CN115850256A - Diazafluorene compound, material for organic electroluminescent device and organic electroluminescent device - Google Patents
Diazafluorene compound, material for organic electroluminescent device and organic electroluminescent device Download PDFInfo
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- -1 Diazafluorene compound Chemical class 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- LOBSPZHDUJUOES-UHFFFAOYSA-N 9-diazofluorene Chemical compound C1=CC=C2C(=[N+]=[N-])C3=CC=CC=C3C2=C1 LOBSPZHDUJUOES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 238000001704 evaporation Methods 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 68
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000002994 raw material Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000012044 organic layer Substances 0.000 description 22
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- 229910052757 nitrogen Inorganic materials 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
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- STGMORHGPQLXMT-UHFFFAOYSA-N 9h-indeno[2,1-c]pyridazine Chemical compound C1=NN=C2CC3=CC=CC=C3C2=C1 STGMORHGPQLXMT-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- BGGALFIXXQOTPY-NRFANRHFSA-N C1(=C(C2=C(C=C1)N(C(C#N)=C2)C[C@@H](N1CCN(CC1)S(=O)(=O)C)C)C)CN1CCC(CC1)NC1=NC(=NC2=C1C=C(S2)CC(F)(F)F)NC Chemical compound C1(=C(C2=C(C=C1)N(C(C#N)=C2)C[C@@H](N1CCN(CC1)S(=O)(=O)C)C)C)CN1CCC(CC1)NC1=NC(=NC2=C1C=C(S2)CC(F)(F)F)NC BGGALFIXXQOTPY-NRFANRHFSA-N 0.000 description 1
- 101100042788 Caenorhabditis elegans him-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N Dibenzofuran Natural products C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 208000027386 essential tremor 1 Diseases 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YGBMCLDVRUGXOV-UHFFFAOYSA-N n-[6-[6-chloro-5-[(4-fluorophenyl)sulfonylamino]pyridin-3-yl]-1,3-benzothiazol-2-yl]acetamide Chemical compound C1=C2SC(NC(=O)C)=NC2=CC=C1C(C=1)=CN=C(Cl)C=1NS(=O)(=O)C1=CC=C(F)C=C1 YGBMCLDVRUGXOV-UHFFFAOYSA-N 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
The application discloses a diazofluorene compound, which takes diazofluorene as a basic structure, and an aryl or heteroaryl is introduced into the basic structure, wherein the diazofluorene compound has the following general formula I: wherein, X 1 ～X 8 Each independently represents an N atom or a C atom, and the number of nitrogen atoms is 2; the aryl or heteroaryl is substituted or unsubstituted aryl or heteroaryl; the refractive index of the compound is greater than or equal to 1.85. The application also discloses a material for the organic electroluminescent device and the organic electroluminescent device. The diazofluorene compound has high refractive index, thermal stability and film-forming property, can be used as a light extraction layer material, and is suitable for manufacturing OLED devices in an evaporation mode.
Description
Technical Field
The invention relates to an organic luminescent material, in particular to a diazofluorene compound, an organic electroluminescent device material and an organic electroluminescent device.
Background
Organic Light-Emitting diodes (OLEDs) have many advantages such as full solid state, active Light emission, low power consumption, high contrast, ultra-thin, large viewing angle, fast response speed, wide temperature adaptation range, and easy implementation of flexible display and 3D display, and are receiving much attention in the scientific and industrial fields. The light emitting principle of the OLED is that electrons and holes are injected into the device from the cathode and the anode, respectively, under the drive of a forward voltage, carriers move toward the opposite electrode in the organic layer, and meet and combine in the light emitting layer to form excitons, and the excitons jump back to the ground state by radiation to emit light. Due to the potential great application value of OLEDs, how to fabricate high-efficiency devices is attracting more and more attention. However, since there is a great gap between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted. Therefore, how to improve the light extraction efficiency of the OLED becomes a hot point of research.
In order to solve the problem of low light extraction efficiency of the OLED, adding a light extraction layer (CPL) on the surface of the device is the most effective way at present, and the preparation process is simple and suitable for industrialization. Problems with existing CPL materials include: (1) the refractive index is not high enough and the light extraction effect is not good enough; (2) The difference in refractive index measured in each wavelength region of blue light, green light, and red light is large. Therefore, high light extraction efficiency cannot be simultaneously obtained for all the lights in the light emitting device emitting blue, green, and red lights. (3) The decomposition temperature of the material is low, which causes severe decomposition during long-time evaporation.
