WO2020073605A1 - 一种有机发光化合物及制法和含该化合物的有机电致发光器件 - Google Patents

一种有机发光化合物及制法和含该化合物的有机电致发光器件 Download PDF

Info

Publication number
WO2020073605A1
WO2020073605A1 PCT/CN2019/078284 CN2019078284W WO2020073605A1 WO 2020073605 A1 WO2020073605 A1 WO 2020073605A1 CN 2019078284 W CN2019078284 W CN 2019078284W WO 2020073605 A1 WO2020073605 A1 WO 2020073605A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
unsubstituted
organic
ring
compound
Prior art date
Application number
PCT/CN2019/078284
Other languages
English (en)
French (fr)
Inventor
林文晶
王辉
汪康
刘琨
刘天娇
张思明
于丹阳
马晓宇
Original Assignee
上海升翕光电科技有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from CN201811180929.1A external-priority patent/CN109180560A/zh
Priority claimed from CN201910184076.7A external-priority patent/CN109776393A/zh
Application filed by 上海升翕光电科技有限公司 filed Critical 上海升翕光电科技有限公司
Publication of WO2020073605A1 publication Critical patent/WO2020073605A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present disclosure relates to the technical field of organic light-emitting materials, in particular to an organic light-emitting compound, a preparation method, and an organic electroluminescent device of the compound.
  • An electroluminescence device is an automatic light-emitting device, which has the advantage that it can provide a wider viewing angle, a larger contrast ratio, and a faster response time.
  • An organic EL element is a self-luminous element that utilizes the principle that by applying an electric field, the recombination of holes injected from the anode and electrons injected from the cathode can cause the fluorescent substance to emit light. It has the following structure: anode, cathode and organic layer between them.
  • the organic material layer includes multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer, an electron transport layer (ETL), and electrons Injection layer (EIL).
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • EIL electrons Injection layer
  • the most important factor that determines the luminous efficiency in organic EL devices is the luminescent material. So far, fluorescent materials have been widely used as light-emitting materials. However, in view of the electroluminescence mechanism, since the phosphorescent material theoretically enhances the luminous efficiency by four (4) times compared with the fluorescent material, the development of the phosphorescent light-emitting material has been extensively studied. Iridium (III) complexes have been widely referred to as phosphorescent doping materials. Currently, 4,4'-N, N'-dicarbazole-biphenyl (CBP), 9,10-bis (2-naphthyl) anthracene (ADN), etc. are widely used as known phosphorescent host materials.
  • CBP N'-dicarbazole-biphenyl
  • ADN 9,10-bis (2-naphthyl) anthracene
  • Organic EL devices containing phosphorescent host materials require higher driving voltages. Meanwhile, in order to improve the efficiency and stability of the organic EL device, it is required to have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • the hole transport layer can change the hole transport efficiency from the hole to the light emitting layer, luminous efficiency, life, etc.
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • NPD 4,4'-diphenyl-N
  • TPD N '-Bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine
  • organic EL devices using these materials have problems in quantum efficiency and service life.
  • the present disclosure provides an organic light emitting compound, the structural formula of which is as follows:
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C 3 -C 30 polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Of heteroatoms;
  • Ring G represents a substituted or unsubstituted C 1 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group;
  • the G ring may or may not exist
  • X, Y, Z represent -O-, -S-, -SO 2- , -C (R 5 ) (R 6 )-, -N (R 7 )-, -Si (R 5 ) (R 6 )-, -Sn (R 7 )-or -Ge (R 7 )-;
  • G ring is preferably benzene ring, naphthalene ring, pyridine ring, 1-phenyl-1H-indole, benzofuran, benzothiophene, 4-phenyl-4H-benzo [b ] [1,4] oxazine, 4-phenyl-4H-benzothiazine, benzothiophene, 1,4-diphenyl-1,4-dihydroquinoxaline or 1,1,4,4 -Tetramethyl-1,4-dihydronaphthalene;
  • R 1 to R 4 each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxyl, substituted or unsubstituted C 1 -C 30 hydrocarbons, substituted or unsubstituted C 1- C 30 alkoxy, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 3 -C 30 cycloalkenyl, substituted or unsubstituted 3-7 membered hetero Cycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, -NR 8 R 9 , -SiR 10 R 11 R 12 , -SR 13 , -OR 14 , -COR 15 or -B (OR 16 ) (OR 17 ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C 3 -C 30
  • R 5 to R 17 each independently represent hydrogen, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3 Up to 30-membered heteroaryl; or linked to adjacent substituents to form substituted or unsubstituted monocyclic or C 3 -C 30 polycyclic aliphatic or aromatic rings;
  • a, b, and d independently represent integers 1 to 4; c represents integers 1 to 3.
  • the present disclosure also provides a method for preparing an organic light-emitting compound, including the following steps:
  • Step 1 After adding Compound 2 and tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, and after stirring the mixture at -78 ° C, It was stirred at room temperature and cooled to -78 ° C; thereafter, Compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was raised to room temperature, and the mixture was stirred; then the chlorination An aqueous ammonium solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, followed by drying the extracted organic layer with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain an intermediate Body 1-1;
  • Step 2 After adding Intermediate 1-1, Compound 3 and methylene chloride to the reaction vessel, fully replace the air with nitrogen three times, and add boron trifluoride ether dissolved in methylene chloride dropwise to the mixture; After stirring the mixture at room temperature, it was quenched with distilled water, and the mixture was extracted with dichloromethane; then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain intermediate 2;
  • Step 3 Intermediate 2, Ar 1 Br and Ar 2 Br, Pd 2 (dba) 3 , P (t-Bu) 3 , NaOt-Bu, toluene are reacted; after the reaction is completed, the organic matter is extracted with ether and water. The concentrated product after the layer was dried with magnesium sulfate was used to obtain the compound of formula 1 by silica gel column and recrystallization method;
  • the synthetic route is as follows:
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C 3 -C 30 polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Hetero atom; G ring means substituted or unsubstituted C 1 -C 30 cycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, or substituted or unsubstituted 3-30 member Heteroaryl; G ring may or may not exist; when G ring is absent, X, Y, Z represent -O-, -S-, -SO 2- , -C (R 5 ) (R 6 )
  • the present disclosure also provides an organic electroluminescence device containing the above organic light-emitting compound.
  • the present disclosure also provides the use of the above-mentioned organic electroluminescent device in an organic light-emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoreceptor (OPC) or an organic thin film transistor (OTFT) .
  • OLED organic light-emitting device
  • OSC organic solar cell
  • e-Paper electronic paper
  • OPC organic photoreceptor
  • OFT organic thin film transistor
  • the technical problems in the present disclosure to be solved by the present disclosure include, for example, providing an organic light-emitting compound and a manufacturing method and an organic electroluminescent device of the compound. Power efficiency and long life.
  • the present disclosure provides an organic light emitting compound, the structural formula of which is as follows:
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C 3 -C 30 polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Of heteroatoms;
  • Ring G represents a substituted or unsubstituted C 1 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group;
  • the G ring may or may not exist
