CN112449639B - Compound and organic light emitting device comprising the same - Google Patents
Compound and organic light emitting device comprising the same Download PDFInfo
- Publication number
- CN112449639B CN112449639B CN201980048250.3A CN201980048250A CN112449639B CN 112449639 B CN112449639 B CN 112449639B CN 201980048250 A CN201980048250 A CN 201980048250A CN 112449639 B CN112449639 B CN 112449639B
- Authority
- CN
- China
- Prior art keywords
- layer
- added
- mmol
- compound
- light emitting
- 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
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present disclosure provides heterocyclic compounds and organic light-emitting devices comprising the same.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2018-013442 filed on 11.6 and korean patent application No. 10-2019-0140606 filed on 11.6.
The present disclosure relates to compounds and organic light emitting devices comprising the same.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to improve efficiency and stability of the organic light emitting device, for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected into the organic material layer from the anode, electrons are injected into the organic material layer from the cathode, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall to the ground state again.
There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.
[ Prior Art literature ]
[ patent literature ]
(patent document 0001) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
An object of the present disclosure is to provide a compound and an organic light emitting device including the same.
Technical proposal
According to one embodiment of the present disclosure, there is provided a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
y is O or S, and the total number of the catalyst is O or S,
each X is independently N or CH, provided that at least one X is N,
Ar 1 is C substituted or unsubstituted comprising one or more heteroatoms selected from N, O and S 5-60 A heteroaryl group, which is a group,
Ar 2 is C substituted or unsubstituted 6-60 An aryl group; or C comprising one or more heteroatoms selected from N, O and S, substituted or unsubstituted 5-60 A heteroaryl group, which is a group,
n is an integer from 0 to 4, and
r is hydrogen; substituted or unsubstituted C 6-60 An aryl group; or C comprising one or more heteroatoms selected from N, O and S, substituted or unsubstituted 5-60 Heteroaryl groups.
According to another aspect of the present disclosure, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises a compound represented by chemical formula 1.
Advantageous effects
The compound represented by chemical formula 1 described above may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device. In particular, the compound represented by chemical formula 1 may be used as a hole injecting material, a hole transporting material, a hole injecting and transporting material, a light emitting material, an electron transporting material, or an electron injecting material.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9, and a cathode 4.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to aid in understanding the present invention.
The present disclosure provides a compound represented by chemical formula 1.
As used herein, a symbolOr->Meaning a bond to another substituent.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; and a heterocyclic group comprising at least one of N, O and S atoms, or a substituent which is unsubstituted or linked via two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl, or it may also be interpreted as a substituent to which two phenyl groups are attached.
In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a group having the following structural formula, but is not limited thereto:
in the present disclosure, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a group having the following structural formula, but is not limited thereto:
in the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a group having the following structural formula, but is not limited thereto:
in the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, and phenylboron group, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be straight or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to yet another embodiment, the cycloalkyl group has a carbon number of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. As the monocyclic aryl group, the aryl group may be phenyl, biphenyl, terphenyl or the like, but is not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A base, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formed Etc. However, the structure is not limited thereto.
In the present disclosure, the heterocyclic group is a heterocyclic group containing one or more of O, N, si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of heterocyclyl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthroline, thiazolyl, iso ∈ ->Azolyl, (-) -and (II) radicals>Diazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present disclosure, the aryl groups in the aralkyl, aralkenyl, alkylaryl, arylamine groups are the same as the foregoing examples of aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamino group are the same as the aforementioned examples of the alkyl group. In the present disclosure, heteroaryl groups in heteroaryl amines may employ the foregoing description of heterocyclyl groups. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the aforementioned examples of alkenyl groups. In the present disclosure, the foregoing description of aryl groups may be applied, except that arylene groups are divalent groups. In the present disclosure, the foregoing description of heterocyclyl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the foregoing description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the foregoing description of the heterocyclic group may be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.
Preferably, chemical formula 1 may be any one selected from compounds represented by the following chemical formulas 1-1 to 1-4:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In chemical formulas 1-1 to 1-4,
X、Y、n、R、Ar 1 and Ar is a group 2 The same as defined above.
Preferably Ar 1 May be any one selected from the following:
preferably Ar 2 May be phenyl, biphenyl or naphthyl, and more preferably phenyl.