In order to improve the light extraction efficiency of the organic light emitting device and to increase the lifetime of the device, it is necessary to introduce a capping layer material having a high refractive index, excellent film stability, and good durability.
Disclosure of Invention
In order to overcome the defects of the prior art, the application aims to provide a diazafluorene compound, and solve the problems of low refractive index and poor film forming stability of the existing organic light-emitting material.
In order to solve the above problems, the technical solution adopted by the present application is as follows:
a diazofluorene compound takes diazofluorene as a basic structure, and an aryl or heteroaryl is introduced into the basic structure, wherein the diazofluorene compound has the following general formula I:
wherein, X 1 ～X 8 Independently represent N atom or C atom, and the number of nitrogen atoms is 2; the aryl or heteroaryl is substituted or unsubstituted aryl or heteroaryl; the refractive index of the compound is greater than or equal to 1.85.
More preferably, R1 and R2 in the general formula I described herein have the same or different structures and represent one of H atom, C1-C30 linear or branched alkyl group, C1-C30 linear or branched alkoxy group, C1-C30 linear or branched alkylthio group, C1-C30 linear or branched alkylamino group, substituted or unsubstituted C6-C60 aryl group, and substituted or unsubstituted C6-C60 heteroaryl group; a is one of H atom, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C6-C60 heteroaryl; l1 and L2 have the same or different structures and represent one of a single bond, a substituted or unsubstituted C6-C60 arylene group and a substituted or unsubstituted C6-C60 heteroarylene group; ar (Ar) 1 And Ar 2 Have the same or different structures and represent any one of a substituted or unsubstituted C6-C60 aryl group and a substituted or unsubstituted C6-C60 heteroaryl group.
As a further preferred embodiment, the basic structure described herein has the following general formula ii, wherein the general formula ii is one of the following structures:
as a further preferred embodiment, L1 and L2 described herein are independently selected from a single bond or one of the following groups:
as a further preferred embodiment, ar described herein 1 、Ar 2 Independently selected from one of the following groups:
as a further preferred embodiment, the general formula I described herein is one of the following compounds represented by structural formula 1 to structural formula 216:
further, the present application also provides an application of the diazafluorene compound in an organic electroluminescent device, wherein the diazafluorene compound is used as a light extraction layer of the organic electroluminescent device.
Further, the present application also provides a material for an organic electroluminescent device, wherein the material is a diazafluorene compound described herein, and the compound is used as a light extraction layer of the organic electroluminescent device.
Further, the present application also provides an organic electroluminescent device, which comprises a substrate, an anode, a first hole injection layer, a second hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode, and a light extraction layer in sequence from bottom to top; the light extraction layer is a film formed on the cathode from the diazafluorene compound described herein.
Compared with the prior art, the invention has the beneficial effects that:
1. the diazofluorene compound has high refractive index, thermal stability and film-forming property, can be used as a light extraction layer material, and is suitable for manufacturing OLED devices in an evaporation mode.
2. The application use diazafluorene as foundation structure in the compound of diazafluorene, diazafluorene is a rigid group, improve the stability and the glass transition temperature of material, substituted or unsubstituted aryl or heteroaryl has been guaranteed to the material not crystallize and have lower coating by vaporization temperature under the thin film state through introducing on diazafluorene as foundation structure in this application, satisfy the demand of volume production, higher refracting index has simultaneously, be applied to in the organic electroluminescent device, the light that can effectively promote the device takes out efficiency.
The present invention will be described in further detail with reference to specific embodiments.
Drawings
FIG. 1 is an ultraviolet-visible (UV-vis) absorption spectrum of a diazafluorene compound of example 1.
FIG. 2 is a thermogravimetric (Tg) diagram of the diazofluorene compound of example 1.
Fig. 3 is a schematic structural diagram of an organic electroluminescent device to which embodiments are applied.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but 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 application.
