CN108623526B - Anthracene substituted derivative and application thereof - Google Patents
Anthracene substituted derivative and application thereof Download PDFInfo
- Publication number
- CN108623526B CN108623526B CN201710153928.7A CN201710153928A CN108623526B CN 108623526 B CN108623526 B CN 108623526B CN 201710153928 A CN201710153928 A CN 201710153928A CN 108623526 B CN108623526 B CN 108623526B
- Authority
- CN
- China
- Prior art keywords
- compound
- layer
- organic electroluminescent
- electroluminescent device
- electron transport
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an anthracene substituted derivative and application thereof. The invention relates to a compound shown as a formula (1), wherein: ar (Ar)1Selected from a hydrogen atom, phenyl, naphthyl, or Ar1Is linked to the phenyl group via a divalent alkylene group to form a fused ring aryl group; ar (Ar)2Is selected from C4～C20Nitrogen-containing heteroaryl of, or Ar2Substituted by nitrile groups. The invention also protects the application of the compound in an organic electroluminescent device, in particular to an electron transport material and a red phosphorescent host material in an OLED device.
Description
Technical Field
The invention relates to a novel organic compound, in particular to a compound for an organic electroluminescent device and application of the compound in the organic electroluminescent device.
Background
The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage direct current drive, full curing, wide viewing angle, light weight, simple composition and process and the like, and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle, low power, 1000 times of response speed of the liquid crystal display, and lower manufacturing cost than the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.
With the continuous advance of the OLED technology in the two fields of illumination and display, people pay more attention to the research of 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 the device structure and various organic materials. 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.
At present, the electron transport material traditionally used in electroluminescent devices is Alq3, but the electron mobility ratio of Alq3 is low (approximately at 10)-6cm2Vs). In order to improve the electron transport properties of electroluminescent devices, researchers have made a great deal of exploratory work. LG patent WO03/060956 discloses compounds of formula (a) having a benzimidazole ring and an anthracene skeleton, which suffer from high voltage and insufficient lifetime. In addition, KR2015024288A discloses a class of quinazoline and anthracene skeleton compounds, as shown in the following formula (b), such materials have the same high voltage and low luminous efficiency.
However, there is still room for improvement in the luminescence property of the conventional organic electroluminescent materials, and there is a need for development of new organic electroluminescent materials.
Disclosure of Invention
The invention aims to provide a novel compound for an organic electroluminescent device so as to further improve the luminous performance of the organic electroluminescent device.
The invention also aims to solve the technical problem of providing an organic electroluminescent device with low working voltage and high luminous efficiency.
In order to solve the above problems, the present inventors have studied and prepared 2,6,9, 10-tetrasubstituted anthracene compounds, and found that when the compounds have the structure shown in the following formula (1), they have suitable HOMO and LUMO energy levels and better carrier transport properties, and thus, when they are applied to OLED devices, they have better practical properties.
The invention aims to provide a compound which can be used for an electron transport layer and/or a light-emitting layer of an organic electroluminescent device. The compounds of the present invention have a structure represented by the following general formula (1):
in the formula (1), Ar1Selected from a hydrogen atom, phenyl, naphthyl, or Ar1Is linked to the phenyl group via a divalent alkylene group to form a fused ring aryl group; ar (Ar)2Selected from C substituted or unsubstituted by nitrile groups4～C20A nitrogen-containing heteroaryl group.
The naphthyl group may be a 1-naphthyl group, a 2-naphthyl group, and particularly preferably a 2-naphthyl group.
Ar is1The condensed ring aryl group formed by connecting the phenyl group via a divalent alkylene group may be a phenanthryl group, a pyrenyl group, a chrysenyl group or the like.
Ar2Selected from C4～C20The nitrogen-containing heteroaryl group is preferably a nitrogen-containing heteroaryl group having 5 to 20 carbon atoms, wherein the nitrogen-containing heteroaryl group is formed by bonding and/or fusing a group in a five-or six-membered aromatic heterocyclic ring containing 1 or 2 nitrogen atoms to a benzene ring through a single bond, and Ar is2Particularly preferred are groups represented by the following formulae (2) to (11):
(. indicates the attachment position).