  • X, Y, Z represent -O-, -S-, -SO 2- , -C (R 5 ) (R 6 )-, -N (R 7 )-, -Si (R 5 ) (R 6 )-, -Sn (R 7 )-or -Ge (R 7 )-;
  • X represents -SO 2- , -N (R 7 )-, -Si (R 5 ) (R 6 )-, Sn (R 7 )-, or -Ge (R 7 )-;
  • Y, Z represent C, N, O, S atoms;
  • R 3 is selected from hydrogen, or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C 3 -C 30 polycyclic aliphatic ring or aromatic ring,
  • G ring Preferred are benzene ring, naphthalene ring, pyridine ring, 1-phenyl-1H-indole, benzofuran, benzothiophene, 4-phenyl-4H-benzo [b] [1,4] oxazine, 4- Phenyl-4H-benzothiazine, benzothiophene, 1,4-diphenyl-1,4-dihydroquinoxaline, 1,1,4,4-t
  • R 1 to R 4 each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxyl, substituted or unsubstituted C 1 -C 30 hydrocarbons, substituted or unsubstituted C 1- C 30 alkoxy, substituted or unsubstituted C 3 -C 30 cycloalkyl, substituted or unsubstituted C 3 -C 30 cycloalkenyl, substituted or unsubstituted 3-7 membered hetero Cycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, -NR 8 R 9 , -SiR 10 R 11 R 12 , -SR 13 , -OR 14 , -COR 15 or -B (OR 16 ) (OR 17 ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C 3 -C 30
  • R 5 to R 17 each independently represent hydrogen, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3 Up to 30-membered heteroaryl; or linked to adjacent substituents to form substituted or unsubstituted monocyclic or C 3 -C 30 polycyclic aliphatic or aromatic rings; in some embodiments, R 7 is benzene , Cyano substituted benzene, or methyl;
  • a, b, and d each independently represent integers 1 to 4; c represents integers 1 to 3; in some embodiments, a, b, c, and d are all 1.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 10 -C 25 aryl group, or a 13-25 membered heteroaryl group; further preferably Ar 1 and Ar 2 each independently represent Substituted or unsubstituted C 14 -C 21 aryl, or 17-23 membered heteroaryl; it is further preferred that Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 16 -C 19 aryl, Or 19-21 membered heteroaryl; further preferably Ar 1 and Ar 2 are benzene, 1,1 ′, 3 ′, 1 ′′ -triphenyl, biphenyl, diaminobenzene, phenanthryl, naphthyl, 1- Phenylnaphthalene or 9,9-dimethylfluorene.
  • the organic light-emitting compound is selected from any one of the following structures:
  • the present disclosure also provides a method for preparing an organic light-emitting compound, including the following steps:
  • Step 1 After adding Compound 2 and tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, and after stirring the mixture at -78 ° C, It was stirred at room temperature and cooled to -78 ° C; thereafter, Compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was raised to room temperature, and the mixture was stirred; then the chlorination An aqueous ammonium solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, followed by drying the extracted organic layer with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain an intermediate Body 1-1;
  • Step 2 After adding Intermediate 1-1, Compound 3 and methylene chloride to the reaction vessel, fully replace the air with nitrogen three times, and add boron trifluoride ether dissolved in methylene chloride dropwise to the mixture; After stirring the mixture at room temperature, it was quenched with distilled water, and the mixture was extracted with dichloromethane; then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain intermediate 2;
  • Step 3 Intermediate 2, Ar 1 Br and Ar 2 Br, Pd 2 (dba) 3 , P (t-Bu) 3 , NaOt-Bu, toluene are reacted; after the reaction is completed, the organic matter is extracted with ether and water. The concentrated product after the layer was dried with magnesium sulfate was used to obtain the compound of formula 1 by silica gel column and recrystallization method;
  • the synthetic route is as follows:
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C 3 -C 30 polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Hetero atom; G ring means substituted or unsubstituted C 1 -C 30 cycloalkyl, substituted or unsubstituted C 6 -C 30 aryl, or substituted or unsubstituted 3-30 member Heteroaryl; G ring may or may not exist; when G ring is absent, X, Y, Z represent -O-, -S-, -SO 2- , -C (R 5 ) (R 6 )
  • the organic electroluminescent compound according to the present disclosure may be included in at least one of the light emitting layer and the hole transport layer.
  • the present disclosure also provides an organic electroluminescence device containing the above organic light-emitting compound.
  • the organic electroluminescent device includes: a first electrode, a second electrode, and an organic layer disposed between the two electrodes, wherein the organic layer includes at least one type 1
  • the compound of the structure shown; the compound of the structure shown in Formula 1 may be in a single form or mixed with other substances in the organic layer.
  • the organic layer includes a light-emitting layer, and preferably includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
  • the organic layer includes at least a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport skills, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer , One or more of the electron injection layer and the layer with both electron transmission and electron injection skills.
  • organic layer in the present disclosure refers to the term of all layers disposed between the first electrode and the second electrode of the organic electroluminescent device.
  • the compound of formula 1 when the compound of formula 1 is present in the light-emitting layer of the organic layer, the compound of formula 1 can be used as a light-emitting host or doped in other fluorescent hosts;
  • the compound of formula 1 when the compound of formula 1 is present in the hole transport layer or hole injection layer in the organic layer, the compound of formula 1 can be used as a hole transport layer, a hole injection layer, and both With hole transport common energy layer.
  • the device prepared by the compound containing the structure of formula 1 described in this disclosure can be used for organic light emitting device (OLED), organic solar cell (OSC), electronic paper (e-Paper), organic photoreceptor (OPC) or organic thin film transistor (OTFT).
  • OLED organic light emitting device
  • OSC organic solar cell
  • e-Paper electronic paper
  • OPC organic photoreceptor
  • OTFT organic thin film transistor
  • the organic electroluminescent device described in the present disclosure can form an anode by vapor-depositing metal, conductive oxides and their alloys on a substrate by thin film evaporation, electron beam evaporation, physical vapor deposition, etc., or spin coating Film (spin-coating) or thin-band lead evaporation; tape-casting, doctor-blading, screen-printing, inkjet printing or thermal imaging (Thermal- Imaging) and other methods to reduce the number of layers manufacturing.
  • the present disclosure relates to an organic light-emitting compound of Formula 1 and a preparation method thereof, and an organic electroluminescent device containing the compound.
  • the present disclosure provides a hole transport material used in an organic EL device that can solve conventional technical problems.
  • the traditional hole transport materials are mainly based on triaryl derivatives. Although it has a hole-transporting ability and a low driving voltage, in order to obtain a suitable glass transition temperature, it has to introduce a large number of substituents in its structure to increase its molecular weight. However, this reduces the triplet energy or LUMO energy, which leads to the deterioration of the organic electroluminescent device.
  • the ideal hole transport material requires a high glass transition temperature, hole injection ability and hole transport ability, as well as suitable triplet energy and LUMO energy.
  • the present disclosure proposes a solution of introducing an arylamine and a heterocyclic ring to the 9-position of fluorene.
  • the organic electroluminescent device prepared from the organic light-emitting compound of the present disclosure has excellent current efficiency and power efficiency and long life.