The terms "comprises," "comprising," and any other variations thereof, as used herein in the specification and claims, are intended to cover a non-exclusive inclusion, that is, a inclusion, a non-exclusive inclusion, that does not include the contents explicitly described in the specification and claims, or an inclusion, or a non-exclusive inclusion, that does not include the steps or elements inherent in the product, method, or structure.
The diazafluorene compound described in the embodiments of the present application uses diazafluorene as a basic structure, and an aryl or heteroaryl group is introduced into the basic structure, and the diazafluorene compound has the following general formula i:
wherein, X 1 ～X 8 Independently represent N atom or C atom, and the number of nitrogen atoms is 2; the aryl or heteroaryl is substituted or unsubstituted aryl or heteroaryl; the refractive index of the compound is greater than or equal to 1.85. Preferably, in some embodiments, the twoThe refractive index of the azafluorene compound is 1.85-2.0. In the application, the diazafluorene has good planarity, larger conjugation area and more ordered molecular stacking; meanwhile, intermolecular hydrogen bonds can be formed, intermolecular action is enhanced, and the film is more compact and has higher refractive index.
Further, in some embodiments, R1 and R2 in the general formula I described herein have the same or different structural groups and represent one of H atom, C1-C30 linear or branched alkyl group, C1-C30 linear or branched alkoxy group, C1-C30 linear or branched alkylthio group, C1-C30 linear or branched alkylamino group, substituted or unsubstituted C6-C60 aryl group, and substituted or unsubstituted C6-C60 heteroaryl group.
Further, in some embodiments, A in formula I described herein is one of a H atom, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C6-C60 heteroaryl group.
Further, in some embodiments, in formula i described herein, L1 and L2 have the same or different structural groups and represent one of a single bond, a substituted or unsubstituted C6 to C60 arylene group, and a substituted or unsubstituted C6 to C60 heteroarylene group.
Further, in some embodiments, in formula I described herein, ar 1 And Ar 2 The substituted or unsubstituted aryl group having 6 to 60 carbon atoms and the substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms have the same or different structures.
The following are specific examples of the present invention, and the raw materials, reaction monomers and reagents used in the following examples can be obtained commercially, unless otherwise specified.
Example 1
This example provides a diazafluorene compound having the formula 1:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
1) Preparation of intermediate M2: raw material M1 (8g, 100mmol) was weighed into a 250mL two-necked round-bottomed flask, dissolved in 50mL of dichloromethane, and Br2 (1691, 100mmol) was added dropwise under ice bath to stop the reaction after 12 hours. Poured into water, extracted with dichloromethane, separated, and the organic layer dried over anhydrous sodium sulfate, filtered, concentrated, and chromatographed over a column to give compound M2 (13.67g, 86mmol), yield: 86 percent.
2) Preparation of intermediate M4: intermediate M2 (7.95g, 50mmol) and starting material M3 (9.84 g, 60mmol) were weighed into a 500mL three-necked round-bottomed flask, dissolved by adding 150mL toluene, 100mL water, 50mL ethanol, evacuated and purged with nitrogen 3 times, and then Pd (PPh) was added 3 ) 4 (2.9g，2.5mmol)、 K 2 CO 3 (20.7g, 150mmol) and heated to 85 ℃ for 24 hours. Samples were taken and the starting material had reacted to completion. Cooled to room temperature, poured into water, extracted with dichloromethane, the layers separated, the organic layer dried over anhydrous sodium sulfate, filtered, concentrated, and chromatographed over a column to give compound M4 (8.13g, 41mmol), yield: 82 percent.
3) Preparation of intermediate M5: mg (1.2g, 50mmol) and 50mL THF were weighed into a 100mL two-necked round bottom flask, evacuated and purged with nitrogen 3 times, and added with CH in small portions 3 Br (4.56g, 48 mmol) was reacted under reflux for 4h. A250 mL two-neck round-bottom flask was taken, added with intermediate M4 (7.93 g,40 mmol) and 50mL THF, evacuated and purged with nitrogen 3 times, and added with CH a small number of times 3 MgBr, and reacting for 12h under reflux. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound M5 (5.14g, 24mmol), yield: 60 percent.
