CN111205269B - Carbazole-based organic electrophosphorescent material composition preparation method and application preparation - Google Patents
Carbazole-based organic electrophosphorescent material composition preparation method and application preparation Download PDFInfo
- Publication number
- CN111205269B CN111205269B CN202010028334.5A CN202010028334A CN111205269B CN 111205269 B CN111205269 B CN 111205269B CN 202010028334 A CN202010028334 A CN 202010028334A CN 111205269 B CN111205269 B CN 111205269B
- Authority
- CN
- China
- Prior art keywords
- layer
- thickness
- drying
- carbazole
- target compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Abstract
The invention discloses a preparation method and application preparation of a carbazole-based organic electrophosphorescent material composition in the technical field related to organic electroluminescent materials; the target compound of structural formula I is prepared by a chemical reaction equation comprising:
the carbazole-based compound as shown in the structural formula I prepared by the invention has good thermal stability, high luminous efficiency, high luminous purity and solution processing; the organic electroluminescent device manufactured by adopting the carbazole-based compound has the advantages of good electroluminescent efficiency, excellent color purity and long service life; the preparation method is simple and convenient, and is convenient to implement and popularize.
Description
Technical Field
The invention relates to the technical field related to organic electroluminescent materials, in particular to a preparation method and application preparation of a carbazole-based organic electrophosphorescent material composition.
Background
Organic electroluminescent devices (OLEDs) are devices prepared by depositing a layer of organic material between two metal electrodes by spin coating or vacuum evaporation, a classical three-layer organic electroluminescent device comprising a hole transporting layer, a light emitting layer and an electron transporting layer. Holes generated from the anode are combined with electrons generated from the cathode through the hole transport layer to form excitons in the light emitting layer through the electron transport layer, and then light is emitted. The organic electroluminescent device can adjust the emission of various desired lights by changing the material of the light emitting layer as needed.
The organic electroluminescent device is used as a novel display technology, has the unique advantages of self-luminescence, wide visual angle, low energy consumption, high efficiency, thinness, rich color, high response speed, wide application temperature range, low driving voltage, flexible and bendable transparent display panel manufacturing, environment friendliness and the like, can be applied to flat panel displays and new-generation illumination, and can also be used as a backlight source of LCD.
Since the end of the 80 s of the 20 th century, organic electroluminescent devices have been industrially used, for example, as screens for cameras and mobile phones, but the current OLED devices are limited in their wider application, particularly for large screen displays, due to low efficiency, short service life, and the like, and thus there is a need to improve the efficiency of the devices. One of the important factors that is limiting is the performance of the organic electroluminescent material in the organic electroluminescent device. In addition, since the OLED device generates joule heat when the OLED device is operated by applying voltage, crystallization of the organic material is easy to occur, which affects the lifetime and efficiency of the device, and thus, it is also required to develop a stable and efficient organic electroluminescent material.
The organic electrophosphorescence breaks through the theoretical limit that the organic electroluminescent quantum efficiency is lower than 25 percent, and is improved to 100 percent (Baldo M.A., forrest S.R.Et al, nature,1998,395,151-154), and the application of the organic electroluminescent quantum efficiency greatly improves the efficiency of the organic electroluminescent device. Generally, electro-phosphorescent requires host-guest doping techniques, and CBP (4, 4' -bis (9-carbazolyl) -biphenyl), which is a commonly used phosphorescent host material, has high efficiency and high triplet energy level, and when it is used as a host material, triplet energy can be efficiently transferred from a light emitting host material to a guest phosphorescent light emitting material. However, due to the characteristic that holes of CBP are easily transported and electrons are difficult to flow, the charge of the light emitting layer is unbalanced, and as a result, the efficiency of the device is reduced.
In view of the fact that the solution spin-on deposition process is easy to realize mass production while achieving high resolution, low cost and large area of OLED display devices, attention is paid. In order to meet the strict requirements of the market, the development of an organic electroluminescent device with better thermal stability, high luminous efficiency and high luminous purity is a problem which needs to be solved urgently in the prior art.
