtain, and the derivative is suitable for industrial production.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the hole transport materials provided herein as a hole transport layer. In the present application, there is no particular limitation on the kind and structure of the organic electroluminescent device as long as the hole transport material provided herein can be used.
The organic electroluminescent device of the present application may be a light-emitting device having a top emission structure, and examples thereof include a light-emitting device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a bottom emission structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a double-sided light-emitting structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode are sequentially provided on a substrate.
In the organic electroluminescent device of the present application, any material used for the layer in the prior art may be used for the other layers except that the hole transport layer contains the hole transport material provided herein.
For convenience, the organic electroluminescent device of the present application is described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the hole transport material of the present application are within the scope of the present invention.
In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass, polymer materials, glass with TFT elements, polymer materials, and the like may be used.
In the present application, the material of the reflective anode electrode 2 is not particularly limited, and may be selected from transparent conductive materials known in the art, such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO), metal materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as PEDOT (poly 3, 4-ethylenedioxythiophene), and a multilayer structure of the above materials.
In the present application, the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as a host material, and a p-type dopant is added, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used, for example, the following p-type dopants may be used:
the hole transport layer 4 comprises at least one of the hole transport materials of the present application, and the hole transport layer 4 may also comprise a combination of at least one of the hole transport materials of the present application with at least one of the following known Hole Transport Materials (HTM).
For example, known Hole Transport Materials (HTMs) may be selected from at least one of the following HT-1 to HT-32 compounds:
in the present application, the light emitting material in the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art may be used, for example, the light emitting material may include a host material (GPH) and a light emitting dye (RPD). The host material may be selected from at least one of the following GPH-1 to GPH-80 compounds:
in a preferred embodiment of the present application, the light-emitting layer 5 employs the technique of phosphorescent electroluminescence. The light-emitting layer 5 contains a phosphorescent dopant, and the dopant may be at least one selected from the following compounds RPD-1 to RPD-28. The amount of the dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the electron transport layer 6 may be selected from at least one of the following known electron transport materials ET-1 to ET-57:
in the present application, the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3At least one of BaO, Na, Li, Ca and the like.
In the present application, the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, magnesium silver mixture, LiF/Al, ITO, Al, and other metals, metal mixtures, oxides, and the like.
A fourth aspect of the present application provides a display apparatus comprising an organic electroluminescent device as provided herein. The display device includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.
The method for preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be used, for example, the present application may be prepared by the following preparation method:
(1) cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection layer on the reflective anode electrode 2, wherein the main material of the hole injection layer is HTM, and the hole injection layer contains P-type dopant (P-dopant);
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) a luminescent layer 5 is vacuum evaporated on the hole transport layer 4, and the luminescent layer contains a host material and a guest material;
(5) vacuum evaporating an electron transport material containing an n-type dopant (n-dopant) as an electron transport layer 6 on the light emitting layer 5; (6) vacuum evaporating electron injection material selected from LiQ, LiF, NaCl, CsF, and Li on the electron transport layer 6 as electron injection layer 72O、Cs2CO3One or a combination of more of materials such as BaO, Na, Li, Ca and the like;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The above description has been made only of the structure of a typical organic electroluminescent device and a method for manufacturing the same, and it should be understood that the present application is not limited to this structure. The electron transport material of the present application can be used for an organic electroluminescent device of any structure, and the organic electroluminescent device can be manufactured by any manufacturing method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and the synthesis can be carried out by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthetic examples
Synthesis of a 1:
100mmol of 5-bromobenzo [ b ] was added to the reaction flask]Naphtho [1,2-d ]]Thiophene, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of N, N-Dimethylformamide (DMF) and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300mmol), 800ml of DMF, 200ml of water and 1 mol% of Pd (PPh) were added to the reaction flask3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h, and the disappearance of starting material was monitored by Thin Layer Chromatography (TLC). Column chromatography and isolation gave intermediate M3.
Adding 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M4 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M3.
100mmol of M4, 100mmol of 4-benzidine-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 1. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.45(s,1H),7.96-7.90(m,3H),7.88(t,J＝8.4Hz,3H),7.87–7.70(m,6H),7.64–7.53(m,8H),7.49(d,J＝8.0Hz,3H),7.43–7.29(m,5H),7.24-7.10(m,4H),1.69(s,6H)。
Synthesis of a 5:
100mmol of 5-bromobenzo [ b ] was added to the reaction flask]Naphtho [1,2-d ]]Thiophene, 120mmol of pinacol diboron, 40g of potassium carbonate (300mmol), 800ml of DMF and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300mmol), 800ml of DMF and 200ml of water were charged in a reaction flask, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h and TLC monitored for disappearance of starting material. Column chromatography and isolation gave intermediate M3.