4) Preparation of intermediate M6: intermediate M5 (4.28g, 20mmol) was weighed into a 500mL two-necked round-bottomed flask, dissolved by adding 200mL of AcOH, HCl (10 mL) was slowly added dropwise under ice bath, and after completion of the reaction, filtration was performed to obtain Compound M6 (2.83g, 14.4 mmol), yield: 72 percent.
5) Preparation of intermediate A1: intermediate M6 (1.96g, 10mmol) was weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 50mL of methylene chloride, and Br was added dropwise under ice bath 2 (3.2g, 20mmol), and the reaction was stopped after 12 hours. Poured into water, extracted with dichloromethane, separated, and the organic layer dried over anhydrous sodium sulfate, filtered, concentrated, and chromatographed over a column layer to give compound A1 (3g, 8.5mmol), yield: 85 percent.
6) Preparation of compound 1: intermediate A1 (1.77g, 5 mmol) and raw material B1 (1.79 g,11 mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、 K 2 CO 3 (2.07g, 15mmol), and the reaction mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 1 (1.74g, 4.05mmol), yield: 81 percent.
Fig. 1 is an ultraviolet-visible (UV-vis) absorption spectrum of compound 1, and fig. 2 is a thermogravimetric (Tg) spectrum of compound 1. The absorption edge of the compound 1 in fig. 1 is about 420nm, and there is substantially no absorption in the visible light region over 420nm, which is beneficial to obtain higher light extraction and external quantum efficiency of the OLED device. In fig. 2, it can be seen that the thermal decomposition temperature of the compound 1 exceeds 380 ℃, and the compound has good thermal stability, and is suitable for preparing a thin film by an evaporation process, thereby being beneficial to obtaining an OLED device with high stability.
Example 2
This example provides a diazafluorene compound having the formula 5:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A1 (1.77g, 5 mmol) and raw material B2 (1.97g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to give compound 5 (1.94g, 4.2mmol), yield: 84 percent.
Example 3
This example provides a diazafluorene compound having the formula 9:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A1 (1.77g, 5 mmol) and raw material B3 (2.62g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating the layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and passing through a column to obtain a layerThe spectrum gave compound 9 (2.18g, 3.75mmol), yield: 75 percent.
Example 4
This example provides a diazafluorene compound having the formula 17:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A1 (1.77g, 5 mmol) and raw material B4 (2.63g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water and 5mL of ethanol, evacuated and charged with nitrogen gas 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 17 (2.33g, 4 mmol), yield: 80 percent.
Example 5
This example provides a diazafluorene compound having a formula as shown in fig. 32:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A1 (1.77g, 5 mmol) and raw material B5 (3.47g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and charged with nitrogen gas 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 32 (3.05g, 4.15mmol), yield: 83 percent.
Example 6
This example provides a diazafluorene compound having the formula 74:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
1) Preparation of intermediate N2: raw material N1 (10.55g, 50mmol) was weighed into a 500mL three-necked round-bottomed flask, dissolved in 200mL of benzene, and after bubbling with dry HCl gas for 5min, amyl nitrite (7.03g, 60mmol) was slowly added. The mixture was heated to 40 ℃ and stirred for 5h while passing dry HCl gas. After stirring at room temperature for 12h, the reaction was filtered and rinsed with MeOH, DCM to give compound N2 (10.08g, 42mmol), yield: 84 percent.
2) Preparation of intermediate N3: intermediate N2 (6 g, 25mmol) and sodium dithionite (13 g, 75mmol) were weighed into a 500mL three-necked round-bottomed flask, and 50mL of ethanol was added. The mixture was evacuated and purged with nitrogen 3 times, 50mL of a 14.5% ammonia solution was added, and the mixture was stirred at room temperature for 3 days in the dark. After 50mL of distilled water was added to the reaction system, the mixture was heated under reflux in air for 24 hours. After the reaction was completed, it was cooled to room temperature, and 100mL of distilled water was added. After stirring, the mixture was filtered and rinsed well with MeOH, ether to give compound N3 (3.21g, 7.75mmol), yield: 62 percent.