Disclosure of Invention
Aiming at the technical problems of the prior art that an organic electroluminescent device with better thermal stability, high luminous efficiency and high luminous purity needs to be developed, the invention provides a preparation method and application preparation of a carbazole-based organic electrophosphorescent material composition.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing carbazole-based organic electrophosphorescent material compositions, which prepares a target compound of structural formula I by a chemical reaction equation comprising:
further, the reaction process and conditions include:
sa: adding 4-bromo-2-chloroiodobenzene, 3-pyridine pinacol borate, potassium carbonate, an organic solvent, water and a palladium catalyst into a reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying a crude product by column chromatography to obtain an intermediate 1;
sb: adding the intermediate 1, arylboronic acid, potassium carbonate, an organic solvent, water and a palladium catalyst into the reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying the crude product by column chromatography to obtain an intermediate 2;
sc: adding the mixed catalyst of the intermediate 2, carbazolyl boric acid, potassium carbonate, an organic solvent, water, palladium acetate and X-phos into the reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying the crude product by column chromatography to obtain the target compound;
the organic solvent is selected from toluene, ethanol, tetrahydrofuran, dioxane and dimethylformamide; the palladium catalyst is selected from tetraphenylphosphine palladium phosphine palladium, palladium acetate and dichloro diphenylphosphine palladium.
Preferably Ar represents a singly-bound C6-C30 substituted or unsubstituted aryl group, a singly-bound C3-C30 substituted or unsubstituted heteroaryl group; cz represents a substituted or unsubstituted carbazolyl group of C6-C30.
Preferably Ar is independently selected from phenyl, biphenyl, naphthyl, triphenylene, N-aryl (C6-C30) or C1-C4 alkyl-substituted carbazolyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, (9, 9-dialkyl) fluorenyl, (9, 9-disubstituted or unsubstituted aryl) fluorenyl, 9-spirofluorenyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted dibenzofuranyl.
Preferably, the target compound is a compound of the following structural formulae 1 to 22:
further, the target compound 15 is prepared by a chemical reaction equation including:
further, the specific operation of the synthesis of the intermediate 1 is as follows: in a reaction vessel, 75.4-83.4 mmole of 4-bromo-2-chloroiodobenzene, 75.4-83.4 mmole of 3-pyridine boric acid pinacol ester, 152-168 mmole of potassium carbonate, 285-315 mL of tetrahydrofuran, 95-105 mL of water and 0.9-1.1 g of tetraphenylphosphine palladium are added, the mixture is heated and refluxed for 9-11 hours under the protection of nitrogen, cooled, extracted by methylene dichloride, dried and concentrated, and a crude product is purified by column chromatography to obtain the intermediate 1.
Further, the specific operation of the synthesis of the intermediate 2' is as follows: in a reaction vessel, 10.7-11.9 mmol of the intermediate 1, 10.7-11.9 mmol of 2-benzophenanthrene boric acid, 19-21 mmol of potassium carbonate, 19-21 mL of tetrahydrofuran, 9.5-10.5 mL of water, 0.19-0.21 g of triphenylphosphine palladium, heating and refluxing for 9-11 h under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying the crude product by column chromatography to obtain the intermediate 2'.
Further, the specific operation of the synthesis of the target compound 15 is as follows: 5.7 to 6.3mmol of the intermediate 2',5.7 to 6.3mmol of 9-phenylcarbazole-3-boric acid, 9.5 to 10.5mmol of potassium carbonate, 19 to 21mL of tetrahydrofuran, 9.5 to 10.5mL of water, 0.1 to 0.11g of palladium acetate and 0.19 to 0.21g of X-Phos are added into a reaction vessel, heated and refluxed for 23 to 25 hours under the protection of nitrogen, cooled, extracted by methylene dichloride, dried and concentrated, and the crude product is purified by column chromatography to obtain the target compound 15.