  • the preparation method of the organic light-emitting compound of the present disclosure has good repeatability and high yield.
  • Example 19 Manufacturing an organic electroluminescent device containing Compound 1
  • the coating thickness is The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, repeatedly washed with distilled water twice, and ultrasonically washed for 10 minutes. After the distilled water was cleaned, isopropyl alcohol, acetone, methanol and other solvents were ultrasonically washed in sequence and dried. Transfer to a plasma cleaner, wash the substrate for 5 minutes, and send it to a vapor deposition machine. 4,4 ', 4 "-tri [2-naphthylphenylamino] triphenylamine (2-TNATA) with a thickness of 50nm was deposited on the prepared ITO transparent electrode as a hole injection layer.
  • Compound 1 vacuum-deposits a hole transport layer with a thickness of 30 nm on the formed hole injection layer. Then, a blue host material 9,10-bis (2-naphthyl) with a thickness of 30 nm is vapor-deposited on the hole transport layer ) Anthracene (ADN) and doped material bis (4,6-difluorophenylpyridine-N, C 2 ) pyridineformyl iridium (FIrpic). The weight ratio of host material and doped material is 95: 5. TPBi with a thickness of 40 nm is vacuum-evaporated on the light-emitting layer as a hole blocking layer and an electron transport layer.
  • ADN Anthracene
  • FIrpic doped material bis (4,6-difluorophenylpyridine-N, C 2 ) pyridineformyl iridium
  • Lithium fluoride (LiF) with a thickness of 0.5 nm is vacuum-evaporated on the electron-transport layer as an electron injection layer. Aluminium plated with a thickness of 150nm was used as the cathode to complete the preparation of the organic electroluminescent device.
  • the luminescence characteristics were tested by using a KEITHLEY 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate Driving voltage, luminous brightness, luminous efficiency.
  • Example 20 Fabrication of an organic electroluminescent device containing compound 7
  • Example 19 The compound 1 in Example 19 was replaced with the compound 7, and the organic electroluminescent device containing the compound 7 was produced in the same manner as the other methods.
  • Example 21 Fabrication of an organic electroluminescent device containing compound 13
  • Example 19 The compound 1 in Example 19 was replaced with the compound 13, and the organic EL device containing the compound 13 was produced in the same manner as in the other methods.
  • Example 22 Fabrication of an organic electroluminescent device containing compound 17
  • Example 19 The compound 1 in Example 19 was replaced with the compound 17, and the organic electroluminescent device containing the compound 17 was produced in the same manner as the other methods.
  • Example 23 Fabrication of an organic electroluminescent device containing compound 18
  • Example 19 The compound 1 in Example 19 was replaced with the compound 18, and other methods were the same. An organic electroluminescent device containing the compound 18 was produced.
  • Example 24 Manufacture of an organic electroluminescent device containing compound 20
  • Example 19 The compound 1 in Example 19 was replaced with the compound 20, and the organic EL device containing the compound 20 was produced in the same manner as the other methods.
  • Example 25 Fabrication of an organic electroluminescent device containing compound 28
  • Example 19 The compound 1 in Example 19 was replaced with the compound 28, and the organic EL device containing the compound 28 was produced in the same manner as in the other methods.
  • Example 26 Fabrication of an organic electroluminescent device containing compound 31
  • Example 19 The compound 1 in Example 19 was replaced with the compound 31, and the organic EL device containing the compound 31 was produced in the same manner as the other methods.
  • Example 27 Fabrication of an organic electroluminescent device containing compound 35
  • Example 19 The compound 1 in Example 19 was replaced with the compound 35, and other methods were the same, and an organic electroluminescence device containing the compound 35 was produced.
  • Example 28 Manufacture of an organic electroluminescent device containing compound 40
  • Example 19 The compound 1 in Example 19 was replaced with the compound 40, and the organic EL device containing the compound 40 was produced in the same manner as in the other methods.
  • Example 29 Manufacture of an organic electroluminescent device containing compound 41
  • Example 19 The compound 1 in Example 19 was replaced with the compound 41, and the organic EL device containing the compound 41 was produced in the same manner as in the other methods.
  • Example 30 Fabrication of an organic electroluminescent device containing compound 42
  • Example 19 The compound 1 in Example 19 was replaced with the compound 42, and other methods were the same, and an organic electroluminescence device containing the compound 42 was produced.
  • Example 31 Fabrication of an organic electroluminescent device containing compound 45
  • Example 19 The compound 1 in Example 19 was replaced with the compound 45, and other methods were the same, and an organic electroluminescence device containing the compound 45 was produced.
  • Example 32 Manufacture of an organic electroluminescent device containing compound 46
  • Example 19 The compound 1 in Example 19 was replaced with the compound 46, and other methods were the same, and an organic electroluminescence device containing the compound 46 was produced.
  • Example 33 Fabrication of an organic electroluminescent device containing compound 51
  • Example 19 The compound 1 in Example 19 was replaced with the compound 51, and other methods were the same, and an organic electroluminescence device containing the compound 51 was produced.
  • Example 34 Fabrication of an organic electroluminescent device containing compound 54
  • Example 19 The compound 1 in Example 19 was replaced with the compound 54, and other methods were the same, and an organic electroluminescence device containing the compound 54 was produced.
  • Example 35 Fabrication of an organic electroluminescent device containing compound 61
  • Example 19 The compound 1 in Example 19 was replaced with the compound 61, and other methods were the same, and an organic electroluminescence device containing the compound 61 was produced.
  • Example 36 Manufacture of an organic electroluminescent device containing compound 77
  • Example 19 The compound 1 in Example 19 was replaced with the compound 77, and other methods were the same, and an organic electroluminescence device containing the compound 77 was produced.
  • the material of the hole transport layer was replaced by Compound 1 with N'-bis (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4 , 4'-diamine (NPD).
  • Table 1 shows the test results of the luminescence characteristics of the compounds prepared by the examples of the present disclosure and the organic electroluminescent devices prepared by a-NPD.
  • the compounds provided by the cost disclosure have suitable glass transition temperatures, and the luminous efficiency and life span of the organic electroluminescent devices prepared from them are significantly improved compared to the organic electroluminescent devices prepared from a-NPD.
  • the present disclosure provides an organic light-emitting compound, hole injection capability / transport capability, high power efficiency, and long life are obtained by introducing an arylamine; an appropriate glass transition temperature is obtained by introducing a heterocyclic ring, thereby obtaining high-quality organic electricity Luminescent material.
  • the preparation method of the organic luminescent compound provided by the present disclosure has good repeatability and high yield.
  • the organic electroluminescent device prepared from the organic light emitting compound of the present disclosure has excellent current efficiency and power efficiency and long life.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本公开涉及有机发光材料技术领域，具体涉及一种有机发光化合物及制法和该化合物的有机电致发光器件。本公开提出向芴的9-位引入芳基胺和杂环的解决方案。通过引入芳基胺获得了空穴注入能力/传输能力，高功率效率、长寿命；通过引入杂环获得适当玻璃态转变温度，从而获得了优质的有机电致发光材料。由本公开的机发光化合物制备的有机电致发光器件具有极佳电流效率和功率效率以及长寿命。本公开的有机发光化合物的制备方法，重复性好，产率高。