3) Preparation of intermediate N4: intermediate N3 (4.14g, 10mmol) and sodium dichromate dihydrate (29.8g, 100mmol) were weighed out and charged into a 500mL three-necked round-bottomed flask, and acetic acid (250 mL) and acetic anhydride (50 mL) were added, and the mixture was heated to 40 ℃ and stirred for 3 days. After the reaction is over, water and NaHCO are added 3 The aqueous solution was filtered, and the resulting precipitate was purified by column chromatography to obtain compound N4 (2.92g, 6.6 mmol), yield: 66 percent.
4) Preparation of intermediate N5: mg (1.2g, 50mmol) and 50mL THF were weighed into a 100mL two-necked round bottom flask, evacuated and charged with nitrogen 3 times, and 2-bromobiphenyl (20.51 g, 88 mmol) was added in small portions and reacted under reflux for 4 hours. A250 mL double-neck round-bottom flask is taken, added with intermediate N4 (17.68 g, 40mmol) and 50mL THF, vacuumized and charged with nitrogen for 3 times, added with the prepared Grignard reagent in small amount for multiple times, and refluxed for 12h. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and subjecting to column chromatography to obtain compound N5 (18.31g, 24.4mmol), yield: 61 percent.
5) Preparation of intermediate A2: intermediate N5 (15g, 20mmol) was weighed into a 500mL two-necked round-bottomed flask, dissolved by adding 200mL of AcOH, HCl (10 mL) was slowly added dropwise under ice bath, and after completion of the reaction, the mixture was filtered to obtain Compound A2 (10.57g, 14.8mmol) in yield: 74 percent.
6) Preparation of compound 74: intermediate A2 (3.57g, 5 mmol) and raw material B1 (1.79 g,11 mmol) were weighed into a 100mL two-neck round-bottom flask, dissolved by adding 15mL toluene, 10mL water, 5mL ethanol, evacuated and charged with nitrogen 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、 K 2 CO 3 (2.07g, 15mmol), and the mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 74 (3.24g, 4.1mmol), yield: 82 percent.
Example 7
This example provides a diazafluorene compound having the formula 78:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A2 (3.57g, 5 mmol) and raw material B2 (1.97g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water and 5mL of ethanol, evacuated and charged with nitrogen gas 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07g, 15mmol), and the reaction mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extraction with dichloromethane, separation, drying of the organic layer over anhydrous sodium sulfate, filtration, concentration, column chromatography gave compound 78 (3.5g, 4.25mmol), yield: 85 percent.
Example 8
This example provides a diazafluorene compound having the formula 82:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A2 (3.57g, 5 mmol) and a crude product were weighedCharge B3 (2.62g, 11mmol) was charged into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. After cooling to room temperature, pouring into water, extraction with dichloromethane, separation, drying of the organic layer over anhydrous sodium sulfate, filtration, concentration, column chromatography gave compound 82 (3.67g, 3.9mmol), yield: 78 percent.
Example 9
This example provides a diazafluorene compound having the formula 90:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A2 (3.57g, 5 mmol) and raw material B4 (2.63g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to give compound 90 (3.5g, 3.7 mmol), yield: 74 percent.
Example 10
This example provides a diazafluorene compound having the formula 104:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A2 (3.57g, 5 mmol) and raw material B5 (3.47g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07g, 15mmol), and the reaction mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 104 (4.16g, 3.8mmol), yield: and 76 percent.
Example 11
This example provides a diazafluorene compound having the formula 147:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
1) Preparation of intermediate L2: weighing raw material L1 (14.7g, 50mmol) in a 1000mL three-neck round bottom flask, adding 500mL ethanol, and dropwise adding NaBH under ice bath 4 (18.92g, 500mmol), and the reaction mixture was stirred at room temperature for 20 hours. The solvent was removed under reduced pressure, 300mL of water was added, ether was extracted, and the organic layer was extracted with anhydrous sodium sulfateDrying, filtration and spin-drying gave compound L2 (8.7g, 32.5mmol), yield: 65 percent.
2) Preparation of intermediate A3: intermediate L2 (5.36g, 20mmol) and raw material L3 (5.47 g, 30 mmol) are weighed and added into a 1000mL three-neck round-bottom flask, 500mL ethanol and 50mL acetic acid are added, vacuum pumping is carried out, nitrogen gas is filled for 3 times, and the mixture is heated until reflux reaction is carried out for 12 hours. After removal of ethanol under reduced pressure, the residue was dissolved in dichloromethane, washed with water, the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography to give compound A3 (7.17g, 17.4 mmol), yield: 87 percent.