Adding 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M4 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M3.
100mmol of M4, 100mmol of 4-benzidine-2- (N-phenylcarbazole), 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 5. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.43-8.29(m,3H),7.96(s,1H),7.86(s,1H),7.81–7.70(m,4H),7.70–7.53(m,11H),7.49(d,J＝8.0Hz,4H),7.43–7.34(m,7H),7.31(s,1H),7.19(d,J＝10.0Hz,4H),6.40(s,1H)。
Synthesis of a 12:
100mmol of 5-bromo-7, 7-dimethyl-7H-benzo [ c ] is added to the reaction flask]Fluorene, 120mmol of pinacol diboron, 40g of potassium carbonate (300mmol), 800ml of DMF and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 40g of potassium carbonate (300mmol) and 800 mmol of potassium carbonate were placed in a reaction flaskml of DMF and 200ml of water, and 1 mol% of Pd (PPh)3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h and the disappearance of starting material was monitored by TLC. Column chromatography and isolation gave intermediate M3.
Adding 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M4 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M3.
100mmol of M4, 100mmol of 2-benzidine-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 12. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.24-8.10(m,4H),8.05–7.85(m,3H),7.78-7.69(m,5H),7.62(s,1H),7.58(d,J＝8.4Hz,3H),7.50(dd,J＝13.2,9.6Hz,6H),7.45–7.32(m,4H),7.26(d,J＝12.6Hz,2H),7.14(s,1H),7.08(s,2H),6.40(s,1H),1.75(s,6H),1.69(s,6H)。
Synthesis of a 13:
adding 100mmol of 5-bromobenzo [ b ] naphtho [1,2-d ] carbazole, 120mmol of iodobenzene, 40g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M1 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of 5-bromobenzo [ b ] naphtho [1,2-d ] carbazole.
100mmol of M1, 120mmol of pinacol diborate, 41.4g of potassium carbonate (300mmol), 800ml of DMF and 1 mol% of Pd (dppf) Cl were added to a reaction flask2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M2, 100mmol of 2-iodo-5-bromonitrobenzene, 40g of potassium carbonate (300mmol), 800ml of DMF and 200ml of water were added to a reaction flask, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M2.
175.8mmol of M3, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h and TLC monitored for disappearance of starting material. Column chromatography and isolation gave intermediate M4.
Adding 100mmol of M4, 120mmol of iodobenzene, 40g of potassium carbonate (300mmol) and 800ml of DMF (dimethyl formamide) into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M5 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M4.
A reaction flask was charged with 100mmol of M4, 100mmol of bis 2- (9, 9-dimethylfluorene) amine, 28.83g sodium tert-butoxide (300mmol), 800ml xylene, and 1 mol% Pd (dba) was added. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 13. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.55(d,J＝8.0Hz,3H),7.96(s,1H),7.92–7.79(m,5H),7.72(s,1H),7.69–7.55(m,10H),7.51(d,J＝10.0Hz,4H),7.42(s,1H),7.34-7.11(m,9H),6.40(s,1H),1.69(s,12H)。
Synthesis of a 14:
100mmol of 5-bromobenzo [ b ] was added to the reaction flask]Naphtho [1,2-d ]]Thiophene, 120mmol of pinacol diboron, 40g of potassium carbonate (300mmol), 800ml of DMF and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300mmol), 800ml of DMF and 200ml of water were charged in a reaction flask, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h and TLC monitored for disappearance of starting material. Column chromatography and isolation gave intermediate M3.
Adding 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M4 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M3.
100mmol of M4, 100mmol of N- ([1,1' -biphenylyl ] -4-yl) benzofuran [2,3-b ] pyridin-7-amine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene are added to a reaction flask, and 1 mol% of Pd (dba) is added. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 14. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.42(s,1H),8.03(s,1H),7.97(d,J＝10.0Hz,3H),7.74(d,J＝8.8Hz,4H),7.64–7.52(m,6H),7.49(d,J＝8.0Hz,4H),7.43–7.35(m,6H),7.31(d,J＝7.6Hz,3H),7.26(s,1H),6.40(s,1H)。
Synthesis of a 15:
100mmol of 5-bromobenzo [ b ] was added to the reaction flask]Naphtho [1,2-d ]]Thiophene, 120mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol), 800ml of N, N-Dimethylformamide (DMF) and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M1, 100mmol of 2-iodo-5-bromonitrobenzene, 41.4g of potassium carbonate (300mmol), 800ml of DMF, 200ml of water and 1 mol% of Pd (PPh) were added to the reaction flask3)4. The reaction was carried out at 120 ℃ for 12 h. Reaction ofAfter completion of the reaction, the reaction was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M2 as a white powder. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
175.8mmol of M2, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h, and the disappearance of starting material was monitored by Thin Layer Chromatography (TLC). Column chromatography and isolation gave intermediate M3.
