CN116675706B - Oxazolobenzocarbazole phosphorescent host material and application thereof - Google Patents

Oxazolobenzocarbazole phosphorescent host material and application thereof Download PDF

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CN116675706B
CN116675706B CN202310967923.3A CN202310967923A CN116675706B CN 116675706 B CN116675706 B CN 116675706B CN 202310967923 A CN202310967923 A CN 202310967923A CN 116675706 B CN116675706 B CN 116675706B
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oxazolobenzocarbazole
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phosphorescent host
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汪康
马晓宇
徐佳楠
贾宇
孟范贵
于丹阳
王永光
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The application is applicable to the technical field of materials, provides an oxazolobenzocarbazole phosphorescent host material and application, wherein a mother nucleus in the phosphorescent host material is oxazolobenzocarbazole, the molecular weight is moderate, and a hydrogen bond effect is formed between an N or O atom on oxazole and H on benzocarbazole, so that the oxazolobenzocarbazole phosphorescent host material has higher stability, prolongs the service life of a device, has higher electron migration characteristic, is beneficial to improving the electron mobility and improves the efficiency of the device; and secondly, the connected quinoxaline has the function of regulating and controlling the HOMO energy level, so that the host material has a higher triplet state energy level, the energy transfer between the host and the guest is facilitated, and meanwhile, the HOMO/LUMO energy level which is more matched with an adjacent functional layer is reduced, the injection potential barrier of holes and electrons is reduced, and the driving voltage is reduced. According to the application, the compound with the oxazolobenzocarbazole as a parent nucleus and connected with the quinoxaline/quinazoline is used as a red light phosphorescence main body material, and the prepared light-emitting device has the effects of high light-emitting efficiency, long service life and improvement of driving voltage.

Description

Oxazolobenzocarbazole phosphorescent host material and application thereof
Technical Field
The application belongs to the technical field of materials, and particularly relates to an oxazolobenzocarbazole phosphorescent host material and application thereof.
Background
An organic electroluminescent display (OLED) is an active light emitting display device. At present, an OLED display screen with a medium and small size has been applied to high-end smart phones manufactured by companies such as Hua Cheng, xiao Ji, sanxing and the like in a large scale, and obtaining the optimal luminous efficiency of a device under the condition of low working voltage is a general requirement in the OLED field.
OLED luminescence is divided into fluorescence luminescence and phosphorescence luminescence, in phosphorescence luminescence, singlet state and triplet state excitons are utilized, and compared with fluorescent materials, only singlet state excitons are utilized, and the effective utilization of triplet state excitons with the proportion of up to 75% is achieved, so that the PhOLED based on the phosphorescent materials achieves 100% internal quantum efficiency theoretically. Phosphorescent materials gradually replace traditional fluorescent materials in recent three years, and become a research hot spot of OLED luminescent materials.
The color purity, luminous efficiency, and stability can be improved by combining a host material with a dopant to prepare a luminescent material. The host material greatly influences the efficiency and performance of the organic light-emitting device, and it is important to develop a novel host material meeting the practical requirements. However, further development of phosphorescent materials is urgent because the process for synthesizing phosphorescent materials is complicated, time-consuming and has a low lifetime.
Disclosure of Invention
The application aims to provide an oxazolobenzocarbazole phosphorescent host material, and aims to provide an organic electroluminescent device which is prepared by taking an oxazolobenzocarbazole derivative as a host to be connected with quinoxaline/quinazoline as a red phosphorescent host material, has high luminous efficiency and long service life, and improves the technical effect of driving voltage.
The application is realized in such a way that the structural general formula of the oxazolobenzocarbazole phosphorescent host material is shown as formula I or formula II:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein,
r is independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted 3-to 24-membered heteroaryl;
Ar 1 independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C24 aryl;
l is independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted 3-to 24-membered heteroaryl;
X 1 -X 8 each independently selected from N or C, wherein the number of N is 2 or 3 or 4;
R 1 independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted 3-to 24-membered heteroaryl;
n is an integer from 0 to 4;
substituted or unsubstituted means substituted with one, two or more substituents selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, furanyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, or a substituent linked by two or more of the substituents indicated above, or not.
Another object of the present application is a method for preparing an oxazolobenzocarbazole phosphorescent host material, comprising:
N 2 under the protection, dissolving the reactant A-I, the reactant B-I, a palladium catalyst and alkali in DMF, heating to 85-95 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under the protection, respectively adding the intermediate C-I, the reactant D-I, the palladium catalyst and the alkali and/or phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain the intermediate E-I.
N 2 Under the protection, dissolving an intermediate E-I and triphenylphosphine in o-dichlorobenzene, heating to 160-180 ℃ for reacting for 12-18 hours to obtain the intermediate F-I;
N 2 under protection, in the reaction vessel is addedAfter the intermediate F-I and the reactant G-I are dissolved in xylene, adding a palladium catalyst, a phosphorus ligand and alkali; after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12 hours to obtain the oxazolobenzocarbazole phosphorescent host material shown in the formula I; or alternatively
N 2 Under the protection, adding an intermediate F-I and a reactant g-I into a reaction container, dissolving in dimethylbenzene, adding a palladium catalyst, a phosphorus ligand and alkali, heating to 130-140 ℃, and stirring the mixture for 8-12h to obtain an intermediate h-I;
N 2 under the protection, respectively adding an intermediate h-I, a reactant G-I, a palladium catalyst and alkali and/or phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain an oxazolobenzocarbazole phosphorescent host material shown in a formula I;
the structural formulas of the reactants A-I, the reactants B-I, the intermediate C-I, the intermediate D-I, the intermediate E-I, the intermediate F-I, the reactant G-I, the reactant G-I and the intermediate h-I are respectively shown as follows:
、/>、/>、/>、/>、、/>、/>、/>；Hal 1 -Hal 3 independently selected from chlorine, bromine or iodine.
