CN114315871A - Phenanthroline compound, organic electroluminescent device and display or lighting device - Google Patents
Phenanthroline compound, organic electroluminescent device and display or lighting device Download PDFInfo
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- CN114315871A CN114315871A CN202210228189.4A CN202210228189A CN114315871A CN 114315871 A CN114315871 A CN 114315871A CN 202210228189 A CN202210228189 A CN 202210228189A CN 114315871 A CN114315871 A CN 114315871A
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Abstract
The present invention provides a phenanthroline compound, an organic electroluminescent device, and a display or lighting device, the phenanthroline compound being represented by the following formula 1:
wherein Ar is1Is a substituted or unsubstituted C12-C30 phenanthroline derivative group; ar (Ar)2Is substituted or unsubstituted oxazolo [5,4-h]Quinolyl, phenanthrene [4,3-d ]]Oxazolyl, oxazolo [4',5':3, 4)]Benzo [1,2-h ]]Quinolyl or oxazolo [5',4':3,4]Benzo [1,2-h ]]A quinolyl group; ar (Ar)3And Ar4Each independently selected from hydrogen, deuterium, halogen, C6-C30 aryl or C5-C30 heteroaryl, wherein at least one is C12-C30 aryl or C12-C30 heteroaryl; l is phenyl, pyridyl,Pyrimidinyl, pyrazinyl or imidazolyl. The organic electroluminescent device comprising the phenanthroline compound of the present invention minimizes the energy level difference between the n-type charge generation layer and the p-type charge generation layer, and increases the electron injection amount of the light emitting part, thereby reducing the driving voltage and improving the efficiency.
Description
Technical Field
The present invention relates to a phenanthroline compound, and more particularly, to a phenanthroline compound, an organic electroluminescent device, and a display or lighting apparatus.
Background
A light emitting device is a device that converts electric energy into light energy using an organic substance, and includes a structure of an organic layer that is possible to emit light between an anode and a cathode.
The organic light emitting device may be formed in various structures, and among them, an organic light emitting device in which a plurality of light emitting cells are overlapped (tentem) is being studied.
In the overlap (tentem) type organic electroluminescent device, light emitting cells including a light emitting layer are stacked between an anode and a cathode.
There is a charge generation layer between adjacent light emitting portions for generation and movement of charges.
The charge generation layer requires a low driving voltage and high efficiency.
Disclosure of Invention
The present invention provides an organic electroluminescent device comprising a phenanthroline compound, minimizing an energy level difference between an n-type charge generation layer and a p-type charge generation layer, and increasing an electron injection amount of a light emitting part, thereby reducing a driving voltage and improving efficiency.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the invention provides a phenanthroline compound, which has a structure shown in formula 1:
wherein Ar is1Is a substituted or unsubstituted C12-C30 phenanthroline derivative group;
Ar2is substituted or unsubstituted oxazolo [5,4-h]Quinolyl, phenanthrene [4,3-d ]]Oxazolyl, oxazolo [4',5':3, 4)]Benzo [1,2-h ]]Quinolyl or oxazolo [5',4':3,4]Benzo [1,2-h ]]A quinolyl group;
Ar3and Ar4Each independently selected from hydrogen, deuterium, halogen, C6-C30 aryl or C5-C30 heteroaryl, wherein at least one is C12-C30 aryl or C12-C30 heteroaryl;
l is phenyl, pyridyl, pyrimidinyl, pyrazinyl, or imidazolyl.
Preferably, wherein the phenanthroline compound is represented by any one of formulae 1-1 to 1-8 below:
wherein R is1To R14Each independently selected from substituted or unsubstituted hydrogen, deuterium, halogen, alkyl, C6-C30 aryl or C5-C30 heteroaryl;
Ar3and Ar4Each independently selected from hydrogen, deuterium, halogen, C6-C30 aryl or C5-C30 heteroaryl, wherein at least one is C12-C30 aryl or C12-C30 heteroaryl;
Ar5is substituted or unsubstituted C6-C30 aryl or C5-C30 heteroaryl;
X1is carbon or nitrogen.
Preferably, wherein R1To R14Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted naphthyridinyl, or combinations thereof.
Preferably, wherein Ar3To Ar5Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, and substituted or unsubstituted pyrrolylSubstituted or unsubstituted phenanthroline, substituted or unsubstituted naphthyridine or combinations thereof.
More preferably, wherein the phenanthroline compound is any one of:
the present invention further provides an organic electroluminescent device comprising:
a first electrode;
a second electrode, and
an organic layer between the first electrode and the second electrode;
the organic layer includes the phenanthroline compound of the present invention.
Preferably wherein at least one of the organic layers is a charge generation layer or an electron transport layer.
More preferably, the charge generation layer is an n-type charge generation layer.
More preferably, the n-type charge generation layer is composed of a metal or an organic material doped with an n-type, wherein the metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, or Yb.
Preferably wherein the organic layer is a charge generation layer or an electron transport layer, preferably an N-type charge generation layer.
The present invention further provides an organic electroluminescent device comprising:
a first electrode;
a second electrode;
a first light-emitting portion of a first light-emitting layer located between the first electrode and the second electrode;
a second light emitting part of a second light emitting layer between the second electrode and the first light emitting part, and
a first charge generation layer located between the first light-emitting portion and the second light-emitting portion;
at least one of the first light-emitting portion, the second light-emitting portion, or the first charge generation layer includes a phenanthroline compound of the present invention.
The invention further provides an application of the o-phenanthroline compound in the preparation of organic electroluminescent devices.
The invention further provides a display or lighting device comprising the organic electroluminescent device of the invention.
Drawings
Fig. 1 is a structural layer diagram of an organic electroluminescent device according to the present invention.
Detailed Description
An object of the present invention is to provide an o-phenanthroline compound capable of improving an electron injection amount for a light emitting portion by minimizing an energy level difference between an n-type charge generation layer and a p-type charge generation layer, and an organic electroluminescent device including the same.
It is another object of the present invention to provide a phenanthroline compound and an organic electroluminescent device comprising the same, which can minimize the diffusion of alkali metal into a p-type charge generation layer even when an n-type charge generation layer is doped with alkali metal.
According to the present invention, in the case where the n-type charge generation layer is doped with a basic metal, the alkali metal minimizes the diffusion of the alkali metal into the p-type charge generation layer in order to firmly permeate into the main compound, o-phenanthroline compound, thereby improving the lifetime of the organic light emitting device.
Provided are a phenanthroline compound capable of improving the lifetime of a device and an organic electroluminescent device comprising the same.
According to the present invention, in the case where the n-type charge generation layer is doped with a basic metal, the alkali metal minimizes the diffusion of the alkali metal into the p-type charge generation layer in order to firmly permeate into the main compound, o-phenanthroline compound, thereby using the organic electroluminescent device.
The phenanthroline compound shown in formula 1 contains more than four nitrogen atoms, and is represented by formula R1-R14The introduction of aromatic compounds and heteroaryl groups makes the nitrogen atoms more electron-rich, thus having faster electron mobility and facilitating electron transport. In addition, the N-type charge generation layer (N-CGL) contains nitrogen of sp2 hybrid orbital, which combines with a metal doped as the N-type charge generation layer to form a Gap state (Gap state). Therefore, electrons can be smoothly transferred from the P-type charge generation layer (P-CGL) to the N-type charge generation layer (N-CGL) through the gap state. The N-type charge generation layer may be composed of a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, or Yb, or an N-type doped organic material.
Further, by introducing various substituents into the above core structure, a compound having inherent properties of the introduced substituents can be synthesized. For example, a hole injection layer material and a hole transport layer material used for manufacturing an organic light emitting device are a compound that transports holes along the highest energy level orbital (HOMO) and a compound that blocks electrons that cross from the light emitting layer along the lowest energy level orbital (LUMO).
In particular, the core structure of the compound has stable characteristics with respect to electrons, and the device life can be improved. It is possible to prepare materials for the electron transport layer and the hole blocking material having an appropriate energy band gap.
In addition, by introducing various substituents into the core structure, the energy band gap can be finely adjusted, and at the same time, the interfacial properties between organic materials are improved, so that the use of the materials is diversified.
The charge generation layer (CG) includes a P-type charge generation layer (CGP) and an N-type charge generation layer (CGN), is located between a first light emitting part including a first hole transport layer, a first light emitting layer, and a first electron transport layer, and a second light emitting part including a second hole transport layer, a second light emitting layer, and a second electron transport layer in this order, and is composed of a PN connection structure connecting the first light emitting part and the second light emitting part.
That is, the above-described first electron transport layer has a PN junction structure above, and provides a charge generation layer including a P-type charge generation layer (CGP) and an N-type charge generation layer (CGN), and the above-described N-type charge generation layer material may use the phenanthroline compound represented by formula 1 according to the present invention. Here, the N-type charge generation layer supplies electrons to the first electron transport layer of the first light emitting portion, the first electron transport layer supplies electrons to the first light emitting layer, the P-type charge generation layer supplies holes to the second hole transport layer of the second light emitting portion, and the second hole transport layer supplies holes to the second light emitting layer.
Here, for the first light-emitting layer of the first light-emitting part; and a second light emitting layer of the second light emitting part, each of which may include the same or different host and the same or different dopant. In addition, in the organic light emitting device according to the embodiment of the present invention, the hole injection layer (30) is positioned between the anode (20) and the first hole transport layer (40-1), and the second electron transport layer (60-2) is positioned between the electron injection layer (70) and the second light emitting layer (50-2).
The organic electroluminescent device may have various variations, for example, a part of the organic layer may be omitted or added, may not be an overlapping structure, and may be an overlap of 2 or more than 4 light emitting layers. In addition, the organic light emitting device may include an electron transport layer and an electron injection layer, in which case the electron transport layer and the electron injection layer may use the phenanthroline compound of the present invention.
The method for preparing the organic electroluminescent device of the present invention is not particularly limited, and may be prepared by using a method and materials for preparing a light emitting device, which are well known to those skilled in the art, in addition to the phenanthroline compound represented by formula 1.
Examples
Example 1: synthesis of Compound 1-1
1) Synthesis of intermediate 1-1-2
4, 6-dibromopyridine-2-carbaldehyde (13.25g,50mmol) and the compound 1-1-1(12.01g,75 mmol) were dissolved in glacial acetic acid (700ml) and reacted for 12 hours. Introduction of the substance obtained after completion of the reaction into H2O (500ml), the solid obtained is purified and dried with water and methanol. The obtained compound and 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ) (12.5g,55mmol) were dissolved in methylene chloride (300ml) and reacted for 1 hour. The reaction mixture was extracted with benzene solvent and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then filtered and concentrated. Purification by column chromatography or distillation gave intermediate 1-1-2(9.1g, 45% yield). LC-MS: M/Z402.90 (M +).
2) Synthesis of intermediates 1-1-4
After the compound 1-1-3(3.36g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-1-2 (5.87g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-1-4 (4.10g, yield 56%). LC-MS: M/Z503.04 (M +).
3) Synthesis of Compound 1-1
After the compound 1-1-5(3.33g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-1-4(7.31g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-1 (5.23g, yield 60%). LC-MS: M/Z601.19 (M +).
Example 2: synthesis of Compounds 1-5
1) Synthesis of intermediate 1-5-2
3,5, 6-tribromopyrazine-2-carbaldehyde (17.24g,50mmol) and compound 1-5-1(12.01g,75 mmol) were dissolved in glacial acetic acid (700ml) and reacted for 12 hours. Introduction of the substance obtained after completion of the reaction into H2O (500ml), the solid obtained is purified and dried with water and methanol. The obtained compound and 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ) (12.5g,55mmol) were dissolved in methylene chloride (300ml) and reacted for 1 hour. The reaction mixture was extracted with benzene solvent and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then filtered and concentrated. Purification by column chromatography or distillation gave intermediate 1-5-2(9.70g, 40% yield). LC-MS: M/Z481.80 (M +).
2) Synthesis of intermediates 1-5-3
After the compound phenylboronic acid (1.83 g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound phenylboronic acid (1.83 g, 15mmol) was added theretoSubstance 1-5-2(7.03g, 14.5mmol), Pd (PPh)3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-5-3(4.87g, yield 70%). LC-MS: M/Z479.92 (M +).
3) Synthesis of intermediates 1-5-4
After the compound 1-1-3(3.36g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-5-3(6.99g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-5-4 (4.64g, yield 55%). LC-MS: M/Z580.06(M +).
4) Synthesis of Compounds 1-5
After the compound 1-1-5(3.33g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-5-4(8.43g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Drying and then connectingThen filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compounds 1-5 (6.69g, yield 68%). LC-MS: M/Z678.22(M +).
Example 3: synthesis of Compounds 1-16
1) Synthesis of intermediate 1-16-2
4, 6-dibromopyridine-2-carbaldehyde (13.25g,50mmol) and the compound 1-16-1(12.01g,75 mmol) were dissolved in glacial acetic acid (700ml) and reacted for 12 hours. Introduction of the substance obtained after completion of the reaction into H2O (500ml), the solid obtained is purified and dried with water and methanol. The obtained compound and 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ) (12.5g,55mmol) were dissolved in methylene chloride (300ml) and reacted for 1 hour. The reaction mixture was extracted with benzene solvent and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then filtered and concentrated. Purification by column chromatography or distillation gave intermediate 1-16-2(8.1g, 40% yield). LC-MS: M/Z402.91 (M +).
2) Synthesis of intermediates 1-16-4
After the compound 1-1-3(3.36g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-16-2 (5.87g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-16-4 (3.95g, yield 54%). LC-MS: M/Z503.05 (M +).
3) Synthesis of intermediates 1 to 16
After the compound 1-16-5 (3.36g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-16-4(7.31g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compounds 1 to 16 (5.08g, yield 58%). LC-MS: M/Z603.18 (M +).
Example 4: synthesis of Compounds 1-23
1) Synthesis of intermediate 1-23-1
After the compound 1-1-3(3.36g, 15mmol) was dissolved in 1, 4-dioxane (130mL), 4, 6-dibromopyridine-2-carbaldehyde (3.84g, 14.5mmol) and Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-23-1 (2.32g, yield 44%). LC-MS: M/Z363.00(M +).
2) Synthesis of intermediate 1-23-2
After the compound 1-1-5(3.33g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 1-23-1(5.28g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-23-2 (4.75g, yield 71%). LC-MS: M/Z461.15 (M +).
3) Synthesis of intermediates 1-23-3
1-23-2(23.08g,50mmol) and 2-amino-3-bromophenol (14.01g,75 mmol) were dissolved in glacial acetic acid (700ml) and reacted for 12 hours. Introduction of the substance obtained after completion of the reaction into H2O (500ml), the solid obtained is purified and dried with water and methanol. The obtained compound and 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ) (12.5g,55mmol) were dissolved in methylene chloride (300ml) and reacted for 1 hour. The reaction mixture was extracted with benzene solvent and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then filtered and concentrated. Purification by column chromatography or distillation gave intermediate 1-2(12.59g, 40% yield). LC-MS: M/Z628.09 (M +).
4) Synthesis of intermediates 1-23-4
After the compound methyl 2- (2- (1-hydroxyethyl) phenyl) acetate (2.92 g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compounds 1-23-3(9.13g, 14.5mmol), Pd (PPh) and the like were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. In thatAfter the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 1-23-4 (8.62g, yield 85%). LC-MS: M/Z699.23(M +).
5) Synthesis of Compounds 1-23
Compound 1-23-4 (34.99 g,50mmol) was dissolved in 430 mL THF and LTMP (by dissolving 27.2 mL TMP in 250 mL THF at 0 ℃) was added at 0 ℃. After stirring for 8 hours, distilled water was added and extracted with EA. Dried over magnesium sulfate and distilled under reduced pressure. Column chromatography gave intermediates 1-23 (116.29 g, 50%). LC-MS: M/Z651.21(M +).
Example 5: synthesis of Compounds 2-3
1) Synthesis of intermediate 2-3-3
After the compound 2-3-2(4.35g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 2-3-1(5.37g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 2-3-3(3.26g, yield 42%). LC-MS: M/Z535.12 (M +).
2) Synthesis of Compounds 2-3
After the compound 1-1-5(3.33g, 15mmol) was dissolved in 1, 4-dioxane (130mL), 2-3-3(7.77g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 2-3 (5.70g, yield 58%). LC-MS: M/Z677.22 (M +).
Example 6: synthesis of Compounds 2-23
1) Synthesis of intermediate 2-23-2
After the compound 2-23-1 (5.10 g, 15mmol) was dissolved in 1, 4-dioxane (130mL), 2-3-1(5.37g, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g, 0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compound 2-23-2 (3.23g, yield 38%). LC-MS: M/Z585.14 (M +).
2) Synthesis of Compounds 2-23
After the compound 1-1-5(3.33g, 15mmol) was dissolved in 1, 4-dioxane (130mL), the compound 2-23-2(8.50, 14.5mmol), Pd (PPh) were added thereto3)4(0.18g，0.15mmol) and K2CO3(12.8 g, 93mmol), and the resultant was stirred at 100 ℃ for 6 hours. After the reaction was terminated, the resultant was cooled to room temperature and extracted with distilled water and ethyl acetate. The organic layer was MgSO4Dried, and then filtered and concentrated. The concentrated residue was purified by column chromatography using ethyl acetate and hexane as developing agents to obtain the objective compounds 2-23 (5.17g, yield 49%). LC-MS: M/Z727.24 (M +).
Example 7: synthesis of Compounds 2-32
Synthesis of Compounds 2 to 32 by reference to the procedures for Compounds 1 to 16 in example 3 gave compounds 2 to 32 (5.50g, yield 63%). LC-MS: M/Z602.19(M +).
Device embodiments
As shown in fig. 1, the organic electroluminescent device of the present invention includes an anode (20), a first hole transport layer (40-1), a first light emitting layer (50-1) including a host and a dopant, a first light emitting unit including a first electron transport layer (60-1), a charge generation layer (CG) including a P-type charge generation layer (CGP) and an N-type charge generation layer (CGN), and a second light emitting unit including a second hole transport layer (40-2), a second light emitting layer (50-2) including a host and a dopant, a second light emitting unit including a second electron transport layer (60-2) and a cathode (80).
The layers of the organic electroluminescent element of the present invention can be formed by vacuum evaporation, sputtering, ion plating, or the like, or by wet film formation such as spin coating, printing, or the like, and the solvent used is not particularly limited.
< Experimental example 1> production of organic electroluminescent device
First embodiment
Manufacturing of organic electroluminescent device:
the ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. The patterned ITO glass substrate was then washed, and then placed in a vacuum chamber with a standard pressure set at 1X 10-6And (4) supporting. Thereafter evaporating HATCN on the ITO substrate to form a first Hole Injection Layer (HIL) having a thickness of 50A, and evaporating HTL-1 on the above first hole injection layer to form a Hole Transport Layer (HTL) having a thickness of 600A, above which Hole Transport Layer (HTL) is formedCBP + RD-1 (3 wt%) was vapor deposited on the transport layer to form an emitting layer (EML) having a thickness of 200 a, and an N-type charge generation layer having a thickness of 150 a and a P-type charge generation layer (thickness of 150 a) of HATCN were vapor deposited by doping Yb (2 wt%) in Alq3 (thickness of 300 a) and compound 1-1 represented by formula 1 in this order. Then, a second Hole Transport Layer (HTL) having a thickness of 50 a was formed by evaporation of HTL-1, a second light emitting layer (EML) having a thickness of 200 a was formed by evaporation of BH + BD (3 wt%), a second electron transport layer having a thickness of 300 a was formed by evaporation of Alq3 in this order, LiF (having a thickness of 10 a), Al (having a thickness of 2000 a) were evaporated, and an organic electroluminescent device was manufactured.
Second embodiment
An organic electroluminescent device of the second embodiment was fabricated by the same method as the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with compound 1-5 from compound 1-1 of the first embodiment.
Third embodiment
An organic electroluminescent device of the third embodiment was fabricated by the same method as that of the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with the compound 1-16 from the compound 1-1 of the first embodiment.
Fourth embodiment
An organic electroluminescent device of the fourth embodiment was fabricated by the same method as that of the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with the compound 1-23 from the compound 1-1 of the first embodiment.
Fifth embodiment
An organic electroluminescent device of the fifth embodiment was fabricated by the same method as that of the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with compound 2-3 from compound 1-1 of the first embodiment.
Sixth embodiment
An organic electroluminescent device according to the sixth embodiment was fabricated by the same method as that of the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with the compound 2-23 from the compound 1-1 according to the first embodiment.
Seventh embodiment
An organic electroluminescent device according to the sixth embodiment was fabricated by the same method as that of the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with the compounds 2 to 32 from the compound 1-1 according to the first embodiment.
Comparative example 1
The organic electroluminescent device of comparative example 1 was prepared in the same manner as in the first embodiment described above, except that the N-type charge generation layer (N-CGL) of the organic electroluminescent device was replaced with the compound Ref-1 instead of the compound 1 of the first embodiment.
The organic electroluminescent device was fabricated using standard methods known in the art at 10mA/cm2Voltage and efficiency were tested under current conditions.
Table 1 shows the performance test results of the organic electroluminescent devices prepared in the examples and comparative examples of the present invention.
TABLE 1
As shown in table 1, the organic electroluminescent device including the specific compound according to the present disclosure as a CGL material has a reduced driving voltage and improved current efficiency compared to the organic electroluminescent device in the comparative example.
The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. The structure of the phenanthroline compound is shown as a formula 1:
wherein Ar is1Is a substituted or unsubstituted C12-C30 phenanthroline derivative group;
Ar2is substituted or unsubstituted oxazolo [5,4-h]Quinolyl, phenanthrene [4,3-d ]]Oxazolyl, oxazolo [4',5':3, 4)]Benzo [1,2-h ]]Quinolyl or oxazolo [5',4':3,4]Benzo [1,2-h ]]A quinolyl group;
Ar3and Ar4Each independently selected from hydrogen, deuterium, halogen, C6-C30 aryl or C5-C30 heteroaryl, wherein at least one is C12-C30 aryl or C12-C30 heteroaryl;
l is phenyl, pyridyl, pyrimidinyl, pyrazinyl, or imidazolyl.
2. The phenanthroline compound according to claim 1, wherein the phenanthroline compound is represented by any one of formulae 1-1 to 1-8 below:
wherein R is1To R14Each independently selected from substituted or unsubstituted hydrogen, deuterium, halogen, alkyl, C6-C30 aryl or C5-C30 heteroaryl;
Ar3and Ar4Each independently selected from hydrogen, deuterium, halogen, C6-C30 aryl or C5-C30 heteroaryl, wherein at least one is C12-C30 aryl or C12-C30 heteroaryl;
Ar5is substituted or unsubstituted C6-C30 aryl or C5-C30 heteroaryl;
X1is carbon or nitrogen.
3. The phenanthroline compound according to claim 2, wherein R is1To R14Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted naphthyridinyl, or combinations thereof.
4. The phenanthroline compound according to claim 2, wherein Ar is3To Ar5Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted naphthyridinyl, or combinations thereof.
5. The phenanthroline compound of claim 2, wherein the phenanthroline compound is any one of:
6. an organic electroluminescent device comprising:
a first electrode;
a second electrode, and
an organic layer between the first electrode and the second electrode;
the organic layer comprises the phenanthroline compound of any one of claims 1-5.
7. The organic electroluminescent device according to claim 6, wherein at least one of the organic layers is a charge generation layer or an electron transport layer.
8. The organic electroluminescent device according to claim 7, wherein the charge generation layer is an n-type charge generation layer.
9. The organic electroluminescent device according to claim 8, wherein the n-type charge generation layer is composed of a metal or an organic material doped with n-type, wherein the metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, or Yb.
10. An organic electroluminescent device comprising:
a first electrode;
a second electrode;
a first light-emitting portion of a first light-emitting layer located between the first electrode and the second electrode;
a second light emitting part of a second light emitting layer between the second electrode and the first light emitting part, and
a first charge generation layer located between the first light-emitting portion and the second light-emitting portion;
at least one of the first luminescent moiety, the second luminescent moiety, or the first charge generation layer comprises an o-phenanthroline compound according to any one of claims 1-5.
11. Use of a phenanthroline compound according to any one of claims 1-5 for the manufacture of organic electroluminescent devices.
12. A display or lighting apparatus comprising the organic electroluminescent device according to claim 6 or 10.
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