As a preferable mode of the compound represented by the general formula (1), Ar1When selected from phenyl or naphthyl, Ar2A group represented by the formula (2)
As still another preferable mode of the compound represented by the general formula (1), Ar1Selected from hydrogen atoms, Ar2A group selected from formulae (3) to (11):
some specific examples of the compounds of the present invention are given below, but these are merely illustrative and not limitative.
Researchers carry out structure screening-experiment-feedback-structure adjustment through a large amount of quantitative calculation, and find that substituents exist at 2,6,9 and 10 positions of anthracene, and 2 and 6 positions are connected with a strong electron-withdrawing group through phenylene bridge, so that HOMO and LUMO values of a compound can be adjusted, the energy levels of adjacent layers are better matched, a coplanar structure is kept, the film-forming property of molecules is facilitated, and the carrier mobility is high; on the other hand, the active site is protected, which has positive significance for maintaining the stability of the compound. The groups shown in the formulas (2) to (11) can induce the electron cloud distribution of the anthracene skeleton to be properly expanded to the substituent group, so that the electron cloud distribution is wider, the carrier mobility is improved, and the material with higher performance is obtained.
The compound can be used as an electron transport material in an organic electroluminescent device and can also be used as a host material of a light-emitting layer in the organic electroluminescent device.
When used as an electron transport material, the compound represented by the general formula (1)The compound shown is preferably, Ar1When selected from phenyl or naphthyl, Ar2The group represented by the formula (2) is particularly preferably a structure represented by A1
When used as a host material of a light-emitting layer, the compound represented by the general formula (1) is preferably a structure represented by formula a5 to a14, more preferably a structure represented by formula a7 to a 14.
The invention also provides an organic electroluminescent device, which comprises a substrate, and an anode layer, an organic functional layer containing at least one luminescent layer and a cathode layer which are sequentially formed on the substrate, and is characterized in that at least one layer of the organic functional layer contains the compound of the invention singly or as a mixed component.
In a preferred embodiment of the organic electroluminescent element according to the present invention, the organic functional layer includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer, and the electron transport layer includes the compound according to the present invention.
In still another preferred embodiment of the organic electroluminescent element according to the present invention, the organic functional layer includes a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and the light-emitting layer includes a light-emitting host material and a light-emitting dye, and the light-emitting layer includes a compound according to the present invention as a host material. The preferred light-emitting layer is a red phosphorescent light-emitting layer.
Further, in the organic electroluminescent device of the present invention, the thickness of the light-emitting layer is preferably 5nm to 50nm, and more preferably 10nm to 30 nm. Preferably, the electron transport layer has a thickness of 30 to 80nm, more preferably 40 to 60nm
In the organic electroluminescent device of the present invention, the mass ratio of the luminescent dye to the luminescent host material is preferably controlled by controlling the evaporation rate of the luminescent dye and the luminescent host material in the device preparation process, and the evaporation rate ratio of the luminescent dye to the host material is usually controlled to be 1% to 8%, and more preferably, the evaporation rate ratio of the luminescent dye to the host material is controlled to be 3% to 5%.
Compared with the prior art, the compound has the following advantages:
(1) the compound has good electron transport capacity, can be used as an electron transport material, can be better matched with the LUMO energy level of a luminescent layer main body material, can effectively reduce the working voltage of a device, improve the luminescent efficiency of the device, prolong the service life of the device, and has very important practical significance in the manufacturing of organic electroluminescent devices.
(2) The novel material can be used as an electron transport material in a high-efficiency OLED device and also can be used as a host material of a red phosphorescent light-emitting layer.
(3) The preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is the Highest Occupied Molecular Orbital (HOMO) of Compound A5 according to the present invention;
FIG. 2 is the lowest unoccupied orbital (LUMO) of Compound A5 according to the present invention;
FIG. 3 is a highest occupied molecular orbital HOMO of Compound A7 according to the present invention;
FIG. 4 is the lowest unoccupied orbital LUMO of Compound A7 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Synthesis examples:
compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. Various chemicals used in examples such as petroleum ether, ethyl acetate, N-hexane, toluene, tetrahydrofuran, methylene chloride, carbon tetrachloride, acetone, 1, 2-bis (bromomethyl) benzene, CuI, phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, acetic acid, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-fluorenone, sodium tert-butoxide, methanesulfonic acid, 1-bromo-2-methylnaphthalene, o-dibromobenzene, butyllithium, dibromoethane, o-dibromobenzene, benzoyl peroxide, 1- (2-bromophenyl) -2-methylnaphthalene, N-bromosuccinimide, methoxymethyltrimethylphosphonium chloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, 1, 3-bis (diphenylphosphinopropane nickel chloride, potassium chloride, Basic chemical raw materials such as carbazole, 3, 6-dimethylcarbazole, 3- (2-naphthyl) -6-phenylcarbazole, N-phenylcarbazole-3-boric acid, 9- (2-naphthyl) carbazole-3-boric acid and the like can be purchased in domestic chemical product markets.