Description

一种有机发光化合物及制法和含该化合物的有机电致发光器件
相关申请的交叉引用
本申请要求于2019年03月12日提交中国专利局的申请号为201910184076.7、名称为“一种有机发光化合物及制法和该化合物的有机电致发光器件”的中国专利申请的优先权，以及于2018年10月11日提交中国专利局的申请号为201811180929.1、名称为“一种有机发光化合物及制法和含该化合物的有机电致发光器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及有机发光材料技术领域，具体涉及一种有机发光化合物及制法和该化合物的有机电致发光器件。
背景技术
电致发光装置(EL装置)为自动发光装置，其优点在于其可提供较宽的视角、较大的对比率和较快的响应时间。
有机EL元件是利用了如下原理的自发光元件：通过施加电场，利用由阳极注入的空穴与由阴极注入的电子的复合能使荧光性物质发光。它具有如下结构:阳极、阴极以及介于两者之间的有机物层。为了提高有机EL元件的效率和稳定性，有机材料层包括具有不同材料的多层，例如空穴注入层(HIL)、空穴传输层(HTL)、发光层、电子传输层(ETL)和电子注入层(EIL)。
在这种有机发光二极管中，当在阳极和阴极之间施加电压时，来自阳极的空穴和来自阴极的电子注入有机材料层。产生的激子在迁移至基态时产生具有特定波长的光。
决定有机EL装置中的发光效率的最重要因素是发光材料。到目前为止，荧光材料已经广泛用作发光材料。然而，鉴于电致发光机制，由于磷光材料在理论上与荧光材料相比使发光效率增强四(4)倍，因此磷光发光材料的开发得到广泛研究。铱(III)络合物已广泛地被称为磷光掺杂材料。目前，4,4’-N,N’-二咔唑-联苯(CBP)、9,10-二(2-萘基)蒽(ADN)等作为已知的磷光主体材料得到广泛的应用。尽管这些材料提供良好发光特征，但其具有以下缺点：(1)由于其较低玻璃态转变温度和不良热稳定性，导致装置的寿命降低。(2)包含磷光主体材料的有机EL装置需要较高的驱动电压。同时，为了提高有机EL装置的效率和稳定性，需要其具有包含空穴注入层、空穴传输层、发光层、电子传输层和电子注入层的多层结构。其中空穴传输层可改变空穴到发光层的空穴传输效率、发光效率、寿命等。因此，使用铜酞菁(CuPc)、4,4’-双[N-(1-萘基)-N-苯基氨基]联苯(NPB)、N,N’-二苯基-N,N’-双(3-甲基苯基)-(1,1’-联苯)-4,4’-二胺(TPD)等作为空穴传输材料。然而，使用这些材料的有机EL装置在量子效率和使用寿命方面有问题。
发明内容
本公开提供一种有机发光化合物，其结构式如下：
Figure PCTCN2019078284-appb-000001
式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；
G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；
G环可以存在也可以不存在；
当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；
当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；G环优选苯环、萘环、吡啶环、1-苯基-1H-吲哚、苯并呋喃、苯并噻吩、4-苯基-4H-苯并[b][1,4]噁嗪、4-苯基-4H-苯并噻嗪、苯并噻吩、1,4-二苯基-1,4-二氢喹噁啉或者1,1,4,4-四甲基-1,4-二氢萘；
R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；
R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；
a、b和d各自独立地表示整数1到4；c表示整数1到3。
本公开还提供一种有机发光化合物的制法，包括以下步骤：
步骤1、在反应容器中加入化合物2和四氢呋喃之后，在氮气气氛下使所述容器冷却到-78℃，接着将正丁基锂逐滴添加到混合物中，在-78℃下搅拌混合物后，将其在室温下进行搅拌，并且冷却到-78℃；此后，将溶解于四氢呋喃中的化合物1逐滴添加到混合物中；添加后，使反应温度升温到室温，并且搅拌混合物；接着将氯化铵水溶液添加到反应溶液中以完成反应，并且用乙酸乙酯萃取反应溶液，接着使用硫酸镁干燥经萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用管柱色谱法纯化剩余物质获得中间体1-1；
步骤2、将中间体1-1、化合物3和二氯甲烷加入反应容器中之后，用氮气充分置换空气三次，将溶解于二氯甲烷中的三氟化硼***逐滴添加到混合物中；在室温下搅拌混合物后，用蒸馏水淬灭，并且用二氯甲烷萃取混合物；接着使用硫酸钠干燥萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用柱色谱法纯化剩余物质获得中间体2；
步骤3、将中间体2、Ar 1Br和Ar 2Br、Pd 2(dba) 3、P(t-Bu) 3、NaOt-Bu、甲苯进行反应；反应结束以后用***和水提取有机物，有机层用硫酸镁干燥以后的浓缩产品用硅胶柱和重结晶方法得到式1化合物；
其合成路线如下：
Figure PCTCN2019078284-appb-000002
式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；G环可以存在也可以不存在；当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；a、b和d各自独立地表示整数1到4；c表示整数1到3；Hal为卤素。
本公开还提供一种含有上述有机发光化合物的有机电致发光器件。
本公开还提供了上述有机电致发光器件在有机发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-Paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)中的用途。
具体实施方式
本公开要解决现有技术中的技术问题包括，例如提供一种有机发光化合物及制法和该化合物的有机电致发光器件，由本公开的化合物制备的有机电致发光器件具有极佳电流效率和功率效率以及长寿命。
本公开将通过具体的实施例对本公开进行详细描述。然而，以下描述旨在解释本公开，并且不打算以任何方式限制本公开的范围。
本公开提供一种有机发光化合物，其结构式如下：
Figure PCTCN2019078284-appb-000003
式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；
G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；
G环可以存在也可以不存在；
当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；
当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；R 3选自氢，或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，G环优选苯环、萘环、吡啶环、1-苯基-1H-吲哚、苯并呋喃、苯并噻吩、4-苯基-4H-苯并[b][1,4]噁嗪、4-苯基-4H-苯并噻嗪、苯并噻吩、1,4-二苯基-1,4-二氢喹噁啉、1,1,4,4-四甲基-1,4-二氢萘；
R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；
R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；在一些实施方式中，R 7为苯、氰基取代的苯，或甲基；
a、b和d各自独立地表示整数1到4；c表示整数1到3；在一些实施方式中，a、b、c、d均为1。
在一些实施方式中，Ar 1和Ar 2各自独立地表示经取代或未经取代的C 10-C 25芳基，或者13-25元杂芳基；进一步优选Ar 1和Ar 2各自独立地表示经取代或未经取代的C 14-C 21芳基，或者17-23元杂芳基；再优选Ar 1和Ar 2各自独立地表示经取代或未经取代的C 16-C 19芳基，或者19-21元杂芳基；进一步优选Ar 1、Ar 2为苯、1,1',3',1”-三苯基、联苯基、二氨基苯、菲基、萘基、1-苯基萘或者9,9-二甲基芴。
在一些实施方式中，所述有机发光化合物选自下述结构中的任意一个：
Figure PCTCN2019078284-appb-000004
Figure PCTCN2019078284-appb-000005
Figure PCTCN2019078284-appb-000006
本公开还提供一种有机发光化合物的制法，包括以下步骤：
步骤1、在反应容器中加入化合物2和四氢呋喃之后，在氮气气氛下使所述容器冷却到-78℃，接着将正丁基锂逐滴添加到混合物中，在-78℃下搅拌混合物后，将其在室温下进行搅拌，并且冷却到-78℃；此后，将溶解于四氢呋喃中的化合物1逐滴添加到混合物中；添加后，使反应温度升温到室温，并且搅拌混合物；接着将氯化铵水溶液添加到反应溶液中以完成反应，并且用乙酸乙酯萃取反应溶液，接着使用硫酸镁干燥经萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用管柱色谱法纯化剩余物质获得中间体1-1；
步骤2、将中间体1-1、化合物3和二氯甲烷加入反应容器中之后，用氮气充分置换空气三次，将溶解于二氯甲烷中的三氟化硼***逐滴添加到混合物中；在室温下搅拌混合物后，用蒸馏水淬灭，并且用二氯甲烷萃取混合物；接着使用硫酸钠干燥萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用柱色谱法纯化剩余物质获得中间体2；
步骤3、将中间体2、Ar 1Br和Ar 2Br、Pd 2(dba) 3、P(t-Bu) 3、NaOt-Bu、甲苯进行反应；反应结束以后用***和水提取有机物，有机层用硫酸镁干燥以后的浓缩产品用硅胶柱和重结晶方法得到式1化合物；
其合成路线如下：
Figure PCTCN2019078284-appb-000007
式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；G环可以存在也可以不存在；当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经 取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；a、b和d各自独立地表示整数1到4；c表示整数1到3；Hal为卤素。
在发光层和空穴传输层中的至少一个中可以包含根据本公开的有机电致发光化合物。
本公开还提供一种含有上述有机发光化合物的有机电致发光器件。
在一些实施方式中，所述有机电致发光器件包括：第一电极、第二电极和置于所述两电极之间的有机物层，其中，所述有机物层中包含至少一种式1的所示结构的化合物；式1所示结构的化合物可以是单一形态或与其它物质混合存在于有机物层中。
所述第一和第二电极中的一个是阳极，且另一个是阴极。所述有机物层包含发光层，并且优选包含至少一个选自空穴注入层、空穴传输层、电子传输层、电子注入层、、空穴阻挡层以及电子阻挡层组成的群组的层。
在一些实施方式中，所述有机物层至少包括空穴注入层、空穴传输层、既具备空穴注入又具备空穴传输技能层，电子阻挡层，发光层，空穴阻挡层，电子传输层，电子注入层和既具备电子传输又具备电子注入技能层中的一种或几种。
本公开中“有机物层”指的是有机电致发光器件第一电极和第二电极之间部署的全部层的术语。
当式1结构的化合物存在于所述有机物层中的发光层时，所述式1结构的化合物可以作为发光主体或者掺杂在其它荧光主体中；
当式1结构的化合物存在于所述有机物层中的空穴传输层或者空穴注入层时，所述式1结构的化合物可以作为空穴传输层、空穴注入层以及既具备空穴注入又具备空穴传输公能层。
本公开所述的包含有式1结构的化合物制备的器件可以用于有机发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-Paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)。
本公开所述的有机电致发光器件可以通过薄膜蒸镀、电子束蒸发、物理气相沉积等方法在基板上蒸镀金属以及具有导电性的氧化物及他们的合金形成阳极，也可以采用旋转涂膜(spin-coating)或薄带带头蒸镀；还可以采用成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等方法减少层数制造。
本公开涉及式1的有机发光化合物及其制备方法，包含所述化合物的有机电致发光器件。
本公开的有益效果是：
本公开提供用于有机EL装置中的可解决传统技术问题的空穴传输材料。传统的空穴传输材料基本以三芳基衍生物为主。虽然其具有空穴传输能力和低驱动电压，但是为了获得合适的玻璃态转变温度而不得不在其结构上引入大量的取代基提升其分子量。但是这样却降低三重态能量或LUMO能量，从而导致有机电致发光器件的劣化。理想的空穴传输材 料需要高玻璃态转变温度、空穴注入能力和空穴传输能力，以及适合三重态能量和LUMO能量。因此，为了解决传统空穴传输材料中存在的问题而得到理想的材料，本公开提出向芴的9-位引入芳基胺和杂环的解决方案。通过引入芳基胺获得了空穴注入能力/传输能力，高功率效率、长寿命；通过引入杂环获得适当玻璃态转变温度，从而获得了优质的有机电致发光材料。
由本公开的机发光化合物制备的有机电致发光器件具有极佳电流效率和功率效率以及长寿命。
本公开的有机发光化合物的制备方法，重复性好，产率高。
实施例1：制备化合物1
Figure PCTCN2019078284-appb-000008
在反应容器中加入4-溴-9-苯基咔唑(60mmol)和200mL四氢呋喃之后，在氮气气氛下使所述容器冷却到-78℃。接着将正丁基锂(2.5M，60mmol)缓慢逐滴添加到混合物中。在-78℃下搅拌混合物30分钟后，将其在室温下搅拌3小时，并且冷却到-78℃。此后，将溶解于200mL四氢呋喃中的芴酮(60mmol)缓慢逐滴添加到混合物中。添加后，使反应温度缓慢升温到室温，并且搅拌混合物16小时。接着将氯化铵水溶液添加到反应溶液中以完成反应，并且用乙酸乙酯萃取反应溶液。接着使用硫酸镁干燥经萃取的有机物层，并且使用旋转式蒸发器去除溶剂。用管柱色谱法纯化剩余物质获得化合物1-1(19.04g，75％，质谱值:423.42)。
将化合物1-1(45mmol)、2,3,5,6-氘代苯胺(46mmol)和500L二氯甲烷加入反应容器中之后，用氮气充分置换空气三次，将溶解于100mL二氯甲烷中的三氟化硼***(46mmol)缓慢逐滴添加到混合物中。在室温下搅拌混合物2小时后，用蒸馏水淬灭，并且用二氯甲烷萃取混合物。接着使用硫酸钠干燥萃取的有机物层，并且使用旋转式蒸发器去除溶剂。用柱色谱法纯化剩余物质获得化合物3-1(41.85mmol，93％,质谱值:502.25)。
将27.2mmol化合物3-1和27.2mmol溴苯、Pd 2(dba) 3(2.64g,2.89mmol)、P(t-Bu) 3(1.17g,5.78mmol)、NaOt-Bu(16.7g,173.5mmol)、甲苯600mL于100℃条件下进行反应。反应结束以后用***和水提取有机物，有机层用硫酸镁干燥以后的浓缩产品用硅胶柱和重结晶方法得到18.22mmol化合物1(67％)，质谱值为654.32。
实施例2：制备化合物7
Figure PCTCN2019078284-appb-000009
按照上述合成路线，参照实施例1的方法制备化合物7(产率＝75％质谱值:682.35)。
实施例3：制备化合物13
Figure PCTCN2019078284-appb-000010
按照上述合成路线，参照实施例1的方法制备化合物13(产率＝78％质谱值:780.36)。
实施例4：制备化合物17
Figure PCTCN2019078284-appb-000011
按照上述合成路线，参照实施例1的方法制备化合物17(产率＝83％质谱值:846.41)。
实施例5：制备化合物18