3) Preparation of compound 147: intermediate A3 (2.06g, 5 mmol) and raw material B1 (1.79 g,11 mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and purged with nitrogen 3 times, and then added with Pd (PPh) 3 ) 4 (289mg，0.25mmol)、 K 2 CO 3 (2.07g, 15mmol), and the reaction mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 147 (2.12g, 4.35mmol), yield: 87 percent.
Example 12
This example provides a diazafluorene compound having the formula 151:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A3 (2.06g, 5 mmol) and raw material B2 (1.97g, 11mmol) were weighed and charged into a 100mL two-neck round-bottom flask, dissolved by adding 15mL toluene, 10mL water, 5mL ethanol, and evacuatedNitrogen was bubbled 3 times, then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 151 (2.13g, 4.1mmol), yield: 82 percent.
Example 13
This example provides a diazafluorene compound having the formula 155:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A3 (2.06g, 5 mmol) and raw material B3 (2.62g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and charged with nitrogen gas 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07g, 15mmol), and the mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extraction with dichloromethane, separation, drying of the organic layer over anhydrous sodium sulfate, filtration, concentration, column chromatography gave compound 155 (2.71g, 4.25mmol), yield: 85 percent.
Example 14
This example provides a diazafluorene compound having the formula 162:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A3 (2.06g, 5 mmol) and raw material B4 (2.63g, 11mmol) were weighed into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL of toluene, 10mL of water, and 5mL of ethanol, evacuated and charged with nitrogen gas 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07 g,15 mmol), heated to 85 ℃ and reacted for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, extracting with dichloromethane, separating layers, drying the organic layer with anhydrous sodium sulfate, filtering, concentrating, and column chromatography to obtain compound 162 (2.59g, 4.05mmol), yield: 81 percent.
Example 15
This example provides a diazafluorene compound having the formula 177:
the reaction formula for preparing the diazafluorene compound is as follows:
the process for preparing the compound is as follows:
intermediate A3 (2.06g, 5 mmol) and raw material B5 (3.47g, 11mmol) were weighed and charged into a 100mL two-necked round-bottomed flask, dissolved by adding 15mL toluene, 10mL water, and 5mL ethanol, evacuated and charged with nitrogen 3 times, and then Pd (PPh) was added 3 ) 4 (289mg，0.25mmol)、K 2 CO 3 (2.07g, 15mmol), and the reaction mixture was heated to 85 ℃ to react for 24 hours. The sample point is the plate, and the raw materials have reacted completely. Cooling to room temperature, pouring into water, IIMethyl chloride extraction, separation, drying of the organic layer over anhydrous sodium sulfate, filtration, concentration, column chromatography gave compound 177 (3.33g, 4.2mmol), yield: 84 percent.
[ PROPERTIES DETECTION ]
The compounds of examples 1-15 above were tested for thermal properties and refractive index, respectively, and comparative example 1, which is a CPL layer material currently used in light emitting devices, was defined as Alq3 (8-hydroxyquinoline aluminum). Wherein the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC200F3 differential scanning calorimeter of Germany Chi-resistant company), and the heating rate is 10 ℃/min; the refractive index is measured by an ellipsometer (J.A.Woollam Co. Model: ALPHA-SE, USA) and tested in an atmospheric environment. The results are shown in Table 1.
Table 1: results comparing the properties of examples 1 to 15 with those of the prior art
As can be seen from the data in the table above, compared with the currently applied Alq3 material, the organic compound of the present invention has high glass transition temperature and high refractive index, and simultaneously, due to the containing of the diazafluorene rigid group, the thermal stability of the material is ensured. Therefore, after the organic material taking the diazafluorene as the basic structure is applied to a CPL layer of an OLED device, the light extraction efficiency of the device can be effectively improved.