Another object of the present application is a method for preparing a phosphorescent host material, comprising:
N 2 under the protection, dissolving the reactant A-II, the reactant B-II, a palladium catalyst and alkali in DMF, heating to 85-95 ℃, and reacting for 8-12h to obtain an intermediate C-II;
N 2 under the protection, respectively adding the intermediate C-II, the reactant D-II, the palladium catalyst, the alkali and/or the phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain an intermediate E-II;
N 2 under the protection, dissolving an intermediate E-II and triphenylphosphine in o-dichlorobenzene, heating to 160-180 ℃ for reacting for 12-18 hours to obtain the intermediate F-II;
N 2 under the protection, adding an intermediate F-II and a reactant G-I into a reaction container, dissolving in dimethylbenzene, adding a palladium catalyst, a phosphorus ligand and alkali, heating the reaction temperature to 130-140 ℃, and stirring the mixture for 8-12 hours to obtain an oxazolobenzocarbazole phosphorescent host material shown in a formula II; or alternatively
N 2 Under the protection, adding an intermediate F-II and a reactant g-I into a reaction container, dissolving in dimethylbenzene, adding a palladium catalyst, a phosphorus ligand and alkali, heating the reaction temperature to 130-140 ℃, and stirring the mixture for 8-12h to obtain an intermediate h-II;
N 2 under the protection, respectively adding an intermediate h-II, a reactant G-I, a palladium catalyst, alkali and/or phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain an oxazolobenzocarbazole phosphorescent host material shown in a formula II;
the structural formulas of the reactants A-II, the reactants B-II, the intermediate C-II, the reactant D-II, the intermediate E-II, the intermediate F-II, the reactant G-I, the reactant G-I and the intermediate h-II are respectively shown as follows:
、/>、/>、/>、/>、、/>、/>、/>；Hal 1 -Hal 3 independently selected from chlorine, bromine or iodine.
Another object of the present application is a light emitting device comprising the above-described oxazolobenzocarbazole phosphorescent host material.
The beneficial effects are that: 1. the mother nucleus of the application is oxazolobenzocarbazole, has moderate molecular weight and higher thermal stability, wherein N or O atoms on the oxazoles and H on the benzocarbazole have hydrogen bond action, so that the compound of the application has higher stability and prolongs the service life of the device. Meanwhile, the oxazole has higher electron migration characteristic, which is beneficial to improving electron mobility and improving device efficiency.
2. The connected quinoxaline and quinazoline have the function of regulating and controlling the HOMO energy level, so that the host material has a higher triplet state energy level, the energy transfer between the host and the guest is facilitated, and meanwhile, the HOMO/LUMO energy level which is more matched with an adjacent functional layer is reduced, the injection barrier of holes and electrons is reduced, the driving voltage is reduced, and the service life of the device is prolonged.
3. The compound of the application, which takes oxazolobenzocarbazole as a parent nucleus to connect with quinoxaline/quinazoline, is used as a red light phosphorescence host material, and the prepared organic electroluminescent device has the technical effects of high luminous efficiency, long service life and improvement of driving voltage.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate F-5 provided in an embodiment of the present application;
fig. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound 5 provided in the embodiment of the present application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The application provides an oxazolobenzocarbazole phosphorescent host material, which has a structure shown in a general formula I or a general formula II:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein,
r is independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted 3-to 24-membered heteroaryl;
Ar 1 independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C24 aryl;
l is independently selected from a bond, a substituted or unsubstituted C6-C24 aryl, a substituted or unsubstituted 3-to 24-membered heteroaryl;
X 1 -X 8 each independently selected from N or C, wherein the number of N is 2 or 3 or 4;
R 1 independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted 3-to 24-membered heteroaryl;
n is an integer from 1 to 4.
Further, formula I, formula II has the structure shown in formulas 1-4:
wherein R, ar 1 Independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, isopropyl, n-propyl, t-butyl, phenyl, methylphenyl, naphthyl, biphenyl, terphenyl, phenyl-substituted naphthyl, pyridyl, phenanthryl, dibenzofuranyl, dimethylfluorenyl, 9-phenyl-9H-carbazole, carbazolyl, 9-diphenyl-9H-fluorene;
n is selected from 0 or 1 or 2;
L，R 1 independently selected from the group consisting of a bond, hydrogen, methyl, ethyl, propyl, phenyl, naphthyl, biphenyl, terphenyl, pyridyl, phenanthryl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, 9-phenyl-9H-carbazole, carbazolyl, 9-diphenyl-9H-fluorene, phenyl-substituted fluorenyl, phenyl-substituted phenanthryl, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, and groups;
；
-connection location.
More preferably, formula I, formula II is selected from the structures shown in formulas 5-10:
。
in the present application, the substituted or unsubstituted aryl group of C6-C24 may be phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenyl-substituted naphthyl, naphthyl-substituted biphenyl, naphthyl-substituted terphenyl, fluorenyl, dimethylfluorenyl, 9-diphenyl-9H-fluorenyl, benzofluorenyl, dibenzofluorenyl, phenyl-substituted fluorenyl, phenanthryl, phenyl-substituted phenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, perylenyl, droyl, naphthonaphthyl, anthracenyl, spirobifluorenyl, azulenyl, methylphenyl, ethylphenyl, methoxyphenyl, cyanophenyl.