Adding 100mmol of M3, 120mmol of iodobenzene, 41.4g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M4 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M3.
100mmol of M4, 100mmol of 3-dibenzothiophene-2- (9, 9-dimethylfluorene), 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 15. Wherein Pd (dba) is added in an amount of 1 mol% based on M4.
1H NMR(400MHz,Chloroform)8.54(s,1H),8.45(s,1H),8.16–7.88(m,3H),7.88–7.67(m,5H),7.68(s,1H),7.68(s,1H),7.64–7.52(m,5H),7.40(dd,J＝10.4,7.6Hz,5H),7.27(d,J＝8.4Hz,6H),7.24-7.03(m,4H),6.40(s,1H),1.69(s,6H)。
Synthesis of a 23:
100mmol of dinaphtho [2,1-b:1',2' -d ] furan, 400ml of dichloromethane and 100mmol of NBS were added to the reaction flask. The reaction is stirred for 12 hours at normal temperature. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1.
100mmol of M1, 120mmol of pinacol diborate, 40g of potassium carbonate (300mmol), 800ml of DMF and 1 mol% of Pd (dppf) Cl were added to a reaction flask2. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein Pd (dppf) Cl2Is added in an amount of 5-bromobenzo [ b ]]Naphtho [1,2-d ]]1 mol% of thiophene.
100mmol of M2, 100mmol of 2-iodo-5-bromonitrobenzene, 40g of potassium carbonate (300mmol), 800ml of DMF and 200ml of water were added to a reaction flask, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M2.
175.8mmol of M4, 159.8mmol of triphenylphosphine and 1000ml of o-dichlorobenzene were added to a single-neck flask, heated to reflux, reacted for 8h and TLC monitored for disappearance of starting material. Column chromatography and isolation gave intermediate M4.
Adding 100mmol of M4, 120mmol of 3-iodobiphenyl, 40g of potassium carbonate (300mmol) and 800ml of DMF into a reaction bottle, and adding 1 mol% of cuprous iodide and 1 mol% of 1, 10-phenanthroline. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give M5 as a yellow powder. Wherein the addition amount of cuprous iodide and 1, 10-phenanthroline is 1 mol% of M4.
100mmol of M5, 100mmol of 2-benzidine-2- (9, 9-dimethylfluorene), 40g of sodium tert-butoxide (300mmol), 800ml of xylene are added to the reaction flask, and 1 mol% of Pd (dba) is added. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 23. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.21(s,1H),7.97(d,J＝12.0Hz,2H),7.81(s,1H),7.70(d,J＝10.0Hz,5H),7.64–7.50(m,12H),7.36(d,J＝13.6Hz,6H),7.29-7.14(m,10H),6.40(s,1H),1.69(s,6H)。
Example 1
Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
then, the glass substrate with the anode is placed in a vacuum chamber and is vacuumized to be less than 10 DEG-5And (3) vacuum evaporating a hole injection layer on the anode layer film by using the Torr, wherein the material of the hole injection layer is HT-11 and a p-type dopant (p-dopant) with the mass ratio of 3%, the evaporation rate is 0.1nm/s, the evaporation film thickness is 10nm, and the material of the hole injection layer and the p-type dopant are as follows:
then, a hole transport material a1 material was vacuum-evaporated on the hole injection layer as a hole transport layer, wherein the evaporation rate was 0.1nm/s, the evaporation film thickness was 80nm, and the material of the hole transport layer was:
then, a luminescent layer is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a host material GHP-16 and a dye material RPD-1, evaporation is carried out by a multi-source co-evaporation method, wherein the evaporation rate of the host material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the host material, the total film thickness of evaporation is 30nm, and the host material and the guest material are respectively the following materials:
then, an electron transporting layer containing an electron transporting material ET42 was vacuum-evaporated over the light emitting layer. Wherein, the evaporation rate is 0.1nm/s, the evaporation film thickness is 30nm, and the selected electron transport material ET42 has the following formula:
then, LiF with the thickness of 0.5nm is subjected to vacuum evaporation on the Electron Transport Layer (ETL) to serve as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
then, an Al layer having a thickness of 150nm was vacuum-evaporated on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate was 1nm/s and the evaporation film thickness was 50 nm.
