Patent Application
20230139051
This application claims the priority of Chinese Patent Application No. 202210883191.5, filed with the China National Intellectual Property Administration on Jul. 26, 2022, and titled with “BENZOXAZOLE DERIVATIVE AND ELECTROLUMINESCENT APPLICATION THEREOF”, which is hereby incorporated by reference.
The present disclosure relates to the field of organic electroluminescent materials, and in particular to a benzoxazole derivative and an electroluminescent application thereof.
The electron transport material used in traditional electroluminescent devices is Alq3, but the electron mobility of Alq3 is relatively low (about 10−6 cm2/Vs), which makes the electron transport and hole transport of the device unbalanced. With the commercialization and practical application of electroluminescent devices, ETL materials with higher transport efficiency and better performance are expected, in the field of which researchers have done a lot of exploratory work.
The glass transition temperature of current materials is low, generally lower than 85° C. When the device is running, the Joule heat generated will lead to molecular degradation and changes in molecular structure, resulting in low efficiency and poor thermal stability of the panel. The materials are easy to be crystallized after a long time, and the intermolecular charge transition mechanism thereof will be different from the mechanism of the amorphous thin film under the normal operation, resulting in a decrease in the performance of electron transport.
It is of very important practical application value to design and develop stable and efficient electron transport materials and/or electron injection materials that can have both high electron mobility and high glass transition temperature, and are effectively doped with metal Yb or Liq, to reduce threshold voltage, improving efficiency of device, and prolonging lifetime of device.
In view of this, the problem to be solved by the present disclosure is to provide a benzoxazole derivative and an electroluminescent application thereof, which can effectively improve the lifetime and efficiency of the device.
The present disclosure provides a benzoxazole derivative having the structure as shown in formula I:
R has any of the following structures:
A is
X1, X2, X3 are independently selected from the group consisting of N, O, S or Si;
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 are independently selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted aryl or heteroaryl;
L1, L2, L3 are independently selected from the group consisting of single bonds, substituted or unsubstituted aryl or heteroaryl, and at least two of L1, L2, and L3 are not single bonds;
Ar1 and Ar2 are independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl;
#indicates the linking site.
The present disclosure provides an organic light-emitting device, the organic light-emitting device includes an anode, a cathode, and an organic thin film layer located between the anode and the cathode, and the organic thin film layer includes an electron transport layer, and the electron transport layer includes at least one of the above-mentioned benzoxazole derivatives.
The present disclosure provides a display panel comprising the above organic light-emitting device.
The present disclosure provides a benzoxazole derivative having a structure as shown in formula I.
R has any of the following structures:
A is
X1, X2, X3 are independently selected from the group consisting of N, O, S or Si;
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 are independently selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted aryl or heteroaryl;
L1, L2, L3 are independently selected from the group consisting of single bonds, substituted or unsubstituted aryl or heteroaryl, and at least two of L1, L2, and L3 are not single bonds;
Ar1 and Ar2 are independently selected from the group consisting of substituted or unsubstituted aryl or heteroaryl;
#indicates the linking site.
In one embodiment, the substituents of the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, L1, L2, L3, Ar1 and Ar2 are independently selected from the group consisting of D, halogen, cyano, aryl or heteroaryl.
In one embodiment, the X2 is O, and the X3 is N.
In one embodiment, the X1 is O.
In one embodiment, the R has any of the following structures:
R11 is selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted aryl or heteroaryl;
#is the linking site.
In one embodiment, the R11 is selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted monocyclic aryl, monocyclic heteroaryl, fused aryl formed by the fusion of 2˜3 aromatic rings, heteroaryl formed by the fusion of 2˜3 aromatic rings and heteroaromatic rings, and heteroaryl formed by the fusion of 2˜3 heteroaromatic rings.
In one embodiment, the monocyclic aryl is phenyl.
In one embodiment, the monocyclic heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the aromatic ring fused to form the fused aryl is a benzene ring.
In one embodiment, the aromatic ring fused to form the heteroaryl is a benzene ring.
In one embodiment, the heteroaromatic ring fused to form the heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the R11 is selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, naphthyl, anthracenyl, phenanthryl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or 1,5-naphthyridinyl.
In one embodiment, the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 are independently selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted monocyclic aryl, monocyclic heteroaryl, fused aryl formed by the fusion of 2˜3 aromatic rings, heteroaryl formed by the fusion of 2˜3 aromatic rings and heteroaromatic rings, and heteroaryl formed by the fusion of 2˜3 heteroaromatic rings.
In one embodiment, the monocyclic aryl is phenyl.
In one embodiment, the monocyclic heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the aromatic ring fused to form the fused aryl is a benzene ring.
In one embodiment, the aromatic ring fused to form the heteroaryl is a benzene ring.
In one embodiment, the heteroaromatic ring fused to form the heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 are independently selected from the group consisting of H, D, halogen, cyano, substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, naphthyl, anthracenyl, phenanthryl, 1,10-phenanthrolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or 1,5-naphthyridinyl.
In one embodiment, the L1, L2, L3 are independently selected from the group consisting of single bonds, substituted or unsubstituted monocyclic aryl, monocyclic heteroaryl, fused aryl formed by the fusion of 2˜3 aromatic rings, heteroaryl formed by the fusion of 2˜3 aromatic rings and heteroaromatic rings, and heteroaryl formed by the fusion of 2˜3 heteroaromatic rings, and at least two of L1, L2, and L3 are not single bonds.
In one embodiment, the monocyclic aryl is phenyl.
In one embodiment, the monocyclic heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the aromatic ring fused to form the fused aryl is a benzene ring.
In one embodiment, the aromatic ring fused to form the heteroaryl is a benzene ring.
In one embodiment, the heteroaromatic ring fused to form the heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the L1, L2, L3 are independently selected from the group consisting of single bonds, substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, naphthyl, anthracenyl, phenanthryl, 1,10-phenanthrolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or 1,5-naphthyridinyl, and at least two of L1, L2 and L3 are not single bonds.
In one embodiment, two or three of the L1, L2, and L3 are not single bonds.
In one embodiment, the Ar1 and Ar2 are independently selected from the group consisting of substituted or unsubstituted monocyclic aryl, monocyclic heteroaryl, fused aryl formed by the fusion of 2˜3 aromatic rings, heteroaryl formed by the fusion of 2˜3 aromatic rings and heteroaromatic rings, and heteroaryl formed by the fusion of 2˜3 heteroaromatic rings, and at least two of L1, L2, and L3 are not single bonds.
In one embodiment, the monocyclic aryl is phenyl.
In one embodiment, the monocyclic heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the aromatic ring fused to form the fused aryl is a benzene ring.
In one embodiment, the aromatic ring fused to form the heteroaryl is a benzene ring.
In one embodiment, the heteroaromatic ring fused to form the heteroaryl is a five-membered or six-membered heteroaryl having 1-3 N atoms.
In one embodiment, the Ar1 and Ar2 are independently selected from the group consisting of substituted or unsubstituted phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, naphthyl, anthracenyl, phenanthryl, 1,10-phenanthrolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or 1,5-naphthyridinyl.
In one embodiment, the benzoxazole derivative has any of the following structures:
The present disclosure provides an organic light-emitting device comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode, and the organic thin film layer includes an electron transport layer, and the electron transport layer includes at least one of the above-mentioned benzoxazole derivatives.
In one embodiment, the electron transport layer includes the benzoxazole derivative and LiQ.
The above-mentioned LiQ refers to 8-hydroxyquinolinolato-lithium.
The present disclosure provides a display panel comprising the above organic light-emitting device.
The organic light-emitting device provided by the present disclosure can be an organic light-emitting device well known to those skilled in the art. In one embodiment of the present disclosure, the organic light-emitting device includes a substrate plate, an ITO anode, a first hole transport layer, a second hole transport layer, an electron blocking layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (magnesium-silver electrode, the mass ratio of magnesium-silver is 1:9) and a capping layer (CPL).
In one embodiment of the present disclosure, the anode material of the organic light-emitting device can be selected from the group consisting of metals-copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc. and alloys thereof; such as metal oxides-indium oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO); such as conductive polymers—polyaniline, polypyrrole, poly(3-methylthiophene). In addition to the above materials and combinations thereof that contribute to hole injection, materials known to be suitable for use as anodes are also included.
In one embodiment of the present disclosure, the cathode material of the organic light-emitting device can be selected from the group consisting of metals-aluminum, magnesium, silver, indium, tin, titanium, etc. and alloys thereof; such as multi-layer metal materials-LiF/Al, LiO2/Al, BaF2/Al; in addition to the above materials and combinations thereof that contribute to electron injection, materials known to be suitable for use as cathodes are also included.
In one embodiment of the present disclosure, the organic thin film layer in the organic photoelectronic device, such as the organic light-emitting device, includes at least one light-emitting layer (EML), and may also include other functional layers, comprising a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a hole blocking layer (HBL), an electron transport layer (ETL), and an electron injection layer (EIL).
In one embodiment of the present disclosure, the organic light-emitting device is prepared according to the following method:
Forming an anode on a transparent or opaque smooth substrate plate, forming an organic thin layer on the anode, and forming a cathode on the organic thin layer.
In one embodiment of the present disclosure, known film forming methods such as vapor deposition, sputtering, spin coating, dipping, and ion plating can be used to form the organic thin layer.
The present disclosure provides a display device comprising the above-mentioned display panel.
In the present disclosure, an organic light-emitting device (OLED device) can be used in a display device, and the organic light-emitting display device can be a mobile phone display, a computer display, a TV display, a smart watch display, a smart car display panel, a VR or AR helmet display, displays of various smart devices, etc.
The following will clearly and completely describe the embodiments of the present disclosure. The described examples are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the examples of the present disclosure, all other examples may be obtained.
Preparation of A1
2-amino-3-dibenzofuranol (20.0 g, 101 mmol) and triethyl formate (20 mL) were added to a reaction vessel. The obtained mixture was refluxed for 9 hours until the reaction was completed. Triethyl formate was then removed. The residue was separated by column chromatography to obtain M1-1 (18.06 g, 86%).
Intermediate 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine (8.7 g, 20.00 mmol), 1,4-diiodonaphthalene (7.6 g, 20.05 mmol), Pd(PPh3)4(1.13 g, 0.98 mmol), and K2CO3 (8.11 g, 58.66 mmol) were mixed into 100 ml of toluene, 25 ml of H2O and 25 ml of EtOH under nitrogen gas stream, and the mixture was stirred at 110° C. for 4 hours. After the reaction was completed, the mixture was extracted with dichloromethane, added with MgSO4, and filtered. After the solvent of the filtered organic layer was removed, the residue was subjected to column chromatography to obtain 9.54 g (yield: 85%) of the target compound M1-2.
Copper (I) thiophene-2-carboxylate (0.1 g, 0.5 mmol), 2,2′-bipyridine (0.1 g, 0.5 mmol), and lithium were added to tert-butoxide (2.0 g, 25 mmol) and dry N,N-dimethylformamide (50 ml, 0.2 M) with a magnetic stir bar under nitrogen atmosphere. After stirring for 5 minutes, the color of the solvent changed from light green to light yellow, and M1-1 (2.1 g, 10 mmol) and M1-2 (22.4 g, 40 mmol) were added to the mixture. The obtained solution was then irradiated with a blue LED and stirred at room temperature for 16 hours. The obtained suspension was filtered on a pad of silica gel using ethyl acetate as eluent and evaporated in vacuum. The residue was separated by column chromatography to obtain 5.14 g of product A1, (yield: 80%).
Preparation of A2
M2-1 was prepared in the same way as M1-2, following the same preparation method of M1-2, using the same molar ratio, except that 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine was replaced by 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine.
A2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-2 was replaced by M2-1.
Preparation of A5
M3-1 was prepared in the same way as M1-2, following the same preparation method of M1-2, using the same molar ratio, except that 1,4-diiodonaphthalene was replaced by 1,4-diiodobenzene, and 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine was replaced with 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-naphthyl]-1,3,5-triazine.
A5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-2 was replaced by M3-1.
Preparation of A12
100 ml of ethanol, 2-amino-3-dibenzofuranol (20.0 g, 101 mmol), NBS (2.5 g, 220 mmol) and copper nitrate (1.3 g, 10 mmol) were sequentially added in a reactor, and the mixture was stirred at room temperature for 0.5 h, then heated up to 50° C. and maintained for 3 h until the reaction was completed. Then the reaction solution was cooled to 20° C., and poured into 100 ml of water, and the mixture was stirred for 2 h. The obtained mixture was suction filtered, and the filter cake was stirred with 100 ml of water at room temperature for 1 h. The mixture was suction filtered, and then dried at 50° C. to obtain M4-1 (23.3 g, 84%).
M4-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by M4-1.
M4-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-2 was replaced with iodobenzene.
Intermediate M4-3 (7.2 g, 19.55 mmol), pinacol bisborate (5.96 g, 23.46 mmol), Pd(OAc)2 (0.13 g, 0.59 mmol), KOAc (3.84 g, 39.11 mmol) and 100 ml of toluene were mixed under nitrogen atmosphere, and the mixture was stirred at 100° C. for 8 hours. After the reaction was completed, the mixture was extracted with dichloromethane, added with MgSO4, and the obtained mixture was filtered. After the solvent of the filtered organic layer was removed, the residue was subjected to column chromatography to obtain 7.2 g (yield: 88%) of intermediate M4-4.
Intermediates M4-4 (6.7 g, 20.0 mmol), M1-2 (11.2 g, 20.0 mmol), Pd(PPh3)4(1.13 g, 0.98 mmol), K2CO3 (8.11 g, 58.66 mmol) were mixed into 100 ml of toluene, 25 ml of H2O and 25 ml of EtOH under nitrogen gas stream, and the mixture was stirred at 110° C. for 4 hours. After the reaction was completed, the mixture was extracted with dichloromethane, added with MgSO4, and the obtained mixture was filtered. After the solvent of the filtered organic layer was removed, the residue was subjected to column chromatography to obtain 12.9 g (yield: 90%) of the target compound A12.
Preparation of A21
M5-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced with 4-amino-6-chloro-1,3-benzenediol.
M5-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M5-1, and M1-2 was replaced by 2-bromo-4-chlorophenol.
M5-2 (5.0 g, 20 mmol) and 1,2-dichlorobenzene (250 mL) were added to a reactor. The reaction mixture was heated at 160° C. for 8 hours. After the reaction was completed, the organic substance was dissolved in chloroform (100 mL). After the solvent was removed, the crude compound was separated by column chromatography to obtain M5-3 (4.6 g, 77%).
M5-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M5-3.
M5-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M5-4, and M1-2 was replaced by 4-iodopyridine.
M5-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M5-5.
A21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M5-6.
Preparation of A24
M6-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M6-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M6-2 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M6-1.
M6-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by M6-2.
M6-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M6-3, and M1-2 was replaced by 1-iodonaphthalene.
M6-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M6-4.
A24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M6-5.
Preparation of B1
M7-1 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 3-amino-2-dibenzofuranol.
B1 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M7-1.
Preparation of B2
B2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced with M7-1, and M1-2 was replaced with M2-1.
Preparation of B5
B5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M7-1, and M1-2 was replaced by M3-1.
Preparation of B12
M8-1 was prepared in the same way as M4-1, following the same preparation method of M4-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 3-amino-2-dibenzofuranol.
M8-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M8-1.
M8-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M8-2, and M1-2 was replaced by iodobenzene.
M8-4 was the same as that of M4-4, following the same preparation method of M4-4, using the same molar ratio, except that M4-3 was replaced by M8-3.
B12 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M8-4.
Preparation of B21
M9-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by 2-amino-5-chloro-1,4-benzenediol.
M9-2
M9-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M9-1, and M1-2 was replaced by 2-bromo-4-chlorophenol.
M9-3 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M9-2.
M9-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M9-3.
M9-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M9-4, and M1-2 was replaced by 4-iodopyridine.
M9-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M9-5.
B21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M9-6.
Preparation of B24
M10-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M9-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M10-2 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M10-1.
M10-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M10-2.
M10-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M10-3, and M1-2 was replaced by 1-iodonaphthalene.
M10-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M10-4.
B24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M10-5.
Preparation of C1
M11-1 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by 3-amino-4-dibenzofuranol.
C1 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M11-1.
Preparation of C2
C2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced with M11-1, and M1-2 was replaced with M2-1.
Preparation of C5
C5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M11-1, and M1-2 was replaced by M3-1.
Preparation of C11
M12-1 was prepared in the same way as M4-1, following the same preparation method of M4-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 3-amino-4-dibenzofuranol.
M12-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M12-1.
M12-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M12-2, and M1-2 was replaced by iodobenzene.
M12-4 was prepared in the same way as M4-4, following the same preparation method of M4-4, using the same molar ratio, except that M4-3 was replaced by M12-3.
C11 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M12-4.
Preparation of C21
M13-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced with 3-amino-6-chloro-1,2-benzenediol.
M13-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M13-1, and M1-2 was replaced by 2-bromo-4-chlorophenol.
M13-3 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M13-2.
M13-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M13-3.
M13-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M13-4, and M1-2 was replaced by 4-iodopyridine.
M13-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M13-5.
C21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M13-6.
Preparation of C24
M14-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M13-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M14-2 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M14-1.
M14-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by M14-2.
M14-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M14-3, and M1-2 was replaced by 1-iodonaphthalene.
M14-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M14-4.
C24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M14-5.
Preparation of D1
M15-1 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 4-amino-3-dibenzofuranol.
D1 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M15-1.
Preparation of D2
D2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M15-1, and M1-2 was replaced by M2-1.
Preparation of D5
D5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M15-1, and M1-2 was replaced by M3-1.
Preparation of D11
M16-1 was prepared in the same way as M4-1, following the same preparation method of M4-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 4-amino-3-dibenzofuranol.
M16-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M16-1.
M16-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M16-2, and M1-2 was replaced by iodobenzene.
M16-4 was prepared in the same way as M4-4, following the same preparation method of M4-4, using the same molar ratio, except that M4-3 was replaced by M16-3.
D11 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M16-4.
Preparation of D21
M17-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced with 2-amino-4-chloro-1,3-benzenediol.
M17-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced with M17-1, and M1-2 was replaced with 2-bromo-4-chlorophenol.
M17-3 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M17-2.
M17-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M17-3.
M17-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M17-4, and M1-2 was replaced by 4-iodopyridine.
M17-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M17-5.
D21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M17-6.
Preparation of D24
M18-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M18-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M18-2 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M18-1.
M18-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M18-2.
M18-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M18-3, and M1-2 was replaced by 1-iodonaphthalene.
M18-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M18-4.
D24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M18-5.
Preparation of E1
M19-1 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 1-amino-2-dibenzofuranol.
E1 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M19-1.
Preparation of E2
E2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M19-1, and M1-2 was replaced by M2-1.
Preparation of E5
E5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M19-1, and M1-2 was replaced by M3-1.
Preparation of E12
M20-1 was prepared in the same way as M4-1, following the same preparation method of M4-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with 1-amino-2-dibenzofuranol.
M20-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M20-1.
M20-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced with M20-2, and M1-2 was replaced with iodobenzene.
M20-4 was prepared in the same way as M4-4, following the same preparation method of M4-4, using the same molar ratio, except that M4-3 was replaced by M20-3.
E12 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M20-4.
Preparation of E21
M21-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced with 2-amino-3-chloro-1,4-benzenediol.
M21-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M21-1, and M1-2 was replaced by 2-bromo-4-chlorophenol.
M21-3 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M21-2.
M21-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M21-3.
M21-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M21-4, and M1-2 was replaced by 4-iodopyridine.
M21-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M21-5.
E21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M21-6.
Preparation of E24
M22-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M21-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M22-2 was prepared in the same way as A M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M22-1.
M22-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M22-2.
M22-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M22-3, and M1-2 was replaced by 1-iodonaphthalene.
M22-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M22-4.
E24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M22-5
Preparation of F1
M23-1 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by 2-amino-1-dibenzofuranol.
F1 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M23-1.
Preparation of F2
F2 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M23-1, and M1-2 was replaced by M2-1.
Preparation of F5
F5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M23-1, and M1-2 was replaced by M3-1.
Preparation of F12
M24-1 was prepared in the same way as M4-1, following the same preparation method of M4-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced by 2-amino-1-dibenzofuranol.
M24-2 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M24-1.
M24-3 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced with M24-2, and M1-2 was replaced with iodobenzene.
M24-4 was prepared in the same way as M4-4, following the same preparation method of M4-4, using the same molar ratio, except that M4-3 was replaced by M24-3.
F12 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M24-4.
Preparation of F21
M25-1 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by 4-amino-2-chloro-1,3-benzenediol.
M25-2 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M25-1, and M1-2 was replaced by 2-bromo-4-chlorophenol.
M25-3 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M25-2.
M25-4 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M25-3.
M25-5 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M25-4, and M1-2 was replaced by 4-iodopyridine.
M25-6 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M25-5.
F21 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M25-6.
Preparation of F24
M26-1 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-3 was replaced by M25-1, and M1-2 was replaced by 2-bromo-5-chlorophenol.
M26-2 was prepared in the same way as M5-3, following the same preparation method of M5-3, using the same molar ratio, except that M5-2 was replaced by M26-1.
M26-3 was prepared in the same way as M1-1, following the same preparation method of M1-1, using the same molar ratio, except that 2-amino-3-dibenzofuranol was replaced with M26-2.
M26-4 was prepared in the same way as A1, following the same preparation method of A1, using the same molar ratio, except that M1-1 was replaced by M26-3, and M1-2 was replaced by 1-iodonaphthalene.
M26-5 was prepared in the same way as M4-3, following the same preparation method of M4-3, using the same molar ratio, except that M4-2 was replaced by M26-4.
F24 was prepared in the same way as A12, following the same preparation method of A12, using the same molar ratio, except that M4-4 was replaced by M26-5.
The compounds synthesized in the above examples were identified by matrix-assisted laser desorption ionization time-of-flight mass spectrometry and elemental analysis, and the results thereof are shown in Table 1 below.
For the organic compounds provided by the present disclosure, the distribution of the molecular frontier orbitals HOMO and LUMO was optimized and calculated through the Gaussian 09 program package (Gaussian Inc.) at the B3LYP/6-31G(d) calculation level using density functional theory (DFT). In one embodiment, the singlet energy level ES and triplet energy level ET of compound molecules were simulated and calculated based on time-dependent density functional theory (TDDFT). The results are shown in Table 2.
A glass substrate plate coated with ITO (indium tin oxide) in a thin film at a thickness of 1000 Å was put into distilled water in which a detergent was dissolved, and washed with ultrasonic waves. The ITO was washed for 30 minutes, ultrasonic washed for 10 minutes with distilled water twice. After the ITO was washed with distilled water, it was ultrasonic washed with a solvent of isopropanol, acetone, and methanol, dried, and then transported to a plasma cleaning machine. In one embodiment, after the above substrate plate was washed for 5 minutes by oxygen plasma, it was transported to a vacuum deposition machine.
On the ITO transparent electrode prepared above, the following compound [HI] was thermally vacuum-deposited to a thickness of 600 Å to form a hole injection layer. On the above hole injection layer, hexacyano hexaazatriphenylene (HAT) of the following chemical formula and the following compound [HT] were sequentially vacuum-deposited to 50 Å and 600 Å respectively to form a hole transport layer.
Next, on the above hole transport layer, the following compounds [BH] and [BD] were vacuum deposited at a weight ratio of 25:1 to a film thickness of 200 Å to form a light-emitting layer.
On the above light-emitting layer, the following compounds [ET] and [LiQ] (8-hydroxyquinolinolato-lithium) were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer in a thickness of 150 Å. On the above electron injection and transport layer, lithium fluoride (LiF) and aluminum were sequentially vapor deposited to a thickness of 10 Å and 1000 Å respectively to form a cathode.
In the above process, the vapor deposition rate of organic substance was maintained at 0.4 to 0.9 Å/sec, the vapor deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and the vapor deposition rate of aluminum was maintained at 2 Å/sec, during vapor deposition, the vacuum degree was maintained at 1×10−7 to 5×10−8 Torr, to produce an organic light-emitting device.
Organic light-emitting devices were produced by the same method as in the Comparative Example, according to the above Comparative Example, except that the compound [ET] was replaced with the compounds synthesized in Example 1.
The driving voltage and luminous efficiency were measured at a current density of 10 mA/cm2 for the organic light-emitting devices fabricated using the respective compounds as electron transport layers in the above-mentioned Experimental Examples and Comparative Example, and the time required to reach 95% of the initial brightness (LT95) was measured at a current density of 20 mA/cm2. The results are shown in Table 3 below.
As shown in Table 3, the organic light-emitting devices of Experimental Examples using the compounds provided by the present disclosure as electron transport layer materials exhibited superior device characteristics compared to the organic light-emitting device prepared in Comparative Example using the compound that was not included in formula 1.
In general, considering that the luminous efficiency and lifetime characteristics of organic light-emitting devices have a trade-off relationship with each other, it can be seen that compared with the device of the Comparative Example, when the substituents in formula 1 are changed, the electron transport rate can be adjusted, and the balance of current carrier of the device can be adjusted, which shows a marked improvement.
The descriptions of the above examples are only used to help understand the method and the embodiments of the present disclosure. It should be noted that several improvements and modifications can be made to the present disclosure, and these improvements and modifications also fall within the claims and the embodiments of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210883191.5 | Jul 2022 | CN | national |