The preparation of the target compound prepared by the preparation method of the carbazole-based organic electrophosphorescent material composition, which comprises the following steps:
s1: cleaning a transparent conductive ITO glass substrate with an anode through deionized water, ethanol, acetone and deionized water in sequence, and then treating the transparent conductive ITO glass substrate with the anode with oxygen plasma for 20-40 s;
s2: spin-coating PEDOT with the thickness of 30-40 nm on the anode, wherein PSS is used as a hole injection layer, and drying is carried out for 20-40 min at 145-155 ℃;
s3: spin-coating TFB with the thickness of 10-30 nm on the hole injection layer as a hole transport layer, and drying for 20-40 min at 145-155 ℃;
s4: spin-coating a luminescent layer with the thickness of 10-30 nm on the hole transport layer, and drying for 20-40 min at 85-95 ℃; the light-emitting layer comprises 80 to 99w% of the target compound and 1 to 20w% of Ir (ppy) 2 acac；
S5: evaporating TmPyPB with the thickness of 5-15 nm on the light-emitting layer to serve as a hole blocking and transporting layer;
s6: evaporating TPBi with the thickness of 5-15 nm on the hole blocking transmission layer to serve as an electron transmission layer;
s7: evaporating LiF with the wavelength of 0.5-1.5 nm on the electron transport layer to serve as an electron injection layer;
s8: evaporating 115-125 nm Al on the electron injection layer to serve as a cathode, and obtaining the organic electroluminescent device.
The invention has the following advantages:
1. the carbazole-based compound as shown in the structural formula I prepared by the invention has good thermal stability, high luminous efficiency, high luminous purity and solution processing;
2. the organic electroluminescent device manufactured by adopting the carbazole-based compound has the advantages of good electroluminescent efficiency, excellent color purity and long service life;
3. the preparation method is simple and convenient, and is convenient to implement and popularize.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a hydrogen nuclear magnetic spectrum of compound 15;
FIG. 2 is a schematic diagram of an organic electroluminescent device according to the present invention;
FIG. 3 is a graph showing the voltage and luminance relationship of an organic electroluminescent device;
FIG. 4 is a graph of current density versus current efficiency for an organic electroluminescent device;
FIG. 5 is a graph of current density and power efficiency of an organic electroluminescent device;
FIG. 6 is a graph of current density and external quantum efficiency of an organic electroluminescent device;
in fig. 2: 110-a glass substrate; 120-anode; 130-a hole injection layer; 140-a hole transport layer; 150-a light emitting layer; 160-hole blocking layer; 170-an electron transport layer; 180-an electron injection layer; 190-cathode.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In the following description, descriptions of well-known structures, techniques and operations are omitted so as not to unnecessarily obscure the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
It should be noted that, in the description of the present invention, the directions or positional relationships indicated by the terms "upper", "lower", etc. are descriptions of the structure of the present invention based on fig. 2, only for convenience of description of the present invention, and are not meant to indicate or imply that the apparatus or element to be referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In addition, unless explicitly stated and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., the connection may be a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two structures. It will be apparent to those skilled in the art that the specific meaning of the terms described above in this application may be understood in the light of the general inventive concept in connection with the present application.
In the preparation method of the carbazole-based organic electrophosphorescent material composition, the target compound of the structural formula I is prepared by the following chemical reaction equation:
wherein, the reaction process and conditions include:
sa: adding 4-bromo-2-chloroiodobenzene, 3-pyridine pinacol borate, potassium carbonate, an organic solvent, water and a palladium catalyst into a reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying a crude product by column chromatography to obtain an intermediate 1;
sb: adding the intermediate 1, arylboronic acid, potassium carbonate, an organic solvent, water and a palladium catalyst into a reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying the crude product by column chromatography to obtain an intermediate 2;
sc: adding a mixed catalyst of an intermediate 2, carbazolyl boric acid, potassium carbonate, an organic solvent, water, palladium acetate and X-phos into a reaction container, heating and refluxing under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying a crude product by column chromatography to obtain a target compound;
in specific implementation, the organic solvent can be selected from toluene, ethanol, tetrahydrofuran, dioxane and dimethylformamide; the palladium catalyst can be selected from tetraphenylphosphine palladium phosphine palladium, palladium acetate and dichloro diphenylphosphine palladium.