Figure PCTCN2019078284-appb-000012
按照上述合成路线，参照实施例1的方法制备化合物18(产率＝79％质谱值:862.40)。
实施例6：制备化合物20
Figure PCTCN2019078284-appb-000013
按照上述合成路线，参照实施例1的方法制备化合物20(产率＝85％质谱值:888.46)。
实施例7：制备化合物28
Figure PCTCN2019078284-appb-000014
按照上述合成路线，参照实施例1的方法制备化合物28(产率＝86％质谱值:819.34)。
实施例8：制备化合物31
Figure PCTCN2019078284-appb-000015
按照上述合成路线，参照实施例1的方法制备化合物31(产率＝77％质谱值:984.43)。
实施例9：制备化合物35
Figure PCTCN2019078284-appb-000016
按照上述合成路线，参照实施例1的方法制备化合物35(产率＝81％质谱值:925.34)。
实施例10：制备化合物40
Figure PCTCN2019078284-appb-000017
按照上述合成路线，参照实施例1的方法制备化合物40(产率＝82％质谱值:986.44)。
实施例11：制备化合物41
Figure PCTCN2019078284-appb-000018
按照上述合成路线，参照实施例1的方法制备化合物41(产率＝87％质谱值:655.32)。
实施例12：制备化合物42
Figure PCTCN2019078284-appb-000019
按照上述合成路线，参照实施例1的方法制备化合物42(产率＝79％质谱值:858.40)。
实施例13：制备化合物45
Figure PCTCN2019078284-appb-000020
按照上述合成路线，参照实施例1的方法制备化合物45(产率＝86％质谱值:910.42)。
实施例14：制备化合物46
Figure PCTCN2019078284-appb-000021
按照上述合成路线，参照实施例1的方法制备化合物46(产率＝85％质谱值:704.32)。
实施例15：制备化合物51
Figure PCTCN2019078284-appb-000022
按照上述合成路线，参照实施例1的方法制备化合物51(产率＝88％质谱值:895.40)。
实施例16：制备化合物54
Figure PCTCN2019078284-appb-000023
按照上述合成路线，参照实施例1的方法制备化合物54(产率＝83％质谱值:740.57)。
实施例17：制备化合物61
Figure PCTCN2019078284-appb-000024
按照上述合成路线，参照实施例1的方法制备化合物61(产率＝84％质谱值:804.06)。
实施例18：制备化合物77
Figure PCTCN2019078284-appb-000025
按照上述合成路线，参照实施例1的方法制备化合物77(产率＝85％质谱值:829.64)。
实施例19：制造含有化合物1的有机电致发光器件
将涂层厚度为
Figure PCTCN2019078284-appb-000026
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀厚度为50nm的4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)作为空穴注入层。然后将化合物1在形成的空穴注入层上面真空蒸镀厚度为30nm的空穴传输层。然后在上述空穴传输层上蒸镀厚度为30nm的蓝色主体材料9,10-二(2-萘基)蒽(ADN)和掺杂材料双(4,6-二氟苯基吡啶-N,C 2)吡啶甲酰合铱(FIrpic)。主体材料和掺杂材料的重量比为95:5。接着在上述发光层上真空蒸镀厚度为40nm的TPBi作为空穴阻挡层及电子传输层。在上述电子传输层上真空蒸镀厚度为0.5nm氟化锂(LiF)，作为电子注入层。最后蒸镀厚度为150nm的铝作为阴极，以此完成了有机电致发光器件的制备。对得到的器件的性能发光特性测试，测量采用KEITHLEY 2400型源测量单元，CS-2000分光辐射亮度计，以评价驱动电压，发光亮度，发光效率。
实施例20：制造含有化合物7的有机电致发光器件
将实施例19中的化合物1置换为化合物7，其他方法相同，制作含有化合物7的有机电致发光器件。
实施例21：制造含有化合物13的有机电致发光器件
将实施例19中的化合物1置换为化合物13，其他方法相同，制作含有化合物13的有机电致发光器件。
实施例22：制造含有化合物17的有机电致发光器件
将实施例19中的化合物1置换为化合物17，其他方法相同，制作含有化合物17的有机电致发光器件。
实施例23：制造含有化合物18的有机电致发光器件
将实施例19中的化合物1置换为化合物18，其他方法相同，制作含有化合物18的有 机电致发光器件。
实施例24：制造含有化合物20的有机电致发光器件
将实施例19中的化合物1置换为化合物20，其他方法相同，制作含有化合物20的有机电致发光器件。
实施例25：制造含有化合物28的有机电致发光器件
将实施例19中的化合物1置换为化合物28，其他方法相同，制作含有化合物28的有机电致发光器件。
实施例26：制造含有化合物31的有机电致发光器件
将实施例19中的化合物1置换为化合物31，其他方法相同，制作含有化合物31的有机电致发光器件。
实施例27：制造含有化合物35的有机电致发光器件
将实施例19中的化合物1置换为化合物35，其他方法相同，制作含有化合物35的有机电致发光器件。
实施例28：制造含有化合物40的有机电致发光器件
将实施例19中的化合物1置换为化合物40，其他方法相同，制作含有化合物40的有机电致发光器件。
实施例29：制造含有化合物41的有机电致发光器件
将实施例19中的化合物1置换为化合物41，其他方法相同，制作含有化合物41的有机电致发光器件。
实施例30：制造含有化合物42的有机电致发光器件
将实施例19中的化合物1置换为化合物42，其他方法相同，制作含有化合物42的有机电致发光器件。
实施例31：制造含有化合物45的有机电致发光器件
将实施例19中的化合物1置换为化合物45，其他方法相同，制作含有化合物45的有机电致发光器件。
实施例32：制造含有化合物46的有机电致发光器件
将实施例19中的化合物1置换为化合物46，其他方法相同，制作含有化合物46的有机电致发光器件。
实施例33：制造含有化合物51的有机电致发光器件
将实施例19中的化合物1置换为化合物51，其他方法相同，制作含有化合物51的有机电致发光器件。
实施例34：制造含有化合物54的有机电致发光器件
将实施例19中的化合物1置换为化合物54，其他方法相同，制作含有化合物54的有机电致发光器件。
实施例35：制造含有化合物61的有机电致发光器件
将实施例19中的化合物1置换为化合物61，其他方法相同，制作含有化合物61的有机电致发光器件。
实施例36：制造含有化合物77的有机电致发光器件
将实施例19中的化合物1置换为化合物77，其他方法相同，制作含有化合物77的有机电致发光器件。
对比例1：
按照实施例19的方法，将空穴传输层的材料由化合物1置换为N'-二(1-萘基)-N,N'-二苯基-(1,1'-联苯)-4,4'-二胺(NPD)。
表1为本公开实施例制备的化合物以及a-NPD制备的有机电致发光器件的发光特性测试结果。
表1
Figure PCTCN2019078284-appb-000027
从上表可看成本公开提供的化合物有适合的玻璃态转变温度，由其制备的有机电致发光器件的发光效率及寿命相对于由a-NPD制备的有机电致发光器件有显著的提高。
以上实施例的说明只是用于帮助理解本公开的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。
工业实用性
本公开提供了一种有机发光化合物，通过引入芳基胺获得了空穴注入能力/传输能力，高功率效率、长寿命；通过引入杂环获得适当玻璃态转变温度，从而获得了优质的有机电致发光材料。本公开提供的有机发光化合物的制备方法，重复性好，产率高。由本公开的有机发光化合物制备的有机电致发光器件具有极佳电流效率和功率效率以及长寿命。