Synthesis example 1 Synthesis of Compound A1
Under nitrogen protection, intermediate M1(36.5g, 100mmol) was reacted with 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole (2.30eq), potassium carbonate (5eq), Pd2(dba)3(2% eq) toluene 1000mL + ethanol 500mL + water 300mL, stirring, heating to 100 deg.C under reflux, reacting for 12h, washing the reaction solution with water, drying the organic phase, passing through a silica gel column, concentrating, and washing with petroleum ether to obtain intermediate M2(31.2g, yield 85.4%).
Under the protection of nitrogen, adding 4-bromobiphenyl (2.5eq.) and tetrahydrofuran (200 ml) into a 10L three-neck flask provided with a mechanical stirring and low-temperature thermometer, starting stirring, cooling the flask with ice and ethanol, cooling the flask with liquid nitrogen to-90 to-80 ℃, dropwise adding n-butyllithium (2.45eq.) within 30min, controlling the temperature to-90 to-80 ℃ during dropwise adding, adding intermediate M2(3.62g, 10mmol), naturally heating after adding, removing the cooling bath, and continuing stirring for 8 hours. Aqueous ammonium chloride was added, the organic phase was separated, dried, concentrated and recrystallized from toluene to give intermediate M3(4.8g, 92.3%)
Under the protection of nitrogen, 100ml of acetic acid is added into a 250ml reaction bottle, stirring and heating are started, when the temperature of a reaction solution is raised to about 60 ℃, an intermediate M3(5.2g,10mmol), KI (5eq.), NaHPO2.H2O (8eq.) are added, and reflux reaction is carried out for 5 hours (about 120 ℃). Filtering, and washing the filtrate with acetic acid, water and ethanol. Toluene was recrystallized to yield A1(4.2g, 87.5%).
Nuclear magnetic spectroscopic data for compound a 1:
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.56(s,1H),8.35(s,1H),8.28(s,2H),7.98–7.72(m,7H),7.57(d,J＝3.0Hz,3H),7.56–7.38(m,8H),7.27(d,J＝12.0Hz,5H).
synthesis example 2 Synthesis of Compound A2
The synthesis procedure was identical to compound A1 except that 4-bromobiphenyl was replaced by an equivalent amount of 4-bromo- (2-naphthalene) benzene and after the reaction was complete, 6.0g of a white solid was isolated in 84.5% yield.
Nuclear magnetic spectroscopic data for compound a 2:
1H NMR(400MHz,Chloroform)δ8.97(s,3H),8.45(d,J＝84.0Hz,5H),8.35–8.31(m,2H),8.28(s,5H),8.07(d,J＝12.0Hz,6H),7.99(s,3H),7.79(t,J＝8.0Hz,5H),7.63(s,3H),7.60–7.47(m,21H),7.38(s,3H),7.26(d,J＝12.0Hz,5H).
synthesis example 3 Synthesis of Compound A3
The synthesis step was carried out with the compound A1, except that 4-bromobiphenyl was replaced with equivalent 2-bromophenanthrene, and after the reaction was completed, 6.2g of a white solid was isolated in 88.3% yield.
1H NMR(400MHz,Chloroform)δ9.11(s,1H),8.97(s,1H),8.70(s,1H),8.56(s,1H),8.43(s,1H),8.35(s,1H),8.28(s,2H),8.15(s,1H),7.91(d,J＝8.0Hz,2H),7.84–7.68(m,8H),7.66(d,J＝10.0Hz,2H),7.59–7.48(m,6H),7.28(s,1H).