In order to facilitate the teaching of the technical solution of the present invention for a person skilled in the art, taking the compound 15 as an example, by showing the synthesis manner of the compound of the structural formula I in the present invention through a specific synthesis process thereof, the person skilled in the art can implement the teaching of the example of the present invention and the prior art and his own experience by himself, without carrying out creative labor, to obtain more embodiments including the above 22 compounds of the structural formula.
Embodiment one: synthesis of Compound 15
The reaction path is as follows:
examples one A1 to 3: synthesis of intermediate 1
Example one A1:
in a flask, 4-bromo-2-chloroiodobenzene (25 g,79.4 mmol), pinacol 3-pyridineboronic acid ester (16.3 g,79.4 mmol), potassium carbonate (22 g,160 mmol), tetrahydrofuran (300 mL), water (100 mL), and palladium tetraphenylphosphine (1 g) were added, heated under reflux under nitrogen for 10 hours, cooled, extracted with dichloromethane, dried, concentrated, and the crude product was purified by column chromatography to give 14.2g of the product in 67% yield.
1 H NMR:(400MHz,CDCl 3 )δ8.66-8.63(m,2H),7.79-7.76(tt,1H),7.69(d,1H),7.53-7.47(dd,1H),7.40-7.36(dd,1H),7.22(d,1H)。
Example one A2:
in a flask, 75.4 mmole of 4-bromo-2-chloroiodobenzene, 83.4 mmole of 3-pyridineboronic acid pinacol ester, 152 mmole of potassium carbonate, 285mL of tetrahydrofuran, 95mL of water and 0.9g of tetraphenylphosphine palladium were added, and the mixture was heated under reflux under nitrogen for 11 hours, cooled, extracted with methylene chloride, dried and concentrated to give 13.6g of a crude product, which was purified by column chromatography.
Example one A3:
in a flask, 83.4 mmole of 4-bromo-2-chloroiodobenzene, 75.4 mmole of 3-pyridineboronic acid pinacol ester, 168 mmole of potassium carbonate, 315mL of tetrahydrofuran, 105mL of water, 1.1g of tetraphenylphosphine palladium were added, heated under reflux under nitrogen for 9 hours, cooled, extracted with dichloromethane, dried, concentrated, and the crude product was purified by column chromatography to give 13.9g of the product.
Examples one B1 to 3: synthesis of intermediate 2
Example one B1:
in a flask, intermediate 1 (3 g,11.3 mmol), 2-benzophenanthrene boronic acid (3.1 g,11.3 mmol), potassium carbonate (2.7 g,20 mmol), tetrahydrofuran (20 mL), water (10 mL), and palladium tetraphenylphosphine (0.2 g) prepared in example A1 were added, heated under reflux for 10 hours under nitrogen, cooled, extracted with dichloromethane, dried, concentrated, and the crude product was purified by column chromatography to give 3.7g of product in 79% yield.
1 H NMR:(400MHz,CDCl 3 )δ8.89(d,1H),8.79-8.75(m,3H),8.71-8.67(m,4H),7.97(d,1H),7.94-7.89(m,2H),7.82-7.80(dd,1H),7.73-7.69(m,4H),7.52(d,1H),7.45-7.42(dd,1H)。
Example one B2:
in a flask, 10.7mmol of intermediate 1 prepared in example A2, 11.9mmol of 2-benzophenanthrene boric acid, 19mmol of potassium carbonate, 19mL of tetrahydrofuran, 9.5mL of water and 0.19g of palladium tetraphenylphosphine were added, the mixture was heated under reflux under nitrogen for 11 hours, cooled, extracted with dichloromethane, dried and concentrated, and the crude product was purified by column chromatography to give 3.6g of the product.
Example one B3:
in a flask were charged 11.9mmol of intermediate 1 prepared in example A3, 10.7mmol of 2-benzophenanthrene boric acid, 21mmol of potassium carbonate, 21mL of tetrahydrofuran, 10.5mL of water, 0.21g of palladium tetraphenylphosphine, heated under reflux under nitrogen for 9h, cooled, extracted with dichloromethane, dried, concentrated and the crude product purified by column chromatography to give 3.7g of the product.