Preferably, n may be 0 to 2.
Also preferably, R may be a substituted or unsubstituted C 6-30 Aryl, more preferably phenyl.
Preferably, all X may be N.
For example, the compound may be selected from the following compounds:
/>
/>
meanwhile, the compound represented by chemical formula 1 may be prepared by a preparation method as shown in the following reaction scheme 1.
Reaction scheme 1
In reaction scheme 1, the definition of substituents is the same as described above, and the preparation method may be further presented in the preparation examples described below.
Further, the present disclosure provides an organic light emitting device including the compound represented by chemical formula 1. In one example, the present disclosure provides an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises a compound represented by chemical formula 1.
The organic material layer of the organic light emitting device of the present disclosure may have a single layer structure, or it may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and it may include a smaller number of organic material layers.
Further, the organic material layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously performing hole injection and transport, wherein the hole injection layer, the hole transport layer, or the layer for simultaneously performing hole injection and transport may include a compound represented by chemical formula 1.
Further, the organic material layer may include a light emitting layer, wherein the light emitting layer may include a compound represented by chemical formula 1. In this case, the compound represented by chemical formula 1 may be used as a host material in the light emitting layer.
Further, the organic material layer may include two or more types of hosts. When the light emitting layer includes two or more types of hosts, at least one of the hosts may be a compound represented by chemical formula 1.
Further, the organic material layer may include an electron transport layer or an electron injection layer, wherein the electron transport layer or the electron injection layer contains the compound represented by chemical formula 1.
Further, the electron transport layer, the electron injection layer, or the layer for simultaneously performing electron transport and electron injection may contain a compound represented by chemical formula 1.
Further, the organic material layer may include a light emitting layer and an electron transporting layer, wherein the electron transporting layer may include a compound represented by chemical formula 1.
Further, the organic light emitting device according to the present disclosure may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present disclosure may be an inverted organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in the light emitting layer.
Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer, and preferably, may be included in the light emitting layer.
The organic light emitting device according to the present disclosure may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes a compound represented by chemical formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, an organic light emitting device according to the present disclosure may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, a metal oxide having conductivity, or an alloy thereof is deposited on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can function as a cathode is deposited on the organic material layer. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
In addition, in manufacturing an organic light emitting device, the compound represented by chemical formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (international publication WO 2003/012890). However, the manufacturing method is not limited thereto.
As an example, the first electrode is an anode and the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.
As the anode material, it is generally preferable to use a material having a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO, al orSnO 2 Sb; conductive compounds, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has an effect of injecting holes in an anode and has an excellent hole injection effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to an electron injection layer or an electron injection material, and also has an excellent capability of forming a thin film. The HOMO (highest occupied molecular orbital) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline, polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport layer is suitably a material having a large hole mobility, which can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
An electron blocking layer is formed on the hole transport layer, preferably disposed in contact with the light emitting layer, and serves to adjust hole mobility, prevent excessive movement of electrons, and increase the probability of hole-electron coupling, thereby improving the efficiency of the organic light emitting device. The electron blocking layer contains an electron blocking material, and as such an electron blocking material, a material having a stable structure in which electrons cannot flow out from the light emitting layer is suitable. Specific examples thereof may include an arylamine-based organic material and the like, but are not limited thereto.
The luminescent material is preferably such a material: which can receive holes and electrons respectively transferred from the hole transport layer and the electron transport layer, combine the holes and electrons to emit light in the visible light region, and have good quantum efficiency for fluorescence or phosphorescence. Specific examples of the light emitting material include: 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; a dimeric styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; based on benzoOxazole, benzothiazole-based and benzimidazole-based compounds; poly (p-phenylene vinylene) (PPV) based polymers; a spiro compound; polyfluorene; rubrene; etc., but is not limited thereto.
The light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
Examples of dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, examples of which include pyrene, anthracene having an arylamino group,Bisindenopyrene, and the like. Styrylamine compounds are aryl groups in which the substituents are or are unsubstitutedA compound substituted with at least one aryl vinyl group in an amine, wherein one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl and arylamino groups are substituted or unsubstituted. Specific examples thereof include styrylamine, styrylenediamine, styrylenetriamine, styrylenetetramine, and the like, but are not limited thereto. Further, the metal complex includes iridium complex, platinum complex, and the like, but is not limited thereto.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is suitably a material such as: which can well receive electrons from the cathode and transport the electrons to the light emitting layer, and has a large electron mobility. Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the relevant art. In particular, suitable examples of cathode materials are typical materials having a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from an electrode, and is preferably a compound that: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and has an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated by the light emitting layer from moving to a hole injecting layer, and also has an excellent ability to form a thin film. Specific examples of the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azole,/->Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and derivatives thereof; a metal complex compound; a nitrogen-containing 5-membered ring derivative; etc.,but is not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
The organic light emitting device according to the present disclosure may be of a front-side emission type, a rear-side emission type, or a double-side emission type, depending on the materials used.
Further, the compound represented by chemical formula 1 may be included in an organic solar cell or an organic transistor, in addition to the organic light emitting device.
The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, these examples are presented for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Synthesis example 1: synthesis of intermediate compound R-4
1-bromo-4-fluoro-3-iodobenzene (50 g,166.6 mmol) and (5-chloro-2-methoxyphenyl) boronic acid (31.1 g,166.6 mmol) were dissolved in 800ml of Tetrahydrofuran (THF). To this was added sodium carbonate (Na 2 CO 3 ) 2M solution (250 mL) and tetrakis (triphenylphosphine) palladium (0) [ Pd (PPh) 3 ) 4 ](3.8 g,3 mol%) and refluxed for 12 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, and the resultant mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and filtered. The filtrate was distilled under reduced pressure, and the resulting mixture was recrystallized three times using chloroform and ethanol to obtain compound R-1 (27.5 g, yield: 51%; MS: [ M+H)] + ＝314)。
Compound R-1 (25.0 g,150 mmol) was dissolved in dichloromethane (300 ml) and then cooled to 0deg.C. Boron tribromide (7.9 ml,83.2 mmol) was slowly added dropwise and then stirred for 12 hours. After the reaction was completed, the mixture was washed three times with water, dried over magnesium sulfate, and filtered. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain compound R-2 (23.7 g, yield: 99%; MS: [ M+H)] + ＝300)。
Compound R-2 (20.0 g,66.4 mmol) was dissolved in distilled Dimethylformamide (DMF) (200 ml). It was cooled to 0℃and sodium hydride (1.8 g,72.9 mmol) was slowly added dropwise thereto. The mixture was stirred for 20 minutes and then at 100 ℃ for 1 hour. After the reaction was completed, the reaction temperature was cooled to room temperature, and 100ml of ethanol was slowly added thereto. The resulting mixture was distilled under reduced pressure, and recrystallized from chloroform and ethyl acetate to obtain compound R-3 (15.2 g, yield: 81%; MS: [ M+H) ] + ＝280)。
Compound R-3 (15.0 g,53.3 mmol) was dissolved in tetrahydrofuran (150 ml) and the temperature was lowered to-78 ℃. To this was slowly added 1.7M t-butyllithium (t-BuLi) (31.8 ml,53.3 mmol). The mixture was stirred at the same temperature for 1 hour, and then triisopropyl borate (B (OiPr) was added thereto 3 ) (14.2 mL,107.0 mmol) and the mixture was stirred for 3 hours while gradually warming to room temperature. To the reaction mixture was added 2N aqueous hydrochloric acid (100 mL) and stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed successively with water and diethyl ether and dried under vacuum. After drying, it was dispersed in diethyl ether, stirred for 2 hours, thenFiltered and dried to prepare compound R-4. (12.2 g, 93% yield; MS: [ M+H)] + ＝247)
Synthesis example 2: synthesis of intermediate compounds sub 1-2
R-4 (20 g,81.3 mmol) and 4-bromodibenzo [ b, d ] are reacted under nitrogen]Furan (20 g,81.3 mmol) was added to 400ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (33.7 g,243.9 mmol) was dissolved in 34ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.8 g,2.4 mmol) was added. After 3 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 598ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to give a white solid compound Sub 1-1 (19.4 g,65%, MS: [ M+H) ] + ＝369.1)。
Sub 1-1 (15 g,40.8 mmol) and bis (pinacolato) diboron (20.7 g,81.5 mmol) are added to 300ml of di under nitrogen atmosphereIn an alkane, and the mixture was stirred and refluxed. Then, potassium acetate (11.8 g,122.3 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.7 g,1.2 mmol) and tricyclohexylphosphine (0.7 g,2.4 mmol) were then added. After the reaction was continued for 5 hours, the reaction mixture was cooled to room temperature, and then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 188ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was taken inDistillation under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare white solid compound Sub 1-2 (12.2 g,65%, MS: [ M+H)] + ＝461.2)。
Synthesis example 3: synthesis of intermediate compound sub 2-2
R-4 (20 g,81.3 mmol) and 3-bromodibenzo [ b, d ] are reacted under nitrogen]Furan (20 g,81.3 mmol) was added to 400ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (33.7 g,243.9 mmol) was dissolved in 34ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.8 g,2.4 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 598ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound Sub 2-1 (18 g,60%, MS: [ M+H) ] + ＝369.1)。
Sub 2-1 (15 g,28.2 mmol) and bis (pinacolato) diboron (14.4 g,56.5 mmol) were added to 300ml of di under a nitrogen atmosphereIn alkane, the mixture was stirred and refluxed. Then, potassium acetate (8.1 g,84.7 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.5 g,0.8 mmol) and tricyclohexylphosphine (0.5 g,1.7 mmol) were then added thereto. After the reaction was continued for 5 hours, the reaction mixture was cooled to room temperature, and then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 130ml chloroform again, dissolved and washed twice with water. The organic layer is then separatedAnhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare yellow solid compound Sub 2-2 (7.5 g,58%, MS: [ M+H)] + ＝461.2)。
Synthesis example 4: synthesis of intermediate compound sub 3-2
R-4 (20 g,81.3 mmol) and 2-bromodibenzo [ b, d ] are reacted under nitrogen]Furan (20 g,81.3 mmol) was added to 400ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (33.7 g,243.9 mmol) was dissolved in 34ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.8 g,2.4 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 598ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound Sub 3-1 (15.3 g,51%, MS: [ M+H) ] + ＝369.1)。
Sub 3-1 (15 g,37.5 mmol) and bis (pinacolato) diboron (19.1 g,75 mmol) are added to 300ml of di under a nitrogen atmosphereIn alkane, the mixture was stirred and refluxed. Then, potassium acetate (10.8 g,112.5 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.6 g,1.1 mmol) and tricyclohexylphosphine (0.6 g,2.3 mmol) were then added. After the reaction was continued for 7 hours, the reaction mixture was cooled to room temperature, and then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. Adding it againTo 173ml of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound Sub 3-2 (10.4 g,60%, MS: [ M+H)] + ＝461.2)。
Synthesis example 5: synthesis of intermediate compound sub 4-2
R-4 (20 g,81.3 mmol) and 1-bromodibenzo [ b, d ] are reacted under nitrogen]Furan (20 g,81.3 mmol) was added to 400ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (33.7 g,243.9 mmol) was dissolved in 34ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.8 g,2.4 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 598ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound Sub 4-1 (22.4 g,75%, MS: [ M+H) ] + ＝369.1)。
Sub 4-1 (15 g,30 mmol) and bis (pinacolato) diboron (15.3 g,60 mmol) were added to 300ml of diboron under a nitrogen atmosphereIn alkane, the mixture was stirred and refluxed. Then, potassium acetate (8.7 g,90 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.5 g,0.9 mmol) and tricyclohexylphosphine (0.5 g,1.8 mmol) were then added thereto. After the reaction was continued for 6 hours, the reaction mixture was cooled to room temperature, and then the organic layer was subjected toThe salt was removed by filtration, and the filtered organic layer was distilled. It was added to 138ml chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare white solid compound Sub 4-2 (9.5 g,69%, MS: [ M+H)] + ＝461.2)。
Synthesis example 6: synthesis of intermediate compound sub 5-2
R-4 (20 g,81.3 mmol) and 4-bromodibenzo [ b, d ] are reacted under nitrogen]Thiophene (21.3 g,81.3 mmol) was added to 400ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (33.7 g,243.9 mmol) was dissolved in 34ml of water, added to the mixture and stirred well, and then tetrakis-triphenylphosphine palladium (2.8 g,2.4 mmol) was added. After the reaction was continued for 1 hour, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was added to 624mL of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare yellow solid compound Sub 5-1 (17.5 g,56%, MS: [ M+H) ] + ＝385)。
Sub 5-1 (15 g,25 mmol) and bis (pinacolato) diboron (12.7 g,50 mmol) were added to 300ml of diboron under a nitrogen atmosphereIn alkane, the mixture was stirred and refluxed. Then, potassium acetate (7.2 g,75 mmol) was added thereto with sufficient stirring, and palladium dibenzylidene acetone palladium (0.4 g,0.8 mmol) and tricyclohexylphosphine (0.4 g,1.5 mmol) were then added thereto. After the reaction was continued for 5 hoursAfter that, the reaction mixture was cooled to room temperature, and then the organic layer was subjected to filtration treatment to remove salts, and then the filtered organic layer was distilled. It was added to 120ml of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare white solid compound Sub 5-2 (6.5 g,54%, MS: [ M+H)] + ＝479.2)。
Preparation example 1: preparation of Compound 1
Sub 1-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 1 (10.4 g,73%, MS: [ M+H ] ] + ＝656.2)。
Preparation example 2: preparation of Compound 2
Sub 2-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Potassium carbonate (9 g,65.2 mmol) was then dissolved in 9ml of water, added to the mixture and stirred thoroughly, howeverAfter that, tetrakis (triphenylphosphine) palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 1 hour, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 2 (8.1 g,57%, MS: [ M+H ]] + ＝656.2)。
Preparation example 3: preparation of Compound 3
Sub 3-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 3 (10.4 g,73%, MS: [ M+H ] ] + ＝656.2)。
Preparation example 4: preparation of Compound 4
Sub 4-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water and addedTo the mixture was stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 4 (7.3 g,51%, MS: [ M+H)] + ＝656.2)。
Preparation example 5: preparation of Compound 5
Sub 5-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was added to 292mL of chloroform, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare yellow solid compound 5 (10.8 g,74%, MS: [ M+H ] ] + ＝672.2)。
Preparation example 6: preparation of Compound 6
Sub 5-2 (10 g,21.7 mmol) and 2- (4-chloro-6-phenyl-1, 3, 5-triazin-2-yl) -9-phenyl-9H-carbazole (9.4 g,21.7 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml water, added to the mixture and stirred well, then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 324mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare yellow solid compound 6 (11.8 g,73%, MS: [ M+H)] + ＝747.2)。
Preparation example 7: preparation of Compound 7
Sub 5-2 (10 g,21.7 mmol) and 4- (4-chloro-6-phenyl-1, 3, 5-triazin-2-yl) -9-phenyl-9H-carbazole (9.4 g,21.7 mmol) were added to 200ml tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare yellow solid compound 7 (10.8 g,76%, MS: [ M+H ] ] + ＝656.2)。
Preparation example 8: preparation of Compound 8
Sub 5-2 (10 g,21.7 mmol) and 9- (4-chloro-6-phenyl-1, 3, 5-triazin-2-yl) -9H-carbazole (7.7 g,21.7 mmol) were added to 200ml of tetrahydrofuran under nitrogen atmosphere and the mixture was stirred and refluxed. However, the method is thatAfter that, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 3 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 291mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 8 (8.9 g,61%, MS: [ M+H ]] + ＝671.2)。
Preparation example 9: preparation of Compound 9
Sub 1-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 1 hour, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 9 (11.2 g,79%, MS: [ M+H ] ] + ＝656.2)。
Preparation example 10: preparation of Compound 10
Sub 1-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuranThe mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 10 (7.3 g,51%, MS: [ M+H ]] + ＝656.2)。
Preparation example 11: preparation of Compound 11
Sub 1-2 (10 g,21.7 mmol) and 2-chloro-4- (dibenzo [ b, d) were reacted under nitrogen]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (7.8 g,21.7 mmol) was added to 200ml tetrahydrofuran and the mixture was stirred and refluxed. Then, potassium carbonate (9 g,65.2 mmol) was dissolved in 9ml of water, added to the mixture and stirred well, and then tetrakis triphenylphosphine palladium (0.8 g,0.7 mmol) was added. After the reaction was continued for 2 hours, the reaction mixture was cooled to room temperature, then the organic layer and the aqueous layer were separated, and the organic layer was distilled. It was added to 285mL of chloroform again, dissolved and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare white solid compound 11 (8.1 g,57%, MS: [ M+H ] ] + ＝656.2)。
Experimental example
Experimental example 1 ]
Coated with a coating having a thickness ofThe glass substrate as a thin film of ITO (indium tin oxide) is put into distilled water in which a cleaning agent is dissolved, and subjected to ultra-treatmentAnd (5) cleaning by sound. At this time, a product manufactured by Fischer co. Was used as a cleaner, and distilled water filtered twice using a filter manufactured by Millipore co. Was used as distilled water. After washing the ITO for 30 minutes, the ultrasonic washing was repeated twice using distilled water for 10 minutes. After the washing with distilled water was completed, the substrate was ultrasonically washed with isopropanol, acetone and methanol solvents, dried, and then transferred to a plasma washer. In addition, the substrate was cleaned using oxygen plasma for 5 minutes and then transferred to a vacuum depositor. />
On the transparent ITO electrode thus prepared, the following HI-1 was thermally vacuum depositedTo form a hole injection layer. Thermally vacuum depositing the following compound HT-1 on the hole injection layer to +.>To form a hole transport layer and vacuum depositing the following compound HT-2 to +.>To form an electron blocking layer. Compound 1 prepared in the previous preparation example 1, the following compound YGH-1 and phosphorescent dopant YGD-1 were co-deposited on the HT-2 deposited layer at a weight ratio of 44:44:12 to form a thickness +. >Is provided. Vacuum depositing the following compound ET-1 to +.>To form an electron transport layer, and vacuum depositing the following compounds ET-2 and Li on the electron transport layer in a weight ratio of 98:2 to form a thickness +.> Electron injection layer of (a) is provided. In the electric fieldDepositing aluminum on the sub-implant layer to +.>To form a cathode.
In the above process, the vapor deposition rate of the organic material is maintained atTo-> The deposition rate of aluminum is kept at +.>And the vacuum degree during deposition is maintained at 1×10 -7 To 5X 10 -8 And (5) a bracket.
Experimental examples 2 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 1, except that the compound shown in the following table 1 was used instead of the compound 1 of preparation example 1 in experimental example 1.
Comparative Experimental examples 1 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 1, except that the compound shown in the following table 1 was used instead of the compound 1 of preparation example 1 in experimental example 1. Compounds CE1 to CE5 shown in table 1 are as follows.
For the organic light-emitting devices manufactured in the experimental examples and comparative experimental examples, the temperature was 10mA/cm 2 Voltage and efficiency were measured at a current density of 50mA/cm 2 The lifetime is measured at the current density of (2). The results are shown in table 1 below. In this case In the case of LT 95 Meaning the time required for the brightness to decrease to 95% of the original brightness.
TABLE 1
As shown in table 1, it was confirmed that when the compound of the present disclosure was used as an organic light emitting layer material, it exhibited excellent characteristics in terms of efficiency and lifetime, compared to comparative experimental examples.
This is believed to be because in the continuous bonding of the triazine and dibenzofuran substituents, the bond is at the 2-and 7-positions of the dibenzofuranyl group and the dibenzofuranyl or dibenzothiophenyl groups are substituted, thereby increasing the electrical stability.
[ description of reference numerals ]
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: electron transport layer
9: electron injection layer
Claims (6)
1. A compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
y is O or S, and the total number of the catalyst is O or S,
each X is independently N or CH, provided that at least one X is N,
Ar 1 is any one selected from the following:
Ar 2 is phenyl, biphenyl or naphthyl,
n is an integer from 0 to 4, and
r is phenyl.
2. The compound according to claim 1, wherein the compound represented by chemical formula 1 is any one selected from compounds represented by the following chemical formulas 1-1 to 1-4:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In chemical formulas 1-1 to 1-4,
X、Y、n、R、Ar 1 and Ar is a group 2 As defined in claim 1.
3. The compound of claim 1, wherein n is 0 to 2.
4. The compound of claim 1, wherein all X are N.
5. The compound according to claim 1, wherein the compound represented by chemical formula 1 is selected from the group consisting of:
6. an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the compound according to any one of claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20180135442 | 2018-11-06 | ||
| KR10-2018-0135442 | 2018-11-06 | ||
| PCT/KR2019/014992 WO2020096350A1 (en) | 2018-11-06 | 2019-11-06 | Novel compound and organic light-emitting element using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112449639A CN112449639A (en) | 2021-03-05 |
| CN112449639B true CN112449639B (en) | 2023-09-12 |
Family
ID=70737202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980048250.3A Active CN112449639B (en) | 2018-11-06 | 2019-11-06 | Compound and organic light emitting device comprising the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102321311B1 (en) |
| CN (1) | CN112449639B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102392659B1 (en) * | 2019-05-22 | 2022-04-29 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102368409B1 (en) * | 2019-05-30 | 2022-02-25 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic device, composition for organic optoelectronic device and organic optoelectronic device and display device |
| WO2022092625A1 (en) * | 2020-10-30 | 2022-05-05 | 엘티소재주식회사 | Heterocyclic compound, organic light-emitting device comprising same, composition for organic layer of organic light-emitting device, and method for manufacturing organic light-emitting device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518103A (en) * | 2013-09-11 | 2016-04-20 | 默克专利有限公司 | Organic electroluminescent device |
| CN105753847A (en) * | 2015-01-07 | 2016-07-13 | 环球展览公司 | Organic Electroluminescent Material, Composition And Device And Method For Manufacturing Same |
| CN105899501A (en) * | 2014-01-09 | 2016-08-24 | 三星Sdi株式会社 | Organic compound, organic optoelectronic device, and display device |
| CN106459018A (en) * | 2014-05-05 | 2017-02-22 | 默克专利有限公司 | Materials for organic light emitting devices |
| KR20180051355A (en) * | 2016-11-07 | 2018-05-16 | 주식회사 엘지화학 | Novel hetero-cyclic compound and organic light emitting device comprising the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100430549B1 (en) | 1999-01-27 | 2004-05-10 | 주식회사 엘지화학 | New organomattalic complex molecule for the fabrication of organic light emitting diodes |
| JP6989029B2 (en) * | 2018-10-22 | 2022-01-05 | エルジー・ケム・リミテッド | New heterocyclic compounds and organic light emitting devices using them |
-
2019
- 2019-11-06 CN CN201980048250.3A patent/CN112449639B/en active Active
- 2019-11-06 KR KR1020190140606A patent/KR102321311B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518103A (en) * | 2013-09-11 | 2016-04-20 | 默克专利有限公司 | Organic electroluminescent device |
| CN105899501A (en) * | 2014-01-09 | 2016-08-24 | 三星Sdi株式会社 | Organic compound, organic optoelectronic device, and display device |
| CN106459018A (en) * | 2014-05-05 | 2017-02-22 | 默克专利有限公司 | Materials for organic light emitting devices |
| CN105753847A (en) * | 2015-01-07 | 2016-07-13 | 环球展览公司 | Organic Electroluminescent Material, Composition And Device And Method For Manufacturing Same |
| KR20180051355A (en) * | 2016-11-07 | 2018-05-16 | 주식회사 엘지화학 | Novel hetero-cyclic compound and organic light emitting device comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112449639A (en) | 2021-03-05 |
| KR20200052236A (en) | 2020-05-14 |
| KR102321311B1 (en) | 2021-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110709403B (en) | Novel heterocyclic compound and organic light emitting device using the same | |
| CN112703189B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112055705B (en) | Novel compound and organic light emitting device comprising the same | |
| CN111183204B (en) | Organic light emitting device | |
| CN112585115B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112041315B (en) | Compound and organic light emitting device comprising the same | |
| CN111094277B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112424183B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112888683B (en) | Novel compound and organic light emitting device comprising the same | |
| CN110753687B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN110520419B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN111989326B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN111655683B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN112424191B (en) | Compound and organic light emitting device comprising the same | |
| CN112449639B (en) | Compound and organic light emitting device comprising the same | |
| CN110573498B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN111094310B (en) | Organometallic compound and organic light emitting device including the same | |
| CN112533914A (en) | Novel compound and organic light emitting device comprising the same | |
| CN111971281B (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| CN111902407B (en) | Compound and organic light emitting device comprising the same | |
| CN111630038B (en) | Novel compound and organic light emitting device comprising the same | |
| CN113260608B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112739694A (en) | Novel compound and organic light emitting device comprising the same | |
| CN112074512A (en) | Novel compound and organic light emitting device comprising the same | |
| CN112689639B (en) | Compound and organic light emitting device comprising 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 |