Synthesis example 4 Synthesis of Compound A4
The compound A1 was used in the synthesis procedure, except that 4-bromobiphenyl was replaced by equivalent 2-bromopyrene, and after the reaction was completed, 4.6g of white solid was isolated with a yield of 75.9%.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.46(d,J＝84.0Hz,2H),8.34–8.31(m,1H),8.28(s,2H),8.19(s,1H),8.06(d,J＝16.0Hz,5H),7.92(d,J＝1.8Hz,5H),7.79(t,J＝8.0Hz,6H),7.59–7.47(m,6H),7.28(s,1H).
Synthesis example 5 Synthesis of Compound A5
The synthesis procedure was identical to that of compound a1, except that 4-bromobiphenyl was replaced by an equivalent amount of bromobenzene, 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced by an equivalent amount of 2- (4-phenylboronic acid) -pyrazine, and after the reaction was complete, 5.2g of a white solid was isolated in 80.0% yield.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.93–8.86(m,2H),8.86–8.76(m,4H),8.35(s,4H),7.89(s,2H),7.65(s,2H),7.54(d,J＝12.0Hz,4H),7.41(s,2H).
Synthesis example 6 Synthesis of Compound A6
The synthetic procedure was followed with compound A5 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
5- (4-Phenylboronic acid) -pyrimidine, 4.9g of a white solid was isolated after the end of the reaction, with a yield of 72.4%.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),8.35(s,2H),7.65(s,4H),7.54(d,J＝12.0Hz,7H),7.41(s,1H),7.25(s,8H).
Synthesis example 7 Synthesis of Compound A7
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
2- (4-Phenylboronic acid) -5-cyanopyrimidine 5.2g of a white solid was isolated in 78.5% yield after the reaction.
1H NMR(400MHz,Chloroform)δ9.29(s,2H),8.97(s,1H),8.35(s,1H),7.96(s,2H),7.65(s,2H),7.54(d,J＝12.0Hz,4H),7.41(s,2H),7.25(s,2H).
Synthesis example 8 Synthesis of Compound A8
The synthetic procedure was followed with compound A7 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
5- (4-Phenylboronic acid) -pyrimidine, 4.9g of a white solid was isolated after the end of the reaction, with a yield of 72.4%.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),8.35(s,2H),7.65(s,4H),7.54(d,J＝12.0Hz,7H),7.41(s,1H),7.25(s,8H).
Synthesis example 9 Synthesis of Compound A9
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
2- (4-Phenylboronic acid) -1, 8-dinaphthylpyridine was isolated as a white solid in an amount of 4.8g and a yield of 75.3% after completion of the reaction.1H NMR(400MHz,Chloroform)δ8.97(s,2H),8.69(d,J＝8.0Hz,4H),8.37(d,J＝10.0Hz,3H),8.07(d,J＝10.0Hz,3H),7.94(s,1H),7.85(s,3H),7.65(s,3H),7.54(d,J＝12.0Hz,4H),7.41(s,3H).
Synthesis example 10 Synthesis of Compound A10
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
7- (4-Phenylboronic acid) -quinoline, 4.7g of a pale yellow solid was obtained in 73.6% yield.
1H NMR(400MHz,Chloroform)δ9.13(s,2H),8.97(s,3H),8.92(s,1H),8.28(d,J＝10.0Hz,4H),8.07(s,2H),7.65(s,4H),7.63–7.44(m,9H),7.40(d,J＝8.0Hz,3H),7.25(s,8H).
Synthesis example 11 Synthesis of Compound A11
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
2- (4-Phenylboronic acid) -quinoline, 5.9g of a pale yellow solid was obtained in a yield of 92.4%.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.69(s,2H),8.37(d,J＝16.0Hz,2H),8.10(s,2H),8.10(s,1H),8.18–7.79(m,4H),8.18–7.68(m,4H),8.18–7.59(m,4H),8.18–7.43(m,4H),8.18–7.11(m,5H).
Synthesis example 12 Synthesis of Compound A12
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
4, 6-Diphenyl-pyrimidine-2-boronic acid, 3.4g of pale yellow solid is obtained, yield 74.5%.
1H NMR(400MHz,Chloroform)δ8.38(d,J＝12.0Hz,2H),8.23(s,1H),7.94(s,4H),7.81(s,1H),7.65(s,2H),7.55(s,6H),7.49(s,2H),7.41(s,2H).