Examples one C1 to 3: synthesis of target Compound 15
Example one C1:
in a flask was added intermediate 2' (2.5 g,6 mmol) prepared in example one B1, 9-phenylcarbazole-3-boronic acid (1.72 g,6 mmol), potassium carbonate (1.3 g,10 mmol), tetrahydrofuran (20 mL), water (10 mL), palladium acetate (0.1 g), X-Phos (0.2 g), under nitrogen protection, heated under reflux for 24 hours, cooled, extracted with dichloromethane, dried, concentrated, the crude product purified by column chromatography to give 2.6g of product in 68% yield; the hydrogen nuclear magnetic spectrum of the product is shown in figure 1.
1 H NMR:(400MHz,CDCl 3 )δ8.92(d,1H),8.67-8.76(m,5H),8.58-8.59(d,1H),8.50-8.52(m,1H),8.13-8.15(m,2H),7.97-8.00(m,2H),7.88-7.91(m,1H),7.60-7.70(m,5H)，7.40-7.53(m,6H),7.23-7.32(m,4H),7.14-7.18(m,2H)。
Example one C2:
in a flask were charged 5.7mmol of intermediate 2',6.3mmol of 9-phenylcarbazole-3-boronic acid prepared in example B2, 9.5mmol of potassium carbonate, 19mL of tetrahydrofuran, 9.5mL of water, 0.1g of palladium acetate, 0.19g of X-Phos, heated under reflux under nitrogen for 25h, cooled, extracted with dichloromethane, dried and concentrated to give 2.5g of the crude product which was purified by column chromatography.
Example one C3:
in a flask were charged 6.3mmol of intermediate 2',5.7mmol of 9-phenylcarbazole-3-boronic acid prepared in example B3, 10.5mmol of potassium carbonate, 21mL of tetrahydrofuran, 10.5mL of water, 0.11g of palladium acetate, 0.21g of X-Phos, heated under reflux under nitrogen for 23h, cooled, extracted with dichloromethane, dried and concentrated to give 2.6g of the crude product which was purified by column chromatography.
Examples two 1 to 3: preparation of organic electroluminescent device
Example two 1:
s1: transparent conductive ITO glass substrate 110 (with anode 120 thereon) (south glass group, inc. Of china) was subjected to the following processes: deionized water, ethanol, acetone and deionized water were washed and then treated with oxygen plasma for 30s.
S2: spin-coating PEDOT PSS (polyethylene dioxythiophene-poly (styrene sulfonate)) with a thickness of 35nm as the hole injection layer 130 on the anode, and drying at 150deg.C for 30min;
s3: spin-coating TFB (poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine)) having a thickness of 20nm as the hole transport layer 140 on the hole injection layer 130, and drying at 150℃for 30 minutes;
s4: a light-emitting layer 150 having a thickness of 20nm was spin-coated on the hole transport layer 140, wherein the compound 15 synthesized in example C1 was used as the main light-emitting material, and Ir (ppy) was used in an amount of 12% by weight 3 The acac is used as a phosphorescent doped guest material and is dried for 30min at 90 ℃;
s5: evaporating TmPyPB having a thickness of 10nm as a hole blocking layer 160 on the light emitting layer 150;
s6: vapor-depositing TPBi having a thickness of 10nm as the electron transport layer 170 on the hole blocking layer 160;
s7: evaporating LiF with the thickness of 1nm on the electron transport layer 170 to form an electron injection layer 180;
s8: an organic electroluminescent device as shown in fig. 2 was fabricated by vapor deposition of 120nmAl as the device cathode 190 on the electron injection layer 180.
The organic electroluminescent device obtained in this example was measured at 15mA/cm using a Photo Research PR650 spectrometer 2 The current efficiency at the current density is 16.2cd/A, the power efficiency is 4.4lm/W, and the external quantum effect is achievedThe rate was 4.1% and the CIE (x, y) was (0.34,0.62), as shown in fig. 3, 4, 5 and 6.