Examples 2 to 7
The procedure was as in example 1 except that A1 was replaced with A5, A12, A13, A14, A15 and A23, respectively. See table 1 for details.
Comparative example 1
The procedure was as in example 1 except that HT-27 was used in place of A1.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in examples 1 to 5 and comparative example 1 were measured at the same luminance using a digital source meter and a luminance meter, and specifically, the luminance of the organic electroluminescent device reached 5000cd/m when the voltage was increased at a rate of 0.1V/sec2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the lifetime test was as follows: using a luminance meter at 5000cd/m2Organic electroluminescence was measured by maintaining constant current at luminanceThe luminance of the light emitting device was reduced to 4750cd/m2Time in hours.
Table 1 organic electroluminescent device performance results
As can be seen from table 1, the compounds a1, a5, a12, a13, a14, a15 and a23 prepared by the method are used as hole transport materials of organic electroluminescent devices, can effectively reduce driving voltage, improve current efficiency and prolong the service life of the devices, and are hole transport materials with good performance.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (11)
1. A compound of the general formula (I):
wherein,
Ar1and Ar2Each independently selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
l is selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
R1-R4each independently selected from hydrogen and C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl radical, C3-C30Heteroaryl, amine, the hydrogen atoms on the aryl, heteroaryl and amine may each independently be substituted by Ra, R1-R4Wherein two adjacent groups can be connected to form a ring;
x and Y are each independently selected from O, S, CR5R6、NR7，R5And R6Each independently selected from C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl or C3-C30Heteroaryl radical, R7Is selected from C6-C30Aryl or C of3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
Z1-Z8each independently selected from CR8Or N, R8Selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C30Aryl or C3-C30Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted by Ra, the Z1-Z8Any of which is linked to general formula (I) by a chemical bond;
the heteroatoms of the heteroaryl or heteroarylene groups are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
2. The compound according to claim 1, wherein,
Ar1and Ar2Each independently selected from C6-C25Aryl or C of3-C12The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
l is selected from the group consisting of a bond, C6-C18Arylene group of (A) or (C)3-C12The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
R1-R4each independently selected from hydrogen and C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C12Aryl radical, C3-C12Heteroaryl, amine, the hydrogen atoms on the aryl, heteroaryl and amine each independently can be substituted with Ra;
R5and R6Each independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C6-C12Aryl or C3-C12Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Ra;
R7is selected from C6-C18Aryl or C of3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R8selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C6-C12Aryl or C3-C12Heteroaryl, the hydrogen atoms on the aryl and heteroaryl groups each independently can be substituted with Ra.
3. The compound according to claim 1, wherein said Ar is1And Ar2Each independently selected from the following unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
4. The compound of claim 1, wherein L is selected from the group consisting of a bond, a subunit of the following compound unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole.
5. A compound according to claim 1, wherein R is1-R4、R8Each independently selected from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
6. A compound according to claim 1, wherein R is5And R6Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
7. A compound according to claim 1, wherein R is7Selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothiazylA thienyl group, an aza-dibenzothienyl group, a 9, 9-dimethylfluorenyl group, a spirofluorenyl group, an arylamine group, a carbazolyl group.
8. The compound according to claim 1, wherein the compound is selected from the following compounds:
9. a hole transport material comprising at least one of the compounds of any one of claims 1-8.
10. An organic electroluminescent device comprising at least one hole transport material of claim 9.
11. A display device comprising the organic electroluminescent element according to claim 10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924217A (en) * | 2008-07-14 | 2013-02-13 | 葛来西雅帝史派有限公司 | Fluorene and pyrene derivatives and organic electroluminescent device using the same |
| WO2017043835A1 (en) * | 2015-09-08 | 2017-03-16 | 덕산네오룩스 주식회사 | Organic electronic diode compound, organic electronic diode using same, and device therefor |
| CN107619410A (en) * | 2016-07-14 | 2018-01-23 | 株式会社Lg化学 | Compound and the organic electronic element for including it |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924217A (en) * | 2008-07-14 | 2013-02-13 | 葛来西雅帝史派有限公司 | Fluorene and pyrene derivatives and organic electroluminescent device using the same |
| WO2017043835A1 (en) * | 2015-09-08 | 2017-03-16 | 덕산네오룩스 주식회사 | Organic electronic diode compound, organic electronic diode using same, and device therefor |
| CN107619410A (en) * | 2016-07-14 | 2018-01-23 | 株式会社Lg化学 | Compound and the organic electronic element for including it |
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| Title |
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| 陶友田, 知识产权出版社 * |
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