Synthesis example 13 Synthesis of Compound A13
The synthetic procedure was followed with compound A1 except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of
3, 5-bis (2-pyridine) -phenylboronic acid, 4.8g of a pale yellow solid was obtained in 74.5% yield.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.87(s,2H),8.74(s,1H),8.36(d,J＝8.0Hz,3H),7.65(s,2H),7.54(d,J＝12.0Hz,4H),7.39(d,J＝12.0Hz,3H),7.14(s,2H),6.90(s,2H).
Synthesis example 14 Synthesis of Compound A14
Compound a1 was used as the synthetic procedure, except that 1- (4-boranophenyl) -2-phenyl-1H-benzimidazole was replaced with an equivalent amount of 4- (4-phenylboronic acid) -terpyridine to give 3.2g of a pale yellow solid in 75.2% yield.
1H NMR(400MHz,Chloroform)δ9.16(d,J＝16.0Hz,8H),8.97(s,2H),8.45(d,J＝80.0Hz,6H),7.74(s,4H),7.65(s,3H),7.53(d,J＝12.0Hz,7H),7.41(s,1H),7.24(d,J＝8.0Hz,12H).
Analytical testing of intermediates and compounds of the invention use AB SCIEX mass spectrometer (4000QTRAP) and brueck nuclear magnetic resonance spectrometer (400M).
Table 1: analytical examination data of the Compound of synthetic Structure in synthetic example
| Compound (I) | Molecular formula | MS(m/e) | Elemental analysis (%) |
| A1 | C76H50N4 | 1018.2 | C,89.43；H,4.69；N,5.38 |
| A2 | C84H54N4 | 1118.3 | C,90.28；H,4.63；N,4.74 |
| A3 | C80H50N4 | 1066.6 | C,90.37；H,5.00；N,5.32 |
| A4 | C84H50N4 | 1114.9 | C,90.41；H,4.65；N,4.73 |
| A5 | C46H30N4 | 638.4 | C,86.39；H,4.47；N,8.31 |
| A6 | C46H30N4 | 638.7 | C,86.35；H,4.53；N,8.62 |
| A7 | C48H28N6 | 688.4 | C,83.43；H,5.69；N,12.35 |
| A8 | C48H28N6 | 688.7 | C,83.26；H,5.47；N,12.38 |
| A9 | C54H34N4 | 738.4 | C,87.85；H,4.29；N,7.46 |
| A10 | C56H36N2 | 736.8 | C,92.85；H,5.29；N,3.46 |
| A11 | C46H30N4 | 638.5 | C,86.36；H,4.65；N,8.38 |
| A12 | C70H46N4 | 942.4 | C,89.22；H,4.76；N,5.64 |
| A13 | C70H46N4 | 942.2 | C,89.53；H,4.82；N,6.15 |
| A14 | C68H44N6 | 944.2 | C,86.53；H,4.52；N,9.15 |
The compounds were structurally optimized using gaussian software, calculated as the hybridization functional B3LYP and basis set 6-31G (d, p) of Density Functional Theory (DFT), and evaluated for the Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and triplet (T1) energy levels of compounds a1, a5, a7, a9, a13, and known compounds a, B, the results of which are shown in table 2.
Table 2: energy level values for inventive Compounds and comparative document Compounds
From the comparison of the calculation results, compared with the compound in patent KR2015024288A, the compound of the present invention has deeper HOMO and LUMO, which is more favorable for the function of hole blocking, and simultaneously can reduce the energy system difference between the compound and the adjacent functional layer, which is favorable for reducing the voltage of the device; compared with the patent WO03/060956, the active sites on the parent nucleus of the compound are protected, the thermodynamic stability can be improved, the service life of a material device can be prolonged, the commercialization application is more likely to be realized, and the compound has the characteristic of deeper HOMO and LUMO and can play roles in reducing voltage and blocking holes. Compared with the disclosed patent compounds, the compound of the invention has very obvious improvement on the performance.
Device embodiment:
the structure of the organic electroluminescent device of the present invention is not particularly required, and may be a structure known to those skilled in the art, and is preferably a structure composed of:
(1) anode/Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/emission layer (EML)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL)/cathode;
(2) anode/Hole Transport Layer (HTL)/emission layer (EML)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL)/cathode
The "/" mentioned above indicates that different functional layers are stacked in order.
