CN111004248B - Novel organic material and application thereof - Google Patents

Novel organic material and application thereof Download PDF

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CN111004248B
CN111004248B CN201911193193.6A CN201911193193A CN111004248B CN 111004248 B CN111004248 B CN 111004248B CN 201911193193 A CN201911193193 A CN 201911193193A CN 111004248 B CN111004248 B CN 111004248B
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CN111004248A (en
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段陆萌
范洪涛
黄春雪
杭德余
梁现丽
李仲庆
曹占广
刘阳
班全志
李继响
罗忠林
呼建军
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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Abstract

The invention relates to a novel organic material which has any one structure shown in general formulas I to III. The novel organic material provided by the invention is a novel compound which takes the forced occupied ton as the center and has a high T1 energy level, a narrow band gap and a shallow Highest Occupied Molecular Orbital (HOMO) energy level. The perixanthenoxanthene is easily sublimable, stable in air, and does not undergo oxidative decomposition. Has high thermal stability and high glass transition temperature in air. By introducing a group with larger steric hindrance, the luminescent material is not easy to crystallize and quench and has good film-forming property. As a preferable aspect of the present invention, the novel organic material is used as a host material in a light emitting layer.

Description

Novel organic material and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent display, in particular to a novel organic material and application thereof.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
The Peri-xanthoxanthene (PXX) is a condensed ring aromatic compound having 22 pi electrons in a divalent cation and a conjugated system of 22 atoms (20 carbon atoms and 2 oxygen atoms) and is very stable. The xanthenoxanthene is often used as an electron donor in charge transfer complexes and therefore has potential as a hole transport material. The merck company invents the related compounds to increase the efficiency and the service life of electronic devices, but the structure invented by the merck company is unstable, easy to quench and crystallize and poor in film forming property. The invention modifies the structure on the basis, and invents the main material which has high efficiency, long service life, difficult quenching and crystallization and good film forming property.
Disclosure of Invention
The invention aims to provide an OLED (organic light emitting diode) host material which is not easy to quench, crystallize and has good film forming property and an OLED device using the compound.
Specifically, the invention provides a novel organic material, which has any one structure shown in general formulas I to III:
Figure BDA0002294085900000021
in the general formulas I to III, R1By substitution of H atoms at any one or two positions on the phenyl ring in which it is located, R2By substitution of H atoms in any one, two or three positions of the phenyl ring in which they are located, R3By substitution of H atoms in any one, two or three positions of the phenyl ring in which they are located, R4Substituted with H atoms at any one, two or three positions on the phenyl ring on which it is located.
The R is1、R2、R3、R4Each independently represents-H, -F, -Cl, -Br, -I, -n (Ar), -C (═ O) Ar, -P (═ O) Ar, -S (═ O)2Ar、-OAr、-SAr、-CN、-NO2An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a sulfoalkoxy group having 1 to 40 carbon atoms.
The alkyl group having 1 to 40 carbon atoms may be a straight-chain alkyl group having 1 to 40 carbon atoms, a branched-chain alkyl group having 3 to 40 carbon atoms, or a cyclic alkyl group having 3 to 40 carbon atoms.
The alkoxy group having 1 to 40 carbon atoms may be a linear alkoxy group having 1 to 40 carbon atoms, a branched alkoxy group having 3 to 40 carbon atoms, or a cyclic alkoxy group having 3 to 40 carbon atoms.
The thioalkoxy group having 1 to 40 carbon atoms may be a linear thioalkoxy group having 1 to 40 carbon atoms, a branched thioalkoxy group having 3 to 40 carbon atoms, or a cyclic thioalkoxy group having 3 to 40 carbon atoms.
The R is1、R2、R3、R4The groups represented by each may be different, and any two of them may be the same and the remaining two may be the sameThe number of the groups is different, and any three of the groups may be the same and different from the rest, or four of the groups may be the same.
As a specific embodiment of the present invention, R is1、R2、R3、R4All represent H atoms.
In the general formulas I to III of the present invention for Ar1、Ar2The respective substitution positions are preferably selected to enhance the overall performance of the compound.
Specifically, the method comprises the following steps:
in the general formula II, Ar1、Ar2The respective specific substitution positions are preferably as shown in the general formulae II-1 to II-3.
Figure BDA0002294085900000022
In the general formula III, Ar1、Ar2The respective specific substitution positions are preferably as shown in the general formulae III-1 to III-6.
Figure BDA0002294085900000031
As a specific embodiment of the present invention, the novel organic material has a structure represented by the general formula II-1.
As a specific embodiment of the present invention, the novel organic material has a structure represented by the general formula II-1'.
Figure BDA0002294085900000032
Ar of the invention1、Ar2Each independently represents an aromatic group having an electron-withdrawing property having a benzene ring and/or an aromatic heterocyclic ring or represents an H atom, and Ar1、Ar2Not H atoms at the same time.
Preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294085900000033
Figure BDA0002294085900000041
more preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294085900000042
Figure BDA0002294085900000051
ar is1、Ar2The substituents represented by each may be the same or different.
In each of the above-mentioned substituent groups,
Figure BDA0002294085900000052
or "- - -" represents a substituted position.
As a particular embodiment of the invention, the novel organic material is selected from compounds of the following specific structure:
Figure BDA0002294085900000053
Figure BDA0002294085900000061
Figure BDA0002294085900