Example two 2:
s1: washing a transparent conductive ITO glass substrate with an anode by deionized water, ethanol, acetone and deionized water in sequence, and treating the transparent conductive ITO glass substrate with the anode by oxygen plasma for 20 seconds;
s2: spin-coating PEDOT with the thickness of 30nm on an anode, taking PSS as a hole injection layer, and drying at 145 ℃ for 20min;
s3: spin-coating TFB with the thickness of 10nm on the hole injection layer as a hole transport layer, and drying at 145 ℃ for 20min;
s4: spin-coating a luminescent layer with a thickness of 10nm on the hole transport layer, and drying at 85 ℃ for 20min; the light-emitting layer comprises 80w% of the target compound and 20w% of Ir (ppy) 2 acac；
S5: evaporating TmPyPB with the thickness of 5nm on the light-emitting layer as a hole blocking and transporting layer;
s6: evaporating TPBi with the thickness of 5nm on the hole blocking transmission layer as an electron transmission layer;
s7: evaporating LiF with the thickness of 0.5nm on the electron transport layer to serve as an electron injection layer;
s8: and evaporating the electron injection layer to obtain an organic electroluminescent device, wherein the thickness of the electron injection layer is 115nm Al, and the organic electroluminescent device is prepared by taking the electron injection layer as a cathode.
Example two 3:
s1: washing a transparent conductive ITO glass substrate with an anode by deionized water, ethanol, acetone and deionized water in sequence, and then treating the transparent conductive ITO glass substrate with the anode by oxygen plasma for 40 seconds;
s2: spin-coating PEDOT with the thickness of 40nm on an anode, taking PSS as a hole injection layer, and drying at 155 ℃ for 40min;
s3: spin-coating TFB with the thickness of 30nm on the hole injection layer as a hole transport layer, and drying at 155 ℃ for 40min;
s4: spin-coating a light-emitting layer with a thickness of 30nm on the hole transport layer, and drying at 95 ℃ for 40min; the light-emitting layer comprises 99w% of the target compound and 1w% of Ir (ppy) 2 acac；
S5: evaporating TmPyPB with the thickness of 15nm on the light-emitting layer as a hole blocking and transporting layer;
s6: evaporating TPBi with the thickness of 15nm on the hole blocking transmission layer as an electron transmission layer;
s7: evaporating LiF with the thickness of 1.5nm on the electron transport layer to serve as an electron injection layer;
s8: and (3) evaporating Al with the thickness of 125nm on the electron injection layer to serve as a cathode, so as to obtain the organic electroluminescent device.
Comparative examples
The organic electroluminescent device of this example was prepared in the same manner as in example two 1, except that CBP was used as a host material instead of compound 15 to prepare the organic electroluminescent device.
The prepared organic electroluminescent device is measured at 15mA/cm by using a Photo Research PR650 spectrometer 2 The current efficiency at the current density of (3) was 8.8cd/A, the power efficiency was 1.7lm/W, the external quantum efficiency was 2.2%, and the CIE (x, y) was (0.35,0.61), as shown in FIGS. 3, 4, 5 and 6.
By comparison, the compound is used for preparing an organic electroluminescent device, has excellent device efficiency, and can be used as a phosphorescent host material with excellent performance; compared with devices prepared by CBP, the organic electroluminescent device has higher efficiency, brightness and high stability, and the prepared organic electroluminescent device has high efficiency and optical purity.
The structural formulas of the second 1 to 3 and other compounds used in the comparative examples for preparing the organic electroluminescent devices are as follows:
the embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that many changes, modifications, substitutions and variations can be made to these embodiments without departing from the spirit and scope of the invention.