In the preferred embodiment, the organic electroluminescent device has a lower operating voltage and higher luminous efficiency.
The substrate may be a substrate used in a conventional organic light emitting organic electroluminescent device, for example: glass or plastic. As the anode material, a transparent highly conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or the like can be used. In the fabrication of the organic electroluminescent device of the embodiment, a glass substrate and ITO are used as an anode material.
Common hole injection materials are CuPc, TNATA and PEDT: PSS, and the like. The hole injection layer of the organic electroluminescent device adopts 2-TNATA.
As the hole transport layer, triarylamine-based materials such as N, N ' -bis (3-tolyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4 ' -diamine (TPD) and N, N ' -diphenyl-N, N ' -bis (1-naphthyl) - (1,1 ' -biphenyl) -4,4 ' -diamine (NPB) can be used. NPB is selected as the hole transport material in the organic electroluminescent device manufactured by the invention.
The organic electroluminescent device structure can be a single light-emitting layer or a multi-light-emitting layer structure. The embodiment of the invention adopts a structure of a single light-emitting layer. The luminescent layer comprises a luminescent host material and a luminescent dye, wherein the mass ratio of the luminescent dye to the luminescent host material is controlled by regulating the evaporation rate of the luminescent dye to the luminescent host material in the device preparation process, and the evaporation rate ratio of the luminescent dye to the luminescent host material is generally controlled to be 1-8%, preferably 3-5%.
Commonly used luminescent dyes include iridium complexes ir (ppy), FIrpic, as well as pure organic small molecules, rubrene, DPP, DCJ, DCM, and the like.
Commonly used luminescent host materials include Alq3, BAlq, AND, CBP, mCP, TBPe, AND the like.
Common electron transport materials include Alq3, Bphen, BCP, PBD and the like, and Alq3 and the formula (a) are selected as electron transport layer materials to be compared with the compound disclosed by the invention.
The cathode material selected in the fabrication of the organic electroluminescent device of the present invention is LiF/Al.
The specific structures of several materials used in the present invention are as follows:
the above organic electroluminescent material can be prepared by itself or purchased from chemical markets by those skilled in the art based on known methods.
Device example 1 use of Compounds of the invention as Electron transport materials
In this example, 9 organic electroluminescent devices were prepared in total, which were constructed by stacking "Hole Injection Layer (HIL)/Hole Transport Layer (HTL)/emission layer (EML)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL)/cathode" on a substrate in this order, and each of the layers was composed of the following materials:
ITO/2-TNATA(30nm)/NPB(20nm)/CBP：Ir(ppy)3(5%) (20 nm)/inventive compound (50nm)/LiF (1 nm)/Al.
In two comparative organic electroluminescent devices, the electron transport material was Alq3 or the compound of formula (a).
The preparation process of the organic electroluminescent device in the embodiment is as follows:
ultrasonically cleaning a glass substrate coated with an ITO transparent conductive film on the surface in a cleaning solution, ultrasonically treating the glass substrate in deionized water, and performing ultrasonic treatment in ethanol: ultrasonically removing oil in an acetone mixed solution, baking in a clean environment until water is completely removed, etching and performing ozone treatment by using an ultraviolet lamp, and bombarding the surface by using low-energy cation beams;
the glass substrate with the anode is processedPlacing in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form 2-TNATA, adjusting the evaporation rate to be 0.1nm/s, and forming a hole injection layer with the thickness of 30 nm; evaporating a compound NPB on the hole injection layer in vacuum to form a hole transport layer with the thickness of 20nm, wherein the evaporation rate is 0.1 nm/s; the EML is evaporated on the hole transport layer in vacuum and used as a light emitting layer of the device, the EML comprises a main material and a dye material, the evaporation rate of the main material CBP is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the evaporation rate of the dye material Ir (ppy)3 is set according to the doping proportion, and the total evaporation film thickness is 20 nm;
the compound or Alq3 of the invention is used as the material of the electron transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 50 nm;
LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The obtained organic electroluminescent device was observed to have the same luminance (10000 cd/m)2) The driving voltage and current efficiency were measured and the properties are shown in Table 3.