Claims (15)

  1. 一种有机发光化合物，其特征在于，其结构式如下：
    Figure PCTCN2019078284-appb-100001
    式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；
    G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；
    G环可以存在也可以不存在；
    当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；
    当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；
    R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；
    R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；
    a、b和d各自独立地表示整数1到4；c表示整数1到3。
  2. 根据权利要求1所述的有机发光化合物，其特征在于，Ar 1和Ar 2各自独立地表示经取代或未经取代的C 10-C 25芳基、或者13-25元杂芳基。
  3. 根据权利要求1或2所述的有机发光化合物，其特征在于，Ar 1和Ar 2各自独立地表示经取代或未经取代的C 14-C 21芳基、或者17-23元杂芳基。
  4. 根据权利要求1-3中任一项所述的有机发光化合物，其特征在于，Ar 1和Ar 2各自独立 地表示经取代或未经取代的C 16-C 19芳基、或者19-21元杂芳基。
  5. 根据权利要求1-4中任一项所述的有机发光化合物，其特征在于，Ar 1、Ar 2各自独立地表示为苯、1,1',3',1”-三苯基、联苯基、二氨基苯、菲基、萘基、1-苯基萘或者9,9-二甲基芴。
  6. 根据权利要求1-7中任一项所述的有机发光化合物，其特征在于，a、b、c、d均为1。
  7. 根据权利要求1-7中任一项所述的有机发光化合物，其特征在于，G环为苯环、萘环、吡啶环、1-苯基-1H-吲哚、苯并呋喃、苯并噻吩、4-苯基-4H-苯并[b][1,4]噁嗪、4-苯基-4H-苯并噻嗪、苯并噻吩、1,4-二苯基-1,4-二氢喹噁啉、或者1,1,4,4-四甲基-1,4-二氢萘。
  8. 根据权利要求1-7中任一项所述的有机发光化合物，其特征在于，其选自下述结构中的任意一个：
    Figure PCTCN2019078284-appb-100002
    Figure PCTCN2019078284-appb-100003
    Figure PCTCN2019078284-appb-100004
  9. 一种权利要求1所述的有机发光化合物的制法，其特征在于，包括以下步骤：
    步骤1、在反应容器中加入化合物2和四氢呋喃之后，在氮气气氛下使所述容器冷却到-78℃，接着将正丁基锂逐滴添加到混合物中，在-78℃下搅拌混合物后，将其在室温下进行搅拌，并且冷却到-78℃；此后，将溶解于四氢呋喃中的化合物1逐滴添加到混合物中；添加后，使反应温度升温到室温，并且搅拌混合物；接着将氯化铵水溶液添加到反应溶液中以完成反应，并且用乙酸乙酯萃取反应溶液，接着使用硫酸镁干燥经萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用管柱色谱法纯化剩余物质获得中间体1-1；
    步骤2、将中间体1-1、化合物3和二氯甲烷加入反应容器中之后，用氮气充分置换空气三次，将溶解于二氯甲烷中的三氟化硼***逐滴添加到混合物中；在室温下搅拌混合物后，用蒸馏水淬灭，并且用二氯甲烷萃取混合物；接着使用硫酸钠干燥萃取的有机物层，并且使用旋转式蒸发器去除溶剂，用柱色谱法纯化剩余物质获得中间体2；
    步骤3、将中间体2、Ar 1Br和Ar 2Br、Pd 2(dba) 3、P(t-Bu) 3、NaOt-Bu、甲苯进行反应；反应结束以后用***和水提取有机物，有机层用硫酸镁干燥以后的浓缩产品用硅胶柱和重结晶方法得到式1化合物；
    其合成路线如下：
    Figure PCTCN2019078284-appb-100005
    式中：Ar 1和Ar 2各自独立地表示经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；或与相邻取代基连接形成单环或C 3-C 30多环脂环族环或芳香族环，其碳原子可置换为至少一个选自氮、氧和硫的杂原子；G环表示经取代或未经取代的C 1-C 30环烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3-30元杂芳基；G环可以存在也可以不存在；当G环不存在时X、Y、Z表示-O-、-S-、-SO 2-、-C(R 5)(R 6)-、-N(R 7)-、-Si(R 5)(R 6)-、-Sn(R 7)-或者-Ge(R 7)-；当G环存在时X表示-SO 2-、-N(R 7)-、-Si(R 5)(R 6)-、Sn(R 7)或者-Ge(R 7)-；Y、Z表示C、N、O、S原子；R 1到R 4各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、经取代或未经取代的C 1-C 30烃类、经取代或未经取代的C 1-C 30烷氧基、经取代或未经取代的C 3-C 30环烷基、经取代或未经取代的C 3-C 30环烯基、经取代或未经取代的3-7元杂环烷基、经取代或未经取代的C 6-C 30芳基、经取代或未经取代的3-30元杂芳基、-NR 8R 9、-SiR 10R 11R 12、-SR 13、-OR 14、-COR 15或者-B(OR 16)(OR 17)；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环，其碳原子可置换成至少一个选自氮、氧和硫的杂原子；R 5到R 17各自独立地表示氢、经取代或未经取代的C 1-C 30烷基、经取代或未经取代的C 6-C 30芳基、或经取代或未经取代的3到30元杂芳基；或与相邻取代基连接形成经取代或未经取代的单环或C 3-C 30多环脂肪族环或芳香族环；a、b和d各自独立地表示整数1到4；c表示整数1到3；Hal为卤素。
  10. 一种含有权利要求1-8中任一项所述的有机发光化合物的有机电致发光器件。
  11. 根据权利要求10所述的有机电致发光器件，其特征在于，包括第一电极、第二电极和置于所述第一和第二电极之间的有机物层。
  12. 根据权利要求11所述的有机电致发光器件，其特征在于，所述有机物层包含有式1结构的化合物。
  13. 根据权利要求12所述的有机电致发光器件，其特征在于，所述包含有式1结构的化合物可以以单一形态或与其它物质混合存在于有机物层中。
  14. 根据权利要求11所述的有机电致发光器件，其特征在于，所述有机物层至少包括由空穴注入层、空穴传输层、既具备空穴注入又具备空穴传输技能层，电子阻挡层，发光层，空穴阻挡层，电子传输层，电子注入层和既具备电子传输又具备电子注入技能层组成的组中的一种或几种。
  15. 根据权利要求10所述的有机电致发光器件在有机发光器件(OLED)、有机太阳电池 (OSC)、电子纸(e-Paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)中的用途。
PCT/CN2019/078284 2018-10-11 2019-03-15 一种有机发光化合物及制法和含该化合物的有机电致发光器件 WO2020073605A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201811180929.1 2018-10-11
CN201811180929.1A CN109180560A (zh) 2018-10-11 2018-10-11 一种有机发光化合物及制法和含该化合物的有机电致发光器件
CN201910184076.7A CN109776393A (zh) 2019-03-12 2019-03-12 一种有机发光化合物及制法和该化合物的有机电致发光器件
CN201910184076.7 2019-03-12