Application examples
In order to verify the effect of the application of the dibenzofuran compounds described herein to the luminous efficiency of the organic electroluminescent device, the dibenzofuran compounds of examples 1-15 above were used to fabricate organic electroluminescent devices, which are listed as application examples 1-15, respectively, and the application of Alq3 was also used as application comparative example 1. The application examples 1 to 15 and the application comparative example 1 adopt the same manufacturing process, and the specific manufacturing method is as follows:
ITO/Ag/ITO is used as an anode on the glass substrate; performing vacuum evaporation on the anode to form HIM-1 as a first hole injection layer, wherein the evaporation thickness is 60nm; HAT-CN is evaporated on the first hole injection layer in vacuum to be used as a second hole injection layer, and the evaporation thickness is 5nm; carrying out vacuum evaporation on the NPB as a hole transport layer on the second hole injection layer, wherein the evaporation thickness is 60nm; vacuum evaporating BH and 3% BD on the hole transport layer as a light emitting layer, wherein the evaporation thickness is 25nm; performing vacuum evaporation on the light-emitting layer to form an ETM1: liq (1); evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; performing vacuum evaporation on the electron injection layer to form Mg/Ag (9; examples 1 to 15 of the dibenzofuran compound (as application examples 1 to 15) and Alq3 (as application comparative example 1) of comparative example 1 were each vacuum-evaporated as a light extraction layer on a cathode to a thickness of 60nm.
The structural formula of the related materials involved in the preparation process is as follows:
the organic electroluminescent devices of application examples 1 to 15 and application comparative example 1 were tested for their luminous efficiency, and the results are shown in table 2.
Table 2:
as can be seen from the results in table 2, when the organic compound with diazafluorene as a core is applied to the CPL layer of the OLED light emitting device, the light extraction effect is significantly improved compared to comparative example 1 in which Alq3 is used as an existing material.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (9)
1. A diazofluorene compound is characterized in that diazofluorene is used as a basic structure, and an aryl or heteroaryl group is introduced into the basic structure, wherein the diazofluorene compound has the following general formula I:
wherein, X 1 ～X 8 Independently represent N atom or C atom, and the number of nitrogen atoms is 2; the aryl or heteroaryl is substituted or unsubstituted aryl or heteroaryl; the compound has a refractive index of greater than or equal to 1.85.
2. The diazafluorene compound according to claim 1, wherein R1 and R2 in the general formula i have the same or different structural groups and each represents one of an H atom, a C1-C30 linear or branched alkyl group, a C1-C30 linear or branched alkoxy group, a C1-C30 linear or branched alkylthio group, a C1-C30 linear or branched alkylamino group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C6-C60 heteroaryl group; a is one of H atom, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C6-C60 heteroaryl; l1 and L2 have the same or different structures and represent one of a single bond, a substituted or unsubstituted C6-C60 arylene group and a substituted or unsubstituted C6-C60 heteroarylene group; ar (Ar) 1 And Ar 2 Have the same or different structures and represent any one of a substituted or unsubstituted C6-C60 aryl group and a substituted or unsubstituted C6-C60 heteroaryl group.
3. The diazafluorene compound according to claim 1, wherein said basic structure has the following general formula ii, said general formula ii being one of the following structures:
4. the diazafluorene compound according to claim 1, wherein L1 and L2 are independently selected from the group consisting of a single bond and one of the following groups:
5. the diazafluorene compound according to claim 1, wherein Ar is selected from the group consisting of 1 、Ar 2 Independently selected from one of the following groups:
6. the diazafluorene compound according to any of claims 1 to 5, wherein the general formula I represents one of the compounds represented by the following formulae 1 to 216:
7. use of a diazafluorene compound according to any of claims 1 to 6 in an organic electroluminescent device, wherein the diazafluorene compound is used as a light extraction layer in an organic electroluminescent device.
8. A material for an organic electroluminescent device, characterized in that the material is a diazafluorene compound according to any one of claims 1 to 6 as a light extraction layer of an organic electroluminescent device.
9. An organic electroluminescent device comprises a substrate, an anode, a first hole injection layer, a second hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer, a cathode and a light extraction layer from bottom to top in sequence; characterized in that the light extraction layer is a film formed on a cathode from the diazafluorene compound according to any one of claims 1 to 6.