In the present application, a substituted or unsubstituted 3-to 24-membered heteroaryl group, can be furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, dibenzofuranyl, dibenzothienyl, naphthobenzofuranyl, naphthobenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzoindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, benzoquinazolinyl, benzoquinoxalinyl, naphthyridinyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, 9-phenylcarbazolyl, benzoxazolyl, H, and dihydrophenanthrenyl.
The term "substituted or unsubstituted" refers to the number of carbon atoms of a substituent that make up the unsubstituted number of carbon atoms, regardless of the number of carbon atoms in the substituent.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, furanyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, or a substituent linked by two or more of the substituents indicated above, or not.
Aryl refers to monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems, a polycyclic ring may have two or more rings in which two carbons are common to two adjoining rings (the rings being "fused").
Heteroaryl groups include monocyclic aromatic groups and polycyclic aromatic ring systems of at least one heteroatom including, but not limited to O, S, N, P, B, si and Se.
The compounds represented by formula I, formula II may be specifically exemplified by, but not limited to, the following compounds.
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。
The application also provides a synthetic route of the oxazolobenzocarbazole phosphorescent host material shown in the formula I, which is shown as follows:
synthesis of intermediate F-I:
N 2 under the protection, the reactants A-I (1.0 eq), the reactants B-I (1.1-1.3 eq), the palladium catalyst (0.05-0.1 eq) and the alkali (2.0-3.0 eq) are dissolved in DMF, heated to 85-95 ℃ and reacted for 8-12h. The solvent was removed using a rotary evaporator, dichloromethane was added, stirred, filtered, and purified by column chromatography to give intermediate C-I.
N 2 Under the protection, adding the intermediate C-I (1.0 eq), the reactant D-I (1-1.2 eq), the palladium catalyst (0.01-0.02 eq), the alkali (2.0-2.4 eq) and/or the phosphine ligand (0.02-0.15 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, heating to 80-100 ℃, reacting for 8-12H, cooling to room temperature, and adding H 2 And O, filtering after the solid is precipitated, drying a filter cake, purifying by using a column chromatography, removing the solvent by using a rotary evaporator, and drying the obtained solid to obtain an intermediate E-I.
N 2 Under protection, intermediate E-I (1.0 eq), PPh 3 (5.0-6.0 eq) is dissolved in o-DCB (o-dichlorobenzene), the temperature is raised to 160-180 ℃ for reaction for 12-18 hours, the temperature is reduced to room temperature, petroleum ether is added, the solid is filtered after precipitation, the solvent is removed by a rotary evaporator after purification by column chromatography, and the obtained solid is dried to obtain an intermediate F-I.
When L is a bond, synthesis of formula I:
N 2 under the protection, after adding intermediate F-I (1.0 eq) and reactant G-I (1.1-1.3 eq) into a reaction vessel and dissolving in xylene, adding palladium catalyst (0.01-0.05 eq), phosphorus ligand (0.02-0.15 eq) and alkali (2.0-2.4 eq); after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give formula I.
Synthesis of formula I when L is a substituent:
N 2 under the protection, after the intermediate F-I (1.0 eq) and the reactant g-I (1.1-1.3 eq) are added into a reaction vessel and dissolved in dimethylbenzene, a palladium catalyst (0.01-0.05 eq), a phosphorus ligand (0.02-0.15 eq) and a base (2.0-2.4 eq) are added; after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give intermediate h-I.
N 2 Under the protection, respectively adding the intermediate H-I (1.0 eq), the reactant I-I (1-1.2 eq), the palladium catalyst (0.01-0.02 eq), the alkali (2.0-2.4 eq) and/or the phosphine ligand (0.02-0.15 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1), heating to 80-100 ℃, reacting for 8-12H, cooling to room temperature, and adding H 2 And O, filtering after the solid is separated out, drying a filter cake, purifying by using a column chromatography, removing the solvent by using a rotary evaporator, and drying the obtained solid to obtain the formula I.
The application also provides a synthetic route of the oxazolobenzocarbazole phosphorescent host material shown in the formula II, which is shown as follows:
synthesis of intermediate F-II:
N 2 under the protection, the reactant A-II (1.0 eq), the reactant B-II (1.1-1.3 eq), the palladium catalyst (0.05-0.1 eq) and the alkali (2.0-3.0 eq) are dissolved in DMF, heated to 85-95 ℃ and reacted for 8-12h. The solvent was removed using a rotary evaporator, dichloromethane was added, stirred, filtered, and purified by column chromatography to give intermediate C-II.
N 2 Under the protection, adding the intermediate C-II (1.0 eq), the reactant D-II (1-1.2 eq), the palladium catalyst (0.01-0.02 eq), the alkali (2.0-2.4 eq) and/or the phosphine ligand (0.02-0.15 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, heating to 80-100 ℃, reacting for 8-12H, cooling to room temperature, and adding H 2 And O, filtering after the solid is separated out, drying a filter cake, purifying by using a column chromatography, removing the solvent by using a rotary evaporator, and drying the obtained solid to obtain an intermediate E-II.
N 2 Under protection, intermediate E-II (1.0 eq), PPh 3 (5.0-6.0 eq) is dissolved in o-DCB (o-dichlorobenzene), the temperature is raised to 160-180 ℃ for reaction for 12-18 hours, the temperature is reduced to room temperature, petroleum ether is added, the solid is filtered after precipitation, the solvent is removed by a rotary evaporator after purification by column chromatography, and the obtained solid is dried to obtain an intermediate F-II.
When L is a bond, synthesis of formula II:
N 2 under the protection, after the intermediate F-II (1.0 eq) and the reactant G-II (1.1-1.3 eq) are added into a reaction vessel and dissolved in dimethylbenzene, a palladium catalyst (0.01-0.05 eq), a phosphorus ligand (0.02-0.15 eq) and a base (2.0-2.4 eq) are added; after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give formula II.
Synthesis of formula II when L is a substituent:
N 2 under protection, the intermediate F-II (1.0 eq) and the reactant g-II (1.1-1.3 eq) are dissolved in xylene in a reaction vesselThen adding palladium catalyst (0.01-0.05 eq), phosphorus ligand (0.02-0.15 eq) and alkali (2.0-2.4 eq); after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give intermediate h-II.
N 2 Under the protection, respectively adding the intermediate H-II (1.0 eq), the reactant i-II (1-1.2 eq), the palladium catalyst (0.01-0.02 eq), the alkali (2.0-2.4 eq) and/or the phosphine ligand (0.02-0.15 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1), heating to 80-100 ℃, reacting for 8-12H, cooling to room temperature, and adding H 2 And O, filtering after the solid is separated out, drying a filter cake, purifying by using a column chromatography, removing the solvent by using a rotary evaporator, and drying the obtained solid to obtain the formula II.
In the synthesis step of the formula I and the formula II:
R、R 1 、n、X 1 -X 8 、L、Ar 1 hal, as defined in formulae I, II above 1 -Hal 3 Independently selected from chlorine, bromine or iodine.
For the raw materials not disclosed, a classical Suzuki coupling reaction, buchwald-Hartwig coupling reaction was used for synthesis and application in the present application.
The palladium catalyst may be: pd (Pd) 2 (dba) 3 (tris (dibenzylideneacetone) dipalladium) Pd (PPh 3 ) 4 (Tetrakis (triphenylphosphine) palladium), pdCl 2 (Palladium dichloride), pdCl 2 (dppf) (1, 1' -bis (diphenylphosphino) ferrocene palladium chloride), pd (OAc) 2 (Palladium acetate), pd (PPh) 3 ) 2 Cl 2 Any one or a combination of at least two of (bis (triphenylphosphine) palladium dichloride).
The phosphine ligand may be: PPh (PPh) 3 (triphenylphosphine), P (t-Bu) 3 (tri-tert-butylphosphine), X-phos (2-cyclohexyl-2, 4, 6-triisopropylbiphenyl), PET 3 (triethylphosphine)、PMe 3 (trimethylphosphine), PPh 3 (triphenylphosphine), KPPh 2 (Potassium diphenylphosphonate).
The base may be: acOK (Potassium acetate), K 2 CO 3 、K 3 PO 4 、Na 2 CO 3 、CsF、Cs 2 CO 3 Or any one or a combination of at least two of t-BuONa (sodium t-butoxide).
The following description of the embodiments of the present application will be made in detail, with reference to the phosphorescent host material of the present application, but it should be apparent that the embodiments described are only some embodiments of the present application, not all embodiments.
In addition, it should be noted that the numerical values set forth in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be construed as a divisor rather than an absolute precise numerical value due to measurement errors and experimental operation problems that cannot be avoided.
Example 1: synthesis of Compound 5
N 2 Under protection, reactant A-5 (1.0 eq), reactant B-5 (1.1 eq), pdCl 2 (dppf) (0.05 eq) and AcOK (2.5 eq) were dissolved in DMF and heated to 90℃for 8h. The solvent was removed using a rotary evaporator, methylene chloride was added thereto, stirred, filtered, and purified by column chromatography to give intermediate C-5 (yield: 76.1%, test value MS (ESI, M/Z): [ M+H ]]+= 371.41）。
N 2 Under protection, intermediate C-5 (1.0 eq), reactant D-5 (1.2 eq), pd (OAc) 2 (0.015eq），Cs 2 CO 3 (2.2 eq) and X-phos (0.03 eq) are respectively added into a mixed solvent of toluene, ethanol and water (3:1:1), the temperature is raised to 90 ℃, the reaction is carried out for 10 hours, the temperature is cooled to room temperature, and H is added 2 Filtering after the solid is precipitated, drying a filter cake, purifying by column chromatography, removing a solvent by a rotary evaporator, and drying the obtained solid to obtain an intermediateBody E-5 (yield: 68.6%, test value MS (ESI, M/Z): [ M+H ]]+= 366.56）。
N 2 Under protection, intermediate E-5 (1.0 eq), PPh 3 (5.0 eq) was dissolved in o-DCB (o-dichlorobenzene), the temperature was raised to 180℃for 12 hours, the temperature was lowered to room temperature, petroleum ether was added, the solid was precipitated and filtered, the solid was purified by column chromatography, the solvent was removed by a rotary evaporator, and the obtained solid was dried to give intermediate F-5 (yield: 53.4%, test value MS (ESI, M/Z): [ M+H ]]+= 334.62）。
N 2 Under protection, after adding intermediate F-5 (1.0 eq) and reactant G-5 (1.2 eq) to the reaction vessel and dissolving in xylene, pd was added 2 (dba) 3 （0.02eq）、P(t-Bu) 3 (0.04 eq), t-Buona (2.4 eq); after the addition, the reaction temperature was raised to 130 ℃, and the mixture was stirred for 8h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give Compound 5 (yield: 82.7%, test value MS (ESI, M/Z): [ M+H ]]+= 538.87）。
The nuclear magnetism of the intermediate F-5 is shown in figure 1.
The nuclear magnetism of compound 5 is shown in FIG. 2.
Characterization:
HPLC purity: > 99.6%.
Elemental analysis:
theoretical value: c, 82.51, H, 4.12, N, 10.40, O, 2.97
Test value: c, 82.30, H, 4.24, N, 10.49, O, 3.02
Example 2: synthesis of Compound 61
N 2 Under protection, reactant A-61 (1.0 eq), reactant B-61 (1.1 eq), pdCl 2 (dppf) (0.05 eq) and ACOK (2.5 eq) were dissolved in DMF and heated to 90℃for 8h. Using a screwThe solvent was removed by a rotary evaporator, stirred with methylene chloride, filtered, and purified by column chromatography to give intermediate C-61 (yield: 80.6%, test value MS (ESI, M/Z): [ M+H ]]+= 371.48）。
N 2 Under protection, intermediate C-61 (1.0 eq), reactant D-61 (1.2 eq), pd (OAc) 2 (0.015eq），Cs 2 CO 3 (2.2 eq) and X-phos (0.03 eq) are respectively added into a mixed solvent of toluene, ethanol and water (3:1:1), the temperature is raised to 90 ℃, the reaction is carried out for 10 hours, the temperature is cooled to room temperature, and H is added 2 O, after the precipitation of the solid, filtering, drying the filter cake, purifying by column chromatography, removing the solvent by a rotary evaporator, and drying the obtained solid to obtain an intermediate E-61 (yield: 71.9%, test value MS (ESI, M/Z): [ M+H ]]+= 366.62）。
N 2 Under protection, intermediate E-61 (1.0 eq), PPh 3 (5.0 eq) was dissolved in o-DCB (o-dichlorobenzene), the temperature was raised to 180℃for 12 hours, the temperature was lowered to room temperature, petroleum ether was added, the solid was precipitated and filtered, the solid was purified by column chromatography, the solvent was removed by a rotary evaporator, and the obtained solid was dried to give intermediate F-61 (yield: 58.0%, test value MS (ESI, M/Z): [ M+H ]]+= 334.54）。
N 2 Under protection, after adding intermediate F-61 (1.0 eq) and reactant g-61 (1.1 eq) to xylene in a reaction vessel, pd was added 2 (dba) 3 （0.01eq）、P(t-Bu) 3 (0.02 eq), t-Buona (2.2 eq); after the addition, the reaction temperature was raised to 130 ℃, and the mixture was stirred for 12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give intermediate H-61 (yield: 77.5%, test value MS (ESI, M/Z): [ M+H ]]+= 536.65）。
N 2 Under protection, intermediate h-61 (1.0 eq), reactant i-61 (1.2 eq), pd (PPh) 3 ) 4 (0.02eq），K 2 CO 3 (2.2 eq) of the mixture was added to toluene, ethanol and water (3:1:1), respectivelyIn the mixed solvent, heating to 90 ℃, reacting for 12 hours, cooling to room temperature, adding H 2 O, after the precipitation of the solid, filtering, drying the cake, purifying by column chromatography, removing the solvent by rotary evaporator, and drying the obtained solid to obtain compound 61 (yield: 84.2%, test value MS (ESI, M/Z): [ M+H ]]+= 691.09）。
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c, 85.20, H, 4.38, N, 8.11, O, 2.32
Test value: c, 85.07, H, 4.45, N, 8.18, O, 2.38
Example 3: synthesis of Compound 244
Intermediate D-244:CAS:91331-24-7
Intermediate F-244:CAS:2259353-86-9
Intermediate C-5 and intermediate C-244 are the same intermediate, and the synthetic route is the same;
N 2 under protection, intermediate C-244 (1.0 eq), reactant D-244 (1.2 eq), pd (OAc) 2 (0.015eq），Cs 2 CO 3 (2.2 eq) and X-phos (0.03 eq) are respectively added into a mixed solvent of toluene, ethanol and water (3:1:1), the temperature is raised to 90 ℃, the reaction is carried out for 10 hours, the temperature is cooled to room temperature, and H is added 2 O, after the precipitation of the solid, filtering, drying the filter cake, purifying by column chromatography, removing the solvent by a rotary evaporator, and drying the obtained solid to obtain an intermediate E-244 (yield: 77.8%, test value MS (ESI, M/Z): [ M+H ]]+= 442.62）。
N 2 Under protection, intermediate E-244 (1.0 eq), PPh 3 (5.0 eq) was dissolved in o-DCB (o-dichlorobenzene), the temperature was raised to 180℃for 12 hours, the temperature was lowered to room temperature, petroleum ether was added, the solid was precipitated and filtered, the solid was purified by column chromatography, the solvent was removed by a rotary evaporator, and the obtained solid was dried to give intermediate F-244 (yield: 49.1%, measurement)Test value MS (ESI, M/Z) [ M+H ]]+= 410.77）。
N 2 Under protection, after adding intermediate F-244 (1.0 eq) and reactant G-244 (1.2 eq) to the reaction vessel and dissolving in xylene, pd (OAc) was added 2 (0.02 eq), X-Phos (0.05 eq), t-Buona (2.2 eq); after the addition, the reaction temperature was raised to 135 ℃ and the mixture was stirred for 8h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give compound 244 (yield: 73.7%, test value MS (ESI, M/Z): [ M+H ]]+= 705.01）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 83.51, H, 4.00, N, 7.95, O, 4.54
Test value: c, 83.34, H, 4.12, N, 8.02, O, 4.56
Example 4: synthesis of Compound 385
Reactants i-385: CAS:2036123-15-4
Intermediate F-385 and intermediate F-61 are the same intermediate, and the synthetic routes are the same;
N 2 under protection, after adding intermediate F-385 (1.0 eq) and reactant g-385 (1.1 eq) to the reaction vessel and dissolving in xylene, pd was added 2 (dba) 3 （0.01eq）、P(t-Bu) 3 (0.02 eq), t-Buona (2.2 eq); after the addition, the reaction temperature was raised to 130 ℃, and the mixture was stirred for 12h; filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and purified by column chromatography to give intermediate h-385 (yield: 82.0%, assay)Test value MS (ESI, M/Z) [ M+H ]]+= 662.84）。
N 2 Under protection, intermediate h-385 (1.0 eq), reactant i-385 (1.2 eq), pd (PPh) 3 ) 4 (0.02eq），K 2 CO 3 (2.2 eq) are respectively added into a mixed solvent of toluene, ethanol and water (3:1:1), the temperature is raised to 90 ℃, the reaction is carried out for 12 hours, the temperature is cooled to room temperature, and H is added 2 O, after the precipitation of the solid, filtering, drying the cake, purifying by column chromatography, removing the solvent by rotary evaporator, and drying the obtained solid to obtain compound 385 (yield: 75.4%, test value MS (ESI, M/Z): [ M+H ]]+= 817.24）。
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c, 86.74, H, 4.44, N, 6.86, O, 1.96
Test value: c, 86.67, H, 4.51, N, 6.92, O, 1.99
Examples 5 to 42: the synthesis of the compounds of formula I, formula II was accomplished by the synthesis methods of examples 1 to 4, and their molecular formulas and mass spectra are shown in table 1 below.
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Further, since other compounds of the present application can be obtained by referring to the synthetic methods of the above-described examples, they are not exemplified herein. The mass spectrometer model adopted in the mass spectrum test is Waters XEVO TQD, and the ESI source test is performed with low precision.
The present application provides an organic electroluminescent device, which may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, etc. as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller or larger number of organic layers.
According to one embodiment of the present description, the organic layer comprises a light emitting layer consisting of a host material and a dopant material according to the present application of formula I and/or formula II.
In the case of producing an organic light-emitting device, the compound represented by the above formula I or formula II may be formed by vacuum vapor deposition or solution coating. The solution coating method is, but not limited to, spin coating, dip coating, blade coating, ink jet printing, screen printing, spray coating, roll coating, and the like.
The organic light emitting element of the present application may be of a top emission type, a bottom emission type or a bi-directional emission type, depending on the materials used.
The device of the present application may be used in organic light emitting devices including, but not limited to, flat panel displays, computer monitors, a medical monitor, a television, billboards, a light for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, a laser printer, a telephone, a cell phone, a photo album, personal Digital Assistant (PDA), a notebook, a digital camera, video camera, viewfinder, micro-display, three-dimensional display, virtual reality or augmented reality display, video wall including a plurality of displays tiled together, theatre or venue screen, phototherapy device and sign.
As the anode material, a material having a large work function is generally preferable in order to allow holes to be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present application include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO A1 or SnO 2 A combination of metals such as Sb and the like and oxides; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer is preferably a p-doped hole injection layer, by which is meant a hole injection layer doped with a p-dopant. A p-dopant is a material capable of imparting p-type semiconductor characteristics. The p-type semiconductor property means a property of injecting holes or transporting holes at the HOMO level, that is, a property of a material having high hole conductivity.
The P-doped P-dopant may be exemplified by, but not limited to, the following compounds.
A hole transport layer, a hole transport auxiliary layer, an electron blocking layer, a light emitting auxiliary layer, etc. are disposed between the anode and the light emitting layer, which may be used to promote hole injection and/or hole transport, or to prevent electron overflow; the aromatic amine derivative, the conductive polymer, and the block copolymer having both conjugated and non-conjugated portions may be selected.
Specifically, the hole transport layer, the hole transport auxiliary layer, the electron blocking layer, and the light emitting auxiliary layer are selected from the following compounds, but are not limited thereto.
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The light-emitting substance of the light-emitting layer is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in the visible light region.
The compound shown in the formula I or the formula II is used as a main body material of the light-emitting layer.
The light emitting layer is composed of a host material and a dopant material.
The mass ratio of the host material to the doping material is 90-99.5:0.5-10.
The dopant materials of the present application include fluorescent doping and phosphorescent doping. May be selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the doping material of the present application is selected from the following compounds, but is not limited thereto.
The electron transport region may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of an electron transport layer and an electron injection layer. The electron transport region is a layer capable of improving a problem of deterioration of light emission luminance due to a change in current characteristics in the device when the device is exposed to high temperature during a process of manufacturing a panel, and it can control charge flow characteristics.
The material of the electron transport layer (hole blocking layer), such as oxazole, imidazole, thiazole, triazine, and the like, metal chelate, quinoline derivative, quinoxaline derivative, diazoanthracene derivative, phenanthrene derivative, silicon-containing heterocyclic compound, perfluorinated oligomer, and the like, is specifically selected from the following compounds, but is not limited thereto.
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In some embodiments of the present application, the material of the electron injection layer includes, but is not limited to, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylmethane, anthrone and their derivatives, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, etc., or their alloys, metal complexes, nitrogen-containing 5-membered ring derivatives, etc.
The cathode material is generally preferably a material having a small work function in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof: liF/A1 or LiO 2 And (3) multilayer structural materials such as (A1) and Mg/Ag.
The OLED device is not particularly limited with respect to other layer materials except that the host material in the light emitting layer of the present application is composed of formula I or formula II. Existing hole injection materials, hole transport materials, dopant materials, hole blocking layer materials, electron transport layer materials, and electron injection materials may be used.
The organic electroluminescent device provided by the application is specifically described below with reference to specific device application examples.
Application example: preparation of red light organic electroluminescent device
a. ITO anode: washing glass substrate of ITO (indium tin oxide) -Ag-ITO (thickness of 14nm/150nm/14 nm) in distilled water for 2 times, washing with ultrasonic wave for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic wave for 10min, baking with vacuum oven at 220 deg.C for 2 hr, and cooling after baking. Using the substrate as an anode, and using an evaporator to perform an evaporation device process, and evaporating other functional layers on the substrate in sequence;
b. HIL (hole injection layer): the hole injection layer materials HT1-10 and P-5 were vacuum evaporated at an evaporation rate of 1 Å/s, the chemical formulas of which are shown below. The evaporation rate ratio of HT1-10 to P-5 is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating 130nm HT1-10 on the hole injection layer as a hole transport layer at an evaporation rate of 1.0 Å/s;
d. prime (light-emitting auxiliary layer): vacuum evaporating 85nm HT1-24 on the hole transport layer as light emitting auxiliary layer at evaporation rate of 0.5 Å/s;
e. EML (light emitting layer): then, on the above light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant-R-2) of the formula I or II with a total thickness of 40nm were vacuum-evaporated as a light-emitting layer at an evaporation rate of 1 Å/s, and the chemical formulas of Host and Dopant are as follows, with an evaporation rate ratio of Host to Dopant-R-2 of 97:3, a step of;
f. HBL (hole blocking layer): vacuum evaporating the hole blocking layer ET-3 with the thickness of 5.0nm at the evaporation rate of 0.5 Å/s;
g. ETL (electron transport layer): ET-28 and Liq with the thickness of 30nm are vacuum evaporated to be used as electron transport layers at the evaporation rate of 1 Å/s. Wherein the ratio of the evaporation rates of ET-28 and Liq is 1:1, a step of;
h. EIL (electron injection layer): evaporating Yb film layer 1.0nm at an evaporation rate of 0.5 Å/s to form an electron injection layer;
i. and (3) cathode: evaporating magnesium and silver at a ratio of 1:1 Å/s to 13nm, wherein the ratio of the evaporation rates is 1:9, so as to form a cathode;
j. light extraction layer: CPL with the thickness of 65nm is vacuum deposited on the cathode at the vapor deposition rate of 1 Å/s to be used as a light extraction layer;
k. and packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
Application examples 1-100: the organic electroluminescent devices of application examples 1-100 were prepared according to the above-described preparation method of organic electroluminescent device, and the host material was selected from the corresponding compounds of formula I or formula II.
Comparative example 1: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 1.
Comparative example 2: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 2.
Comparative example 3: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 3.
Comparative example 4: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 4.
Comparative example 5: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 5.
Comparative example 6: the organic electroluminescent device is prepared according to the preparation method of the organic electroluminescent device, and the main material is selected from the comparative compound 6.
The structural formula is as follows:
the organic electroluminescent devices obtained in the above device application examples 1 to 100 and device comparative examples 1 to 6 were characterized in terms of driving voltage, luminous efficiency, and lifetime at 6000 (nits) luminance, and the test results are shown in table 2 below:
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as can be seen from Table 2, the driving voltage of the compound of the present application is 3.3-3.47V, the luminous efficiency is 57.1-64.5cd/A, the lifetime is 1520-1660h, the comparative compound is 3.5-3.56V, the luminous efficiency is 52-54.9cd/A, the lifetime is 1420-1473h, and the organic electroluminescent device prepared by using the red light host material provided by the embodiment of the present application has the technical effects of long lifetime, high luminous efficiency and improved driving voltage as compared with the conventional organic electroluminescent device provided by comparative examples 1-6, the organic electroluminescent device provided by the embodiment of the present application has the following advantages.
In addition, the compound 8 and the comparison compound 1 are in parallel comparison, the compound 225 and the compound 2 are in parallel comparison, the parent nucleus adopted by the comparison compound is different from the parent nucleus adopted by the application, and the parent nucleus is oxazolobenzocarbazole, wherein the N or O atom on the oxazole and H on the benzocarbazole have hydrogen bond action, so that the compound has higher stability and prolonged service life. Meanwhile, the oxazole has higher electron migration characteristic, which is beneficial to improving electron mobility and improving device efficiency.
Second, compound 227 of the present application was in parallel comparison with comparative compound 5, and the oxazolophenanthrene molecular weight of comparative compound 5 was small, and the device stability was poor.
The quinoxaline and quinazoline have the function of regulating and controlling the HOMO energy level, so that the host material has a higher triplet state energy level, the energy transfer between the host and the guest is facilitated, meanwhile, the HOMO/LUMO energy level which is more matched with an adjacent functional layer is reduced, the injection barrier of holes and electrons is reduced, the driving voltage is reduced, and the service life of the device is prolonged.
The compound of the application, which takes oxazolobenzocarbazole as a parent nucleus to connect with quinoxaline/quinazoline, is used as a red light phosphorescence host material, and the prepared organic electroluminescent device has the technical effects of high luminous efficiency, long service life and improvement of driving voltage.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. The oxazolobenzocarbazole phosphorescent host material is characterized in that the structural formula of the oxazolobenzocarbazole phosphorescent host material is shown in the formulas 5-10:
；
wherein,
r is independently selected from methyl, ethyl, isopropyl, n-propyl, phenyl, methylphenyl, naphthyl, biphenyl, phenyl-substituted naphthyl, dimethylfluorenyl;
Ar 1 independently selected from hydrogen, phenyl, naphthyl;
l is independently selected from the group consisting of a linkage, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, dibenzofuranyl, dimethylfluorenyl, and:；
R 1 independently selected from the group consisting of hydrogen, ethyl, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, 9-phenyl-9H-carbazole, carbazolyl, phenyl substitutedDibenzofuranyl and the following groups:
；
-connection location.
2. The oxazolobenzocarbazole phosphorescent host material is characterized in that the oxazolobenzocarbazole phosphorescent host material is any one of the following structures:
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
。
3. a method for preparing the oxazolobenzocarbazole phosphorescent host material according to claim 1, comprising:
N 2 under the protection, dissolving the reactant A-I, the reactant B-I, a palladium catalyst and alkali in N, N-dimethylformamide, heating to 85-95 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under the protection, respectively adding the intermediate C-I, the reactant D-I, the palladium catalyst and the alkali and/or phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain an intermediate E-I;
N 2 under the protection, dissolving an intermediate E-I and triphenylphosphine in o-dichlorobenzene, heating to 160-180 ℃ for reacting for 12-18 hours to obtain the intermediate F-I;
N 2 under the protection, adding an intermediate F-I and a reactant G-I into a reaction container, dissolving in dimethylbenzene, and adding a palladium catalyst, a phosphorus ligand and alkali; after the addition, the reaction temperature is raised to 130-140 ℃, and the mixture is stirred for 8-12 hours, so that the oxazolobenzocarbazole phosphorescent host material shown in the formula 5, the formula 6 or the formula 7, wherein L is a connecting bond, is obtained;
wherein, structural formulas of the reactant A-I, the reactant B-I, the intermediate C-I, the reactant D-I, the intermediate E-I, the intermediate F-I and the reactant G-I are respectively shown as follows:、/>、/>、/>、、/>、/>；Hal 1 、Hal 3 independently selected from chlorine, bromine or iodine; r, R 1 、Ar 1 As defined in claim 1; x is X 1 -X 8 Each independently selected from the group consisting of N and C,the number of N is 2; n is 1.
4. A method for preparing the oxazolobenzocarbazole phosphorescent host material according to claim 1, comprising:
N 2 under the protection, dissolving the reactant A-II, the reactant B-II, a palladium catalyst and alkali in N, N-dimethylformamide, heating to 85-95 ℃, and reacting for 8-12h to obtain an intermediate C-II;
N 2 under the protection, respectively adding the intermediate C-II, the reactant D-II, the palladium catalyst, the alkali and/or the phosphine ligand into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain an intermediate E-II;
N 2 under the protection, dissolving an intermediate E-II and triphenylphosphine in o-dichlorobenzene, heating to 160-180 ℃ for reacting for 12-18 hours to obtain the intermediate F-II;
N 2 under the protection, adding an intermediate F-II and a reactant G-I into a reaction container, dissolving in dimethylbenzene, adding a palladium catalyst, a phosphorus ligand and alkali, heating the reaction temperature to 130-140 ℃, and stirring the mixture for 8-12h to obtain an oxazolobenzocarbazole phosphorescent host material shown in formula 8 or formula 9 or formula 10, wherein L is a connecting bond;
wherein, structural formulas of the reactant A-II, the reactant B-II, the intermediate C-II, the reactant D-II, the intermediate E-II, the intermediate F-II and the reactant G-I are respectively shown as follows:
/>
；Hal 1 、Hal 3 independently selected from chlorine, bromine or iodine; r, R 1 、Ar 1 As defined in claim 1; x is X 1 -X 8 Each independently selected from N or C, the number of N is 2; n is 1.
5. A light-emitting device comprising the oxazolobenzocarbazole phosphorescent host material according to any of claims 1 to 2.
CN202310967923.3A 2023-08-03 2023-08-03 Oxazolobenzocarbazole phosphorescent host material and application thereof Active CN116675706B (en)

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CN106866637A (en) * 2017-03-16 2017-06-20 长春海谱润斯科技有限公司 A kind of bipolar phosphorescent compound of carbazolyl-containing group and preparation method thereof and organic luminescent device
CN112266387A (en) * 2020-10-29 2021-01-26 北京八亿时空液晶科技股份有限公司 Benzophenanthrene derivative and application thereof
CN112341466A (en) * 2020-11-04 2021-02-09 浙江华显光电科技有限公司 Organic compound and organic light-emitting device using same
CN114853737A (en) * 2021-02-04 2022-08-05 北京鼎材科技有限公司 Compound and application thereof

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KR102029696B1 (en) * 2013-03-07 2019-10-08 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

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Publication number Priority date Publication date Assignee Title
CN106866637A (en) * 2017-03-16 2017-06-20 长春海谱润斯科技有限公司 A kind of bipolar phosphorescent compound of carbazolyl-containing group and preparation method thereof and organic luminescent device
CN112266387A (en) * 2020-10-29 2021-01-26 北京八亿时空液晶科技股份有限公司 Benzophenanthrene derivative and application thereof
CN112341466A (en) * 2020-11-04 2021-02-09 浙江华显光电科技有限公司 Organic compound and organic light-emitting device using same
CN114853737A (en) * 2021-02-04 2022-08-05 北京鼎材科技有限公司 Compound and application thereof

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