Publications (1)

Publication Number Publication Date
WO2020073605A1 true WO2020073605A1 (zh) 2020-04-16

Family

ID=70164379

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/078284 WO2020073605A1 (zh) 2018-10-11 2019-03-15 一种有机发光化合物及制法和含该化合物的有机电致发光器件

Country Status (1)

Country Link
WO (1) WO2020073605A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210159420A1 (en) * 2019-11-21 2021-05-27 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
CN113387871A (zh) * 2021-06-11 2021-09-14 长春海谱润斯科技股份有限公司 三芳胺衍生物及其有机电致发光器件
WO2022060047A1 (ko) * 2020-09-17 2022-03-24 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
KR20220037363A (ko) * 2020-09-17 2022-03-24 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153031A (zh) * 2015-08-15 2015-12-16 吉林奥来德光电材料股份有限公司 一种新颖的有机电致发光材料及其制备方法和应用
CN105315229A (zh) * 2014-07-05 2016-02-10 吉林奥来德光电材料股份有限公司 含八元氮-硫（或氧）杂环类衍生物类有机发光材料
US20160172593A1 (en) * 2014-12-15 2016-06-16 Samsung Display Co., Ltd. Amine compound and organic electroluminescent device including the same
TW201829738A (zh) * 2017-08-30 2018-08-16 大陸商昆山國顯光電有限公司 有機電致發光裝置
CN109180560A (zh) * 2018-10-11 2019-01-11 吉林奥来德光电材料股份有限公司 一种有机发光化合物及制法和含该化合物的有机电致发光器件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105315229A (zh) * 2014-07-05 2016-02-10 吉林奥来德光电材料股份有限公司 含八元氮-硫（或氧）杂环类衍生物类有机发光材料
US20160172593A1 (en) * 2014-12-15 2016-06-16 Samsung Display Co., Ltd. Amine compound and organic electroluminescent device including the same
CN105153031A (zh) * 2015-08-15 2015-12-16 吉林奥来德光电材料股份有限公司 一种新颖的有机电致发光材料及其制备方法和应用
TW201829738A (zh) * 2017-08-30 2018-08-16 大陸商昆山國顯光電有限公司 有機電致發光裝置
CN109180560A (zh) * 2018-10-11 2019-01-11 吉林奥来德光电材料股份有限公司 一种有机发光化合物及制法和含该化合物的有机电致发光器件

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210159420A1 (en) * 2019-11-21 2021-05-27 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
US11856844B2 (en) * 2019-11-21 2023-12-26 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
WO2022060047A1 (ko) * 2020-09-17 2022-03-24 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
KR20220037363A (ko) * 2020-09-17 2022-03-24 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
KR102649337B1 (ko) 2020-09-17 2024-03-19 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
CN113387871A (zh) * 2021-06-11 2021-09-14 长春海谱润斯科技股份有限公司 三芳胺衍生物及其有机电致发光器件

Similar Documents

Publication Publication Date Title
CN109748898B (zh) 有机电致发光化合物及其制备方法和有机电致发光器件
KR102267451B1 (ko) 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
CN109912431B (zh) 一种含萘的三芳胺类有机化合物及其应用
KR101944699B1 (ko) 유기전기소자용 신규 화합물, 이를 이용하는 유기전기소자 및 그 전자 장치
CN109796960B (zh) 一种有机电致发光化合物及制法和应用
WO2020073605A1 (zh) 一种有机发光化合物及制法和含该化合物的有机电致发光器件
JP5773638B2 (ja) 縮合多環化合物及びこれを用いた有機発光素子
CN112062718B (zh) 有机电致发光化合物和包含所述化合物的有机电致发光装置
CN109970575B (zh) 有机电致发光化合物及其制法和应用
CN109776334B (zh) 有机电致发光化合物及其制法和器件
WO2020000920A1 (zh) 一种有机发光化合物及其制备方法和有机电致发光器件
JP2007131723A (ja) 発光素子材料および発光素子
CN109776393A (zh) 一种有机发光化合物及制法和该化合物的有机电致发光器件
KR20100111037A (ko) 방향족 다환고리 화합물 및 이를 이용한 유기전기소자, 그 단말
CN109970645B (zh) 含氮杂环有机电致发光化合物及其制法和有机电致发光器件
KR101125682B1 (ko) 유기 전기 발광 조성물 및 이를 포함하는 유기 전기 발광 소자
CN113527315A (zh) 一种电致发光材料及器件
KR20110054225A (ko) 유기 전기 발광 조성물 및 이를 포함하는 유기 전기 발광 소자
CN116514752B (zh) 一种发光辅助材料及制备方法与其在有机电致发光器件中的应用
KR102312963B1 (ko) 화합물, 유기 광전자 소자 및 표시 장치
KR101496509B1 (ko) 발광 응용을 위한 안트라센 화합물
KR101159729B1 (ko) 유기 전기 발광 조성물 및 이를 포함하는 유기 전기 발광 소자
KR101508145B1 (ko) 유기 발광 화합물, 이의 제조 방법 및 이를 포함하는 유기 전계 발광 소자
KR20210049544A (ko) 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자
KR20130022232A (ko) 유기전기소자용 신규 화합물, 이를 이용하는 유기전기소자 및 그 전자 장치

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19870580

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19870580

Country of ref document: EP

Kind code of ref document: A1