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| CN202211488827.2A CN115850256A (en) | 2022-11-25 | 2022-11-25 | Diazafluorene compound, material for organic electroluminescent device and organic electroluminescent device |
| PCT/CN2023/077360 WO2024108789A1 (en) | 2022-11-25 | 2023-02-21 | Diazafluorene compound, material for organic light-emitting device, and organic light-emitting device |
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| CN115850256A true CN115850256A (en) | 2023-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202211488827.2A Pending CN115850256A (en) | 2022-11-25 | 2022-11-25 | Diazafluorene compound, material for organic electroluminescent device and organic electroluminescent device |
Country Status (2)
| Country | Link |
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| CN (1) | CN115850256A (en) |
| WO (1) | WO2024108789A1 (en) |
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| JP2004091444A (en) * | 2002-09-04 | 2004-03-25 | Canon Inc | Diazafluorene compound and organic light emitting element using the same |
| WO2006065105A1 (en) * | 2004-12-17 | 2006-06-22 | Doosan Corporation | Compounds and organic electroluminescence display device comprising the same |
| CN1842510A (en) * | 2004-06-16 | 2006-10-04 | 出光兴产株式会社 | fluorene derivative and organic electroluminescent device using the same |
| US20090243476A1 (en) * | 2008-03-28 | 2009-10-01 | Semiconductor Energy Laboratory Co., Ltd. | Acenaphthoquinoxaline Derivative, Light-Emitting Element, Light-Emitting Device, and Electronic Device |
| KR20150102733A (en) * | 2014-02-28 | 2015-09-07 | 머티어리얼사이언스 주식회사 | Organic compounds for forming capping layer of an organic electroluminescent device and an organic electroluminescent device comprising the same |
| CN110099895A (en) * | 2017-07-20 | 2019-08-06 | 株式会社Lg化学 | Compound and Organic Light Emitting Diode comprising it |
| US20210020845A1 (en) * | 2019-07-15 | 2021-01-21 | Samsung Display Co., Ltd. | Compound and organic light-emitting device including the same |
| KR20210040204A (en) * | 2019-10-02 | 2021-04-13 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617835A (en) * | 2012-04-13 | 2012-08-01 | 四川大学 | Conjugated polymer of polyacenaphthylene and quinoxaline, as well as preparation method and application of conjugated polymer |
| KR102068859B1 (en) * | 2015-12-04 | 2020-01-21 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
| CN106243098A (en) * | 2016-04-06 | 2016-12-21 | 新疆大学 | One class condensed hetero ring al thiosemicarbazides fluorescent quenching type mercury ion probe |
| KR102643077B1 (en) * | 2020-06-12 | 2024-03-04 | 주식회사 엘지화학 | Heterocyclic compound and organic light emitting device comprising the same |
| KR20220077279A (en) * | 2020-12-01 | 2022-06-09 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
-
2022
- 2022-11-25 CN CN202211488827.2A patent/CN115850256A/en active Pending
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2023
- 2023-02-21 WO PCT/CN2023/077360 patent/WO2024108789A1/en unknown
Patent Citations (8)
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| JP2004091444A (en) * | 2002-09-04 | 2004-03-25 | Canon Inc | Diazafluorene compound and organic light emitting element using the same |
| CN1842510A (en) * | 2004-06-16 | 2006-10-04 | 出光兴产株式会社 | fluorene derivative and organic electroluminescent device using the same |
| WO2006065105A1 (en) * | 2004-12-17 | 2006-06-22 | Doosan Corporation | Compounds and organic electroluminescence display device comprising the same |
| US20090243476A1 (en) * | 2008-03-28 | 2009-10-01 | Semiconductor Energy Laboratory Co., Ltd. | Acenaphthoquinoxaline Derivative, Light-Emitting Element, Light-Emitting Device, and Electronic Device |
| KR20150102733A (en) * | 2014-02-28 | 2015-09-07 | 머티어리얼사이언스 주식회사 | Organic compounds for forming capping layer of an organic electroluminescent device and an organic electroluminescent device comprising the same |
| CN110099895A (en) * | 2017-07-20 | 2019-08-06 | 株式会社Lg化学 | Compound and Organic Light Emitting Diode comprising it |
| US20210020845A1 (en) * | 2019-07-15 | 2021-01-21 | Samsung Display Co., Ltd. | Compound and organic light-emitting device including the same |
| KR20210040204A (en) * | 2019-10-02 | 2021-04-13 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024108789A1 (en) | 2024-05-30 |
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