Table 3:
as can be seen from the device performance data of device examples 1-1 to 1-9 disclosed in table 3, the ETL material of the device was adjusted under the condition that other materials in the organic electroluminescent device structure were the same, and compared with device comparative examples 1-8 and 1-9, the operating voltage of the device was significantly reduced, and the luminous efficiency of the device was greatly improved. This is related to the deeper LUMO values and better electron mobility of the compounds of the present invention.
Device example 2. the compounds of the present invention act as light emitting host materials.
A total of 8 organic electroluminescent devices were prepared, which had a structure in which each layer was composed of the following materials according to "anode/Hole Transport Layer (HTL)/Emission Layer (EL)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/Electron Injection Layer (EIL)/cathode" on a substrate:
ITO/NPB (50 nm)/H1: d1 (5%) (30nm)/PBD (10nm)/Alq3(50nm)/LiF (0.5nm)/Al (100 nm). H1 is selected as the red light main body material of one device comparative example, and the material of the invention is selected as the red light main body material of the other 7 organic electroluminescent devices.
The preparation process of the organic electroluminescent device is as follows:
a) cleaning of ITO (indium tin oxide) glass: respectively ultrasonically cleaning ITO glass by deionized water, acetone and ethanol for 15 minutes, and then treating the ITO glass in a plasma cleaner for 2 minutes;
b) vacuum evaporation or solution film formation is carried out on the anode ITO glass to form a hole transport layer NPB with the thickness of 50 nm;
c) a luminescent layer H1+ D1 (5%) is vacuum-evaporated on the hole transport layer NPB, and the thickness is 30 nm;
d) a hole blocking layer PBD is evaporated on the luminescent layer in vacuum, and the thickness is 10 nm;
e) vacuum evaporating an electron transport layer Alq3 on the hole blocking layer PBD
f) Vacuum evaporating an electron injection layer LiF on the electron transport layer Alq3, wherein the thickness of the electron injection layer LiF is 0.5 nm;
g) and vacuum evaporating cathode Al on the electron injection layer LiF, wherein the thickness of the cathode Al is 100 nm.
The obtained organic electroluminescent device was observed to have the same luminance of 5000cd/m2The driving voltage and current efficiency were measured and the properties are shown in Table 4.
Table 4:
as can be seen from the device performance data of device examples 2-1 to 2-8 disclosed in Table 4, the host material of the light-emitting layer in the device was adjusted under the condition that the other materials in the structure of the organic electroluminescent device were the same, and compared with the device comparative example 2-1, the organic electroluminescent device using the compound of the present invention could be significantly improved and enhanced in both voltage and luminous efficiency, indicating that the compound of the present invention as the host material of the light-emitting layer could make the red phosphorescent organic electroluminescent device obtain better performance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. A compound having a structure represented by the following general formula (1):
in the formula (1), Ar1Selected from a hydrogen atom, phenyl, naphthyl, or Ar1Is linked to a phenyl group to form a phenanthryl, pyrenyl or
A group; ar (Ar)2To represent
2. The compound of claim 1, wherein Ar is Ar1Selected from phenyl and naphthyl.
3. The compound of claim 1, wherein said compound is one of the compounds represented by the following structural formulae a1 through A3:
4. a compound having the structure shown in structural formula a 4:
5. use of a compound according to any one of claims 1 to 4 in an organic electroluminescent device.
6. Use according to claim 5 of a compound according to any one of claims 1 to 4 as an electron transport material or a light emitting host material in an organic electroluminescent device.
7. An organic electroluminescent device comprises a substrate, and an anode layer, an organic functional layer at least comprising a luminescent layer and a cathode layer which are sequentially formed on the substrate, and is characterized in that: at least one of the organic functional layers contains a compound according to any one of claims 1 to 4, alone or as a mixture.
8. The organic electroluminescent device according to claim 7, wherein the organic functional layers comprise a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, and the organic electroluminescent device is characterized in that: the electron transport layer comprises the compound of any one of claims 1 to 4.
9. The organic electroluminescent device according to claim 8, wherein: the organic functional layer includes a red phosphorescent light-emitting layer, and the host material of the red phosphorescent light-emitting layer includes the compound according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710153928.7A CN108623526B (en) | 2017-03-15 | 2017-03-15 | Anthracene substituted derivative and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710153928.7A CN108623526B (en) | 2017-03-15 | 2017-03-15 | Anthracene substituted derivative and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108623526A CN108623526A (en) | 2018-10-09 |
| CN108623526B true CN108623526B (en) | 2021-03-16 |
Family
ID=63687415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710153928.7A Active CN108623526B (en) | 2017-03-15 | 2017-03-15 | Anthracene substituted derivative and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108623526B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822088A (en) * | 2018-08-12 | 2018-11-16 | 瑞声科技（南京）有限公司 | A kind of compound and its application based on glyoxaline structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570504A (en) * | 2008-04-17 | 2009-11-04 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using the same |
| KR20130098227A (en) * | 2012-02-27 | 2013-09-04 | 주식회사 엘지화학 | Organic light emitting diode |
| KR20140137231A (en) * | 2013-05-22 | 2014-12-02 | 덕산하이메탈(주) | An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same |
| KR20150024288A (en) * | 2013-08-26 | 2015-03-06 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
| CN104557669A (en) * | 2013-08-30 | 2015-04-29 | 三星显示有限公司 | Condensed compound and organic light-emitting diode including the same |
-
2017
- 2017-03-15 CN CN201710153928.7A patent/CN108623526B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570504A (en) * | 2008-04-17 | 2009-11-04 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using the same |
| KR20130098227A (en) * | 2012-02-27 | 2013-09-04 | 주식회사 엘지화학 | Organic light emitting diode |
| KR20140137231A (en) * | 2013-05-22 | 2014-12-02 | 덕산하이메탈(주) | An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same |
| KR20150024288A (en) * | 2013-08-26 | 2015-03-06 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
| CN104557669A (en) * | 2013-08-30 | 2015-04-29 | 三星显示有限公司 | Condensed compound and organic light-emitting diode including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108623526A (en) | 2018-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106699573B (en) | Spiro organic material and organic electroluminescent device using the same | |
| JP5154569B2 (en) | Novel fluorene derivative and organic electronic device using the same | |
| KR101823400B1 (en) | Organic electroluminescent element | |
| KR101861263B1 (en) | Anthracene deriva tives and organic light-emitting diode including the same | |
| KR20140020208A (en) | Organic electroluminescent compound comprising acridine derivative and organic electroluminescent device comprising same | |
| KR20140015202A (en) | Organic electroluminescent compound comprising acridine derivative and organic electroluminescent device comprising same | |
| US20200109138A1 (en) | Organic compound and organic electroluminescence device using the same | |
| KR101661925B1 (en) | Pyrene derivatives and organic electroluminescent device comprising the same | |
| KR102504296B1 (en) | Material for organic electroluminescence device and organic electroluminescence device including the same | |
| KR102471097B1 (en) | Material for organic electroluminiescent device and organic electroluminiscent device using the same | |
| CN109309166B (en) | Organic electroluminescent device and anthracene compound containing 2,6,9, 10-tetra-substitution | |
| KR20140086880A (en) | Novel organic compound and organic electroluminescent device comprising same | |
| CN107663169B (en) | 6H-naphtho [2,1,8,7-klmn ] acridine derivative and application thereof | |
| WO2014024447A1 (en) | Compound having triphenylene ring structure, and organic electroluminescent element | |
| WO2012115219A1 (en) | Compounds having bipyridyl group and carbazole ring, and organic electroluminescent element | |
| CN108807697B (en) | Organic electroluminescent device and phenanthrene derivative | |
| CN108623526B (en) | Anthracene substituted derivative and application thereof | |
| KR20160045019A (en) | Novel compound and organic electroluminescent device comprising same | |
| KR20150095208A (en) | Novel hole injecting· hole-transporting compound and organic electroluminescent device comprising same | |
| KR102518765B1 (en) | Novel compound and organic light-emitting diode using them | |
| KR20140091496A (en) | Novel organic electroluminescent compound substituted with deuterium and organic electroluminescent device comprising same | |
| CN110494436B (en) | Heterocyclic compound and organic light-emitting element comprising same | |
| TWI657081B (en) | An organic electroluminescent device containing a bipolar host material of a 1,2,4-triazine group | |
| CN111909171A (en) | Novel electronic transmission material and application thereof | |
| KR20190117376A (en) | Hole transporting material and Organic electroluminescent display device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |