CN107827879B - Material for flexible display, preparation method thereof and organic electroluminescent device - Google Patents

Material for flexible display, preparation method thereof and organic electroluminescent device Download PDF

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CN107827879B
CN107827879B CN201710826172.8A CN201710826172A CN107827879B CN 107827879 B CN107827879 B CN 107827879B CN 201710826172 A CN201710826172 A CN 201710826172A CN 107827879 B CN107827879 B CN 107827879B
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马晓宇
林文晶
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Olide (Shanghai) Photoelectric Material Technology Co., Ltd.
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Abstract

The invention relates to a material for flexible display, a preparation method thereof and an organic electroluminescent device, and relates to the field of organic electroluminescent devices. The dibenzophenazine derivative is prepared by connecting a dibenzophenazine compound containing a substituent group with dibenzofuran, dibenzothiophene or dibenzoselenophene containing the substituent group, the compound increases the electron mobility, and particularly can be used as a hole transport material for preparing an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is long. The preparation method of the material for flexible display provided by the invention is simple and feasible, and is easy for industrial production. The organic electroluminescent device provided by the present invention is suitably used for flat panel displays, flat light emitters, surface-emitting OLED light emitters for illumination, flexible light emitters, light sources for copying machines, printers, LCD backlights or measuring machines, display panels, signs, and the like.

Description

Material for flexible display, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to a material for flexible display, a preparation method thereof and an organic electroluminescent device.
Background
The phenazine compounds are various in types, wherein natural phenazine compounds mostly have broad-spectrum antibacterial and antitumor activities and are widely applied to the fields of medicines, agriculture and the like. At present, thousands of phenazine compounds are entering the field of research, but only more than 100 of them are natural products. The natural phenazine compound is mostly produced by bacteria or actinomycetes, and can reach higher concentration in vitro under the culture condition; they are generally of a certain color and have a specific absorption spectrum, which is different due to the position of the substituents on the heterocycle, and these substituents also determine the difference in the physicochemical properties of the different compounds. However, the phenazine compounds are applied to the field of organic electroluminescence, and are rarely researched, and particularly, the phenazine compounds are used as hole transport materials of organic electroluminescence devices.
Representative substances of hole transport materials in current organic electroluminescent devices, such as Alq3TmPyPB, TPBi and the like, which are required to have thermal stability, fast electron mobility, high efficiency of a light-emitting body and long life as a hole transport material for an organic electroluminescent device, the above properties of the above conventional hole transport materials need to be further improved to be more satisfactory.
Disclosure of Invention
The invention aims to provide a material for flexible display, a preparation method thereof and an organic electroluminescent device.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a material for flexible display has a general molecular formula:
Figure BDA0001407559820000021
wherein R is1、R2、R3、R8、R9、R10And R11Each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms;
R4、R5、R6and R7Each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylmercapto group having 6 to 50 carbon atoms;
R12、R13、R14and R15Each independently selected from hydrogen, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and substituted or unsubstituted aryl groupAn unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms;
X1selected from O, S or Se.
Preferably, said R is4、R5、R6And R7Each independently selected from a substituted or unsubstituted alkylaryloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, or a substituted or unsubstituted alkylarylthio group having 7 to 50 carbon atoms.
Preferably, said R is1、R2And R3Each independently selected from hydrogen, substituted or unsubstituted alkyl group with 1-10 carbon atoms, substituted or unsubstituted aryl group with 6-20 carbon atoms, and substituted or unsubstituted heterocyclic group with 5-20 carbon atoms; the R is8、R9、R10And R11Each independently selected from hydrogen or substituted or unsubstituted alkyl with 1-10 carbon atoms; the R is4、R5、R6And R7Each independently selected from hydrogen, substituted or unsubstituted alkyl group with 1-10 carbon atoms, or substituted or unsubstituted aryl group with 6-20 carbon atoms; the R is12、R13、 R14And R15Each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.
Preferably, said R is1、R2And R3Each independently selected from hydrogen, methyl, phenyl or pyridyl; the R is8、R9、R10And R11Each independently selected from hydrogen or methyl; the R is4、R5、R6And R7Each independently selected from hydrogen, methyl or phenyl; the R is12、R13、R14And R15Each independently selected from hydrogen, methyl, phenyl, 2-thienyl or methoxy.
Preferably said R4And R7Each independently selected from the following formulae:
Figure BDA0001407559820000041
wherein X and Y are each independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms, and X and Y may be the same or different.
Preferably, X and Y are respectively and independently selected from substituted or unsubstituted C7-30 alkaryloxy or substituted or unsubstituted C7-30 alkaryloxy.
Preferably, the material for flexible display has a general formula of any one of chemical formula 2-1 to chemical formula 2-5:
Figure BDA0001407559820000051
Figure BDA0001407559820000061
preferably, the material for flexible display shown in chemical formula 1 is selected from compounds having a specific structure represented by any one of chemical formulas 001 to 040:
Figure BDA0001407559820000062
Figure BDA0001407559820000071
Figure BDA0001407559820000081
Figure BDA0001407559820000091
Figure BDA0001407559820000101
the invention also provides a preparation method of the material for flexible display, which comprises the following steps:
the material which is generated by a Suzuki coupling reaction of a compound with a structure shown in a formula (M) and a compound with a structure shown in a formula (N) and has a structure shown in a chemical formula 1 and can be used for flexible display;
Figure BDA0001407559820000111
wherein, the compound with the structure of the formula (M) is obtained by the compound of the formula (P) and the compound of the formula (Q) through a cyclization reaction;
Figure BDA0001407559820000112
wherein, the compound with the structure of formula (N) is obtained by a Suzuki reaction of the compound with the structure of formula (N');
Figure BDA0001407559820000113
or the compound of the formula (N) is obtained by the Suzuki coupling reaction of the compound of the formula (Y) and the compound of the formula (Z);
Figure BDA0001407559820000121
wherein R is1、R2、R3、R8、R9、R10And R11Each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms;
R4、R5、R6and R7Each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, or a substituted or unsubstituted arylmercapto group having 6 to 50 carbon atoms;
R12、R13、R14and R15Each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted aromatic amino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms; x1Selected from O, S or Se.
The preparation method of the material for flexible display provided by the invention has no special requirement on the proportion of the raw materials, and the raw materials are in conventional proportion of the reaction well known to those skilled in the art, and the preparation method can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement or the quality requirement. The conditions of the reaction are not particularly required in the present invention, and may be conventional conditions for such reactions, which are well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements or quality requirements, and the solvent used in the present invention is preferably toluene.
In the present invention, the source of the starting compound is not particularly limited, and it may be prepared by a known production method in the art or may be commercially available.
The invention also provides an organic electroluminescent device, which comprises an electroluminescent material; the electroluminescent material includes a material of chemical formula 1 that can be used for a flexible display.
The organic electroluminescent device of the invention preferably has the following structure: the method comprises the following steps:
the display device comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer contains a material which is used for flexible display and has a structure shown in chemical formula 1; the material for the flexible display of the structure of chemical formula 1 may be in a single form or mixed with other materials in the organic layer.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
At least one of the hole injection layer, the hole transport layer and the layer having both hole injection and hole transport functions is a conventional hole injection material, a hole transport material or a material having both hole injection and hole transport functions, and may be a material generated from an electron transport material.
The "organic layer" as referred to in the present invention refers to a term of all layers disposed between the first electrode and the second electrode of the organic electroluminescent device.
For example, the organic layer includes a light emitting layer, and the organic layer includes one or more of a phosphorescent host, a fluorescent host, a phosphorescent dopant and a fluorescent dopant, wherein the light emitting layer includes a compound of the structure of formula 1, such as: i) the fluorescent host may be a compound of the structure of chemical formula 1; ii) the fluorescent dopant may be a compound of the structure of the above chemical formula 1; iii) the fluorescent host and the fluorescent dopant may be a compound having the structure of chemical formula 1.
Specifically, when the compound of the structure of chemical formula 1 is present in the light emitting layer in the organic layer, the compound of the structure of chemical formula 1 may be used as a light emitting host of an electroluminescent material or doped in other fluorescent hosts; for example: the light emitting layer may be a red, yellow or blue light emitting layer. And the compound of the structure of chemical formula 1 is doped on the blue host, so that the efficiency, brightness, resolution and long life of the light emitting device can be improved.
When the compound of the structure of chemical formula 1 is present in the electron transport layer, the electron transport layer further includes a metal-containing compound.
When the organic layer includes a light emitting layer and an electron transport layer, the compound of the structure of chemical formula 1 may be present in one or both of them.
The device prepared by the compound having the structure of formula 1 according to the present invention may be used in an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic Paper (e-Paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT).
The organic electroluminescent device can be used for forming an anode by evaporating metal, conductive oxides and alloys thereof on a substrate by using methods such as thin film evaporation, electron beam evaporation, physical vapor deposition and the like, and can also be used for evaporating a spin-coating (spin-coating) or a thin strip head; the layer number can also be reduced by molding (tape-casting), doctor-blading (sector-Printing), Screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging).
The invention has the beneficial effects that:
the dibenzophenazine derivative is prepared by connecting a dibenzophenazine compound containing a substituent group with dibenzofuran, dibenzothiophene or dibenzoselenophene containing the substituent group, the compound increases the electron mobility, and particularly can be used as a hole transport material for preparing an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is long. The preparation method of the material for flexible display provided by the invention is simple and feasible, and is easy for industrial production. The organic electroluminescent device provided by the present invention is suitably used for flat panel displays, flat light emitters, surface-emitting OLED light emitters for illumination, flexible light emitters, light sources for copying machines, printers, LCD backlights or measuring machines, display panels, signs, and the like.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 Synthesis of intermediate 4- (3-bromo-phenyl) -dibenzothiophene (A-1)
0.132mol of dibenzothiophene-4-boric acid, 0.158mol of m-bromoiodobenzene, 4.5g of palladium tetratriphenylphosphine and 0.264mol of sodium carbonate are added into a four-neck flask, 600mL of toluene and 150mL of water are added, and the mixture is reacted for 24 hours at 60 ℃ under the protection of nitrogen. The treatment process comprises the following steps: cooling, separating, removing water layer, spin-drying organic layer to obtain oil, dissolving the oil with a small amount of dichloromethane, adding into silica gel column, adding ethyl acetate: petroleum ether is 1: 10 washes and collects the target product spot (RF ═ 0.6) to give 0.066mol of a-1 as a white solid in 50% yield.
Example 2 intermediates A-2 and A-29 were synthesized according to the above-described preparation method of intermediate A-1, and Table 1 summarizes the reaction materials, the products, and the yields of example 2 according to the present invention.
TABLE 1
Figure BDA0001407559820000151
Figure BDA0001407559820000161
Figure BDA0001407559820000171
Figure BDA0001407559820000181
Figure BDA0001407559820000191
Figure BDA0001407559820000201
EXAMPLE 3 Synthesis of intermediate 2- (3-dibenzothiophen-4-yl-phenyl) -4,4,5, 5-tetramethyl- [1,3,2] dioxaborolane (B-1)
Figure BDA0001407559820000211
22g of intermediate A-1, 24.8g of pinacol diboron and 12.8g of potassium acetate are added into a three-neck flask, 1.2g of catalyst tris (dibenzylideneacetone) dipalladium and 3.6g of tricyclohexylphosphine and 200mL of 1, 4-dioxane are added, the mixture is stirred for 30 minutes at room temperature under the protection of nitrogen, and then the mixture is heated to 80 ℃ for reaction for 24 hours. The reaction was monitored by spotting, and when the reaction of the starting materials was completed and the temperature was lowered, the reaction solution was poured into about 600mL of water while stirring until a solid precipitated. Dissolve the solid with a small amount of dichloromethane, column pass, ethyl ester: petroleum ether is 1: the column was flushed 10 and product dots were collected to give B-118 g as a white solid in 52% yield.
Example 4 intermediates B-2 and B-29 were synthesized according to the above-described preparation method of intermediate B-1, and Table 2 is a summary of the reaction materials, the resulting materials and the yields of example 4 according to the present invention.
TABLE 2
Figure BDA0001407559820000212
Figure BDA0001407559820000221
Figure BDA0001407559820000231
Figure BDA0001407559820000241
Figure BDA0001407559820000251
Figure BDA0001407559820000261
Example 5 Synthesis of intermediate 11- (3-bromo-phenyl) -dibenzo [ a, C ] phenazine (C-1):
Figure BDA0001407559820000262
adding 10g of 9, 10-phenanthrenequinone and 9g of 4-bromo o-phenylenediamine into a three-neck flask, adding 2g of palladium chloride, adding 700mL of absolute ethyl alcohol serving as a solvent, and heating to 60 ℃ for reacting for 2 hours. Cooling, vacuum filtering to obtain yellow solid, and drying. The solid was dissolved in dichloromethane, the catalyst was removed and the pure product C-1, 14g was obtained by spin drying, yield 72%.
Example 6 intermediates C-2 and C-10 were synthesized according to the above-described preparation method of intermediate C-1, and Table 3 summarizes the reaction materials, the products, and the yields in example 6 of the present invention.
TABLE 3
Figure BDA0001407559820000263
Figure BDA0001407559820000271
Figure BDA0001407559820000281
EXAMPLE 7 Synthesis of the target product 11- (3-dibenzothiophene-4-phenyl) -dibenzo [ a, c ] phenazine (001)
Figure BDA0001407559820000282
10g (0.0278mol) of intermediate 11- (3-bromo-phenyl) -dibenzo [ a, C ] phenazine (C-1), 10.7g (0.0278mol) of intermediate 2- (3-dibenzothiophen-4-yl-phenyl) -4,4,5, 5-tetramethyl- [1,3,2] dioxaborolane (B-1), 1g (3% mol) of palladium tetratriphenylphosphine as a catalyst, and 7.7g (2mol) of potassium carbonate. Then 500mL of toluene and 200mL of water are added, the temperature is raised to 100 ℃ under the protection of nitrogen, the reaction is carried out for 24 hours, and the reaction is monitored. And (3) post-treatment process: after all the raw materials are reacted, cooling and suction filtration are carried out to obtain a solid, and then toluene is used for recrystallization to obtain a yellow solid compound 001 with the purity of 99.95 percent, the purity of 99.99 percent after sublimation and the yield of 80 percent.
The compound 002-040 was synthesized according to the above-mentioned synthesis method for compound 001, and the reactants and the target products and yields are shown in Table 4.
TABLE 4
Figure BDA0001407559820000291
Figure BDA0001407559820000301
Figure BDA0001407559820000311
Figure BDA0001407559820000321
Figure BDA0001407559820000331
Figure BDA0001407559820000341
Figure BDA0001407559820000351
Organic electroluminescent device production example:
comparative example 1
The compound represented by a chemical formula a is used as a main material, the compound 2-TNATA (4,4 ' -tri (N-2-naphthyl) -N-phenylamino) -triphenylamine) represented by a chemical formula b is used as a hole injection layer substance, NPD (N, N ' -di (1-naphthyl) -N, N ' -diphenyl benzidine) is used as a hole transport layer substance, and the device structure is as follows: ITO/2-TNATA (80 nm)/alpha-NPD (30 nm)/compound a + compound b (30 nm)/Alq 3(30nm)/LiF (0.5nm)/Al (60 nm).
Of Corning
Figure BDA0001407559820000361
A glass substrate was cut into a size of 50mm x 50mm x 0.7mm, placed in distilled water and alcohol, ultrasonically cleaned for 15 minutes, UV ozone cleaned for 30 minutes, a hole injection layer 2-TANATA was deposited on the prepared transparent electrode to a thickness of 80nm, and a hole transport layer α -NPD was deposited on the hole injection layer to a thickness of 30nm, wherein the chemical formula shown on the upper surface of the hole transport layer was a, and a light emitting layer was deposited on the upper surface of the hole transport layer to a thickness of 30nm by doping with 8% of a compound b. An electron transport layer Alq3 with a thickness of 30nm, an electron injection layer LiF with a thickness of 0.5nm and Al (cathode) with a thickness of 60nm are evaporated on the upper part of the luminescent layer.
Comparative example 2
The compound represented by a chemical formula a is used as a main material, the compound 2-TNATA (4,4 ' -tri (N-2-naphthyl) -N-phenylamino) -triphenylamine) represented by a chemical formula b is used as a hole injection layer substance, NPD (N, N ' -di (1-naphthyl) -N, N ' -diphenyl benzidine) is used as a hole transport layer substance, and the device structure is as follows: ITO/2-TNATA (80 nm)/alpha-NPD (30 nm)/compound a + compound c (30 nm)/Alq 3(30nm)/LiF (0.5nm)/Al (60 nm).
Of Corning
Figure BDA0001407559820000362
A glass substrate was cut into a size of 50mm x 50mm x 0.7mm, placed in distilled water and alcohol, ultrasonically cleaned for 15 minutes, UV ozone cleaned for 30 minutes, a hole injection layer 2-TANATA was deposited on the prepared transparent electrode to a thickness of 80nm, and a hole transport layer α -NPD was deposited on the hole injection layer to a thickness of 30nm, wherein the chemical formula shown on the upper surface of the hole transport layer was a, and a light emitting layer was deposited on the upper surface of the hole transport layer to a thickness of 30nm by doping with 10% of a compound c. An electron transport layer Alq3 with a thickness of 30nm, an electron injection layer LiF with a thickness of 0.5nm and Al (cathode) with a thickness of 60nm are evaporated on the upper part of the luminescent layer.
Comparative example 3
The compound represented by a chemical formula a is used as a main material, the compound 2-TNATA (4,4 ' -tri (N-2-naphthyl) -N-phenylamino) -triphenylamine) represented by a chemical formula b is used as a hole injection layer substance, NPD (N, N ' -di (1-naphthyl) -N, N ' -diphenyl benzidine) is used as a hole transport layer substance, and the device structure is as follows: ITO/2-TNATA (80 nm)/alpha-NPD (30 nm)/compound a + compound d (30 nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)。
Of Corning
Figure BDA0001407559820000371
A glass substrate was cut into a size of 50mm x 50mm x 0.7mm, placed in distilled water and alcohol, ultrasonically cleaned for 15 minutes, UV ozone cleaned for 30 minutes, a hole injection layer 2-TANATA was deposited on the prepared transparent electrode to a thickness of 80nm, and a hole transport layer α -NPD was deposited on the hole injection layer to a thickness of 30nm, wherein the chemical formula shown on the upper surface of the hole transport layer was a, and a light emitting layer was deposited to a thickness of 30nm by doping with 8% of a compound d. An electron transport layer Alq3 with a thickness of 30nm, an electron injection layer LiF with a thickness of 0.5nm and Al (cathode) with a thickness of 60nm are evaporated on the upper part of the luminescent layer.
<Compound a>
Figure BDA0001407559820000372
<Compound b>
Figure BDA0001407559820000373
<Compound c>
Figure BDA0001407559820000374
<Compound d>
Figure BDA0001407559820000375
Examples 1 to 40
The compound a is replaced by the synthesized 001-040 compound as the main compound of the light-emitting layer, and the same method is respectively adopted for one of the ITO/2-TNATA (80 nm)/alpha-NPD (30 nm)/compound 001-040 + compounds](30nm)/Alq3(30nm)/LiF (0.5nm)/Al (60 nm).
The organic electroluminescent device prepared according to the present invention was tested using a KEITHLEY gishili 2400 type source measuring unit, a CS-2000 spectroradiometer, to evaluate the current density, luminous efficiency and luminous color of the light emitting device, and the results of 90% time was measured using an LTS-1004AC lifetime testing apparatus 15000nit of ENC technology corporation as a reference, and the performance luminous characteristics of the obtained device were tested, and the results are shown in table 5, which is the results of the luminous characteristics of the light emitting devices prepared from the compounds prepared in the examples of the present invention and the comparative materials.
Table 5 results of testing light emitting characteristics of light emitting devices prepared from the compound prepared in the example of the present invention and the comparative material
Figure BDA0001407559820000381
Figure BDA0001407559820000391
From the results of table 5 above, it can be seen that the compounds provided by the present invention significantly improve the light emission efficiency and lifetime characteristics of the device when used as host materials compared to the comparative compounds.
The organic electroluminescent device prepared by the compound provided by the invention can obtain the results of good luminous efficiency and service life, so that the compound provided by the invention has high practicability in the OLED industry. The organic electroluminescent device of the present invention is suitably used for a light source, a display panel, a sign, and the like of a flat panel display, a flat light emitting body, a surface emitting OLED light emitting body for illumination, a flexible light emitting body, a copying machine, a printer, an LCD backlight, a meter, and the like.

Claims (3)

1. A material useful for flexible display, characterized by being selected from compounds of specific structures represented by any one of chemical formulas 001 to 040:
Figure FDA0002923014070000011
Figure FDA0002923014070000021
Figure FDA0002923014070000031
Figure FDA0002923014070000041
Figure FDA0002923014070000051
2. the method for preparing a material usable for a flexible display according to claim 1, characterized by comprising the steps of:
the material which is generated by a Suzuki coupling reaction of a compound with a structure shown in a formula (M) and a compound with a structure shown in a formula (N) and has a structure shown in a chemical formula 1 and can be used for flexible display;
Figure FDA0002923014070000052
Figure FDA0002923014070000061
wherein, the compound with the structure of the formula (M) is obtained by the compound of the formula (P) and the compound of the formula (Q) through a cyclization reaction;
Figure FDA0002923014070000062
wherein, the compound with the structure of formula (N) is obtained by a Suzuki reaction of the compound with the structure of formula (N');
Figure FDA0002923014070000063
or the compound of the formula (N) is obtained by the Suzuki coupling reaction of the compound of the formula (Y) and the compound of the formula (Z);
Figure FDA0002923014070000064
wherein R is1To R15，X1Each corresponding to a specific substituent on a respective compound of claim 1.
3. An organic electroluminescent device comprising an electroluminescent material; characterized in that the electroluminescent material comprises a material for flexible displays as shown in any one of the structures of claim 1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977032A (en) * 2006-09-14 2013-03-20 西巴控股有限公司 Heterocyclic bridged biphenyls and their use in OLEDs
CN103936721A (en) * 2014-04-14 2014-07-23 太原理工大学 Carbazole-derivative-substituted phenazine compounds, and preparation method and application thereof
CN104037340A (en) * 2014-06-25 2014-09-10 上海道亦化工科技有限公司 Organic electroluminescence device
CN104650040A (en) * 2015-02-14 2015-05-27 上海道亦化工科技有限公司 Organic electroluminescent compound of phenazine derivative

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KR101328526B1 (en) * 2012-01-12 2013-11-13 건국대학교 산학협력단 Organic photovoltain polymer and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977032A (en) * 2006-09-14 2013-03-20 西巴控股有限公司 Heterocyclic bridged biphenyls and their use in OLEDs
CN103936721A (en) * 2014-04-14 2014-07-23 太原理工大学 Carbazole-derivative-substituted phenazine compounds, and preparation method and application thereof
CN104037340A (en) * 2014-06-25 2014-09-10 上海道亦化工科技有限公司 Organic electroluminescence device
CN104650040A (en) * 2015-02-14 2015-05-27 上海道亦化工科技有限公司 Organic electroluminescent compound of phenazine derivative

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