Claims (2)
1. A preparation method of a carbazole-based organic electrophosphorescent material composition is characterized by comprising the following steps: target compound 15 was prepared by the following chemical reaction equation:
the specific operation of the synthesis of the intermediate 1 is as follows: adding 75.4-83.4 mmole of 4-bromo-2-chloroiodobenzene, 75.4-83.4 mmole of 3-pyridine boric acid pinacol ester, 152-168 mmole of potassium carbonate, 285-315 mL of tetrahydrofuran, 95-105 mL of water and 0.9-1.1 g of tetraphenylphosphine palladium into a reaction vessel, heating and refluxing for 9-11 h under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying a crude product by column chromatography to obtain the intermediate 1;
the specific operation of the synthesis of intermediate 2' is: adding 10.7-11.9 mmol of the intermediate 1, 10.7-11.9 mmoles of 2-benzophenanthrene boric acid, 19-21 mmoles of potassium carbonate, 19-21 mL of tetrahydrofuran, 9.5-10.5 mL of water and 0.19-0.21 g of triphenylphosphine palladium into a reaction vessel, heating and refluxing for 9-11 h under the protection of nitrogen, cooling, extracting with dichloromethane, drying, concentrating, and purifying a crude product by column chromatography to obtain the intermediate 2;
the specific operation of the synthesis of the target compound 15 is as follows: 5.7 to 6.3mmol of the intermediate 2',5.7 to 6.3mmol of 9-phenylcarbazole-3-boric acid, 9.5 to 10.5mmol of potassium carbonate, 19 to 21mL of tetrahydrofuran, 9.5 to 10.5mL of water, 0.1 to 0.11g of palladium acetate and 0.19 to 0.21g of X-Phos are added into a reaction vessel, heated and refluxed for 23 to 25 hours under the protection of nitrogen, cooled, extracted by methylene dichloride, dried and concentrated, and the crude product is purified by column chromatography to obtain the target compound 15.
2. Use of the target compound prepared by the carbazole-based organic electrophosphorescent material composition preparation method according to claim 1, characterized in that: the method comprises the following steps:
s1: cleaning a transparent conductive ITO glass substrate with an anode through deionized water, ethanol, acetone and deionized water in sequence, and then treating the transparent conductive ITO glass substrate with the anode with oxygen plasma for 20-40 s;
s2: spin-coating PEDOT with the thickness of 30-40 nm on the anode, wherein PSS is used as a hole injection layer, and drying is carried out for 20-40 min at 145-155 ℃;
s3: spin-coating TFB with the thickness of 10-30 nm on the hole injection layer as a hole transport layer, and drying for 20-40 min at 145-155 ℃;
s4: spin-coating a luminescent layer with the thickness of 10-30 nm on the hole transport layer, and drying for 20-40 min at 85-95 ℃; the light emitting layer includes 80 to 99w% of the target compound and 1 to 20w% of Ir (ppy) 2acac;
s5: evaporating TmPyPB with the thickness of 5-15 nm on the light-emitting layer to serve as a hole blocking and transporting layer;
s6: evaporating TPBi with the thickness of 5-15 nm on the hole blocking transmission layer to serve as an electron transmission layer;
s7: evaporating 0.5-1.5 nmLiF on the electron transport layer as an electron injection layer;
s8: and evaporating 115-125 nmAl serving as a cathode on the electron injection layer to prepare the organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010028334.5A CN111205269B (en) | 2020-01-10 | 2020-01-10 | Carbazole-based organic electrophosphorescent material composition preparation method and application preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010028334.5A CN111205269B (en) | 2020-01-10 | 2020-01-10 | Carbazole-based organic electrophosphorescent material composition preparation method and application preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111205269A CN111205269A (en) | 2020-05-29 |
| CN111205269B true CN111205269B (en) | 2023-05-12 |
Family
ID=70785517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010028334.5A Active CN111205269B (en) | 2020-01-10 | 2020-01-10 | Carbazole-based organic electrophosphorescent material composition preparation method and application preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111205269B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934213A (en) * | 2004-03-08 | 2007-03-21 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| WO2011081423A2 (en) * | 2009-12-30 | 2011-07-07 | 주식회사 두산 | Triphenylene compound and organic electroluminescence device including the same |
| CN107417677A (en) * | 2017-08-09 | 2017-12-01 | 上海道亦化工科技有限公司 | A kind of carbazole pyridines organic electroluminescent compounds and its organic electroluminescence device |
| CN107840841A (en) * | 2017-11-02 | 2018-03-27 | 上海道亦化工科技有限公司 | A kind of carbazole pyridine derivate and application thereof and organic electroluminescence device |
| CN107987009A (en) * | 2017-11-28 | 2018-05-04 | 上海道亦化工科技有限公司 | A kind of carbazole derivates and application thereof and organic electroluminescence device |
| CN108299389A (en) * | 2017-12-26 | 2018-07-20 | 上海道亦化工科技有限公司 | A kind of compound based on phenanthrene and carbazole and application thereof and organic electroluminescence device |
| WO2019076844A1 (en) * | 2017-10-18 | 2019-04-25 | Cynora Gmbh | Organic molecules, in particular for use in optoelectronic devices |
-
2020
- 2020-01-10 CN CN202010028334.5A patent/CN111205269B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934213A (en) * | 2004-03-08 | 2007-03-21 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| WO2011081423A2 (en) * | 2009-12-30 | 2011-07-07 | 주식회사 두산 | Triphenylene compound and organic electroluminescence device including the same |
| CN107417677A (en) * | 2017-08-09 | 2017-12-01 | 上海道亦化工科技有限公司 | A kind of carbazole pyridines organic electroluminescent compounds and its organic electroluminescence device |
| WO2019076844A1 (en) * | 2017-10-18 | 2019-04-25 | Cynora Gmbh | Organic molecules, in particular for use in optoelectronic devices |
| CN107840841A (en) * | 2017-11-02 | 2018-03-27 | 上海道亦化工科技有限公司 | A kind of carbazole pyridine derivate and application thereof and organic electroluminescence device |
| CN107987009A (en) * | 2017-11-28 | 2018-05-04 | 上海道亦化工科技有限公司 | A kind of carbazole derivates and application thereof and organic electroluminescence device |
| CN108299389A (en) * | 2017-12-26 | 2018-07-20 | 上海道亦化工科技有限公司 | A kind of compound based on phenanthrene and carbazole and application thereof and organic electroluminescence device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111205269A (en) | 2020-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI388647B (en) | New compound and organic light emitting device using the same | |
| JP5076901B2 (en) | Electron transport material and organic electroluminescent device using the same | |
| KR100940938B1 (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR101678363B1 (en) | Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof | |
| KR101497124B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| KR101779913B1 (en) | Spiro compound and organic electroluminescent devices comprising the same | |
| KR101771531B1 (en) | Spiro compound and organic electroluminescent devices comprising the same | |
| WO2015067155A1 (en) | Organic electroluminescent material and organic electroluminescent device | |
| KR20120009761A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20110049217A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20100112903A (en) | New compounds and organic electronic device using the same | |
| JP2013526014A (en) | Novel organic electroluminescent compound and organic electroluminescent device using the same | |
| KR102358637B1 (en) | Compound for organic electric element, organic electric element comprising the same and electronic device thereof | |
| TWI567069B (en) | Organic electroluminescent device | |
| KR20140125061A (en) | An organoelectro luminescent compound and an organoelectroluminescent device using the same | |
| WO2022242521A1 (en) | Condensed azacyclic compound, use thereof, and organic electroluminescent device comprising condensed azacyclic compound | |
| CN112707894A (en) | Acenaphthene imidazole compound and application thereof in organic electroluminescent device | |
| CN106892903B (en) | Organic electroluminescent compound based on phenazine and carbazole and luminescent device thereof | |
| CN113416175B (en) | Compound with anthracene benzofuran as core framework and application thereof | |
| CN109755415B (en) | Device of bipolar material containing 4, 6-diphenyl sulfone dibenzofuran | |
| KR101736119B1 (en) | Organic metal compound and organic electroluminescent devices comprising the same | |
| CN110183302B (en) | Condensed terphenyl compound and preparation method and application thereof | |
| Ding et al. | Novel spiro-based host materials for application in blue and white phosphorescent organic light-emitting diodes | |
| CN109748908B (en) | Bipolar host material based on 4, 6-diphenyl sulfone dibenzofuran and application | |
| CN111187254B (en) | Carbazole-based organic electrophosphorescent material composition and application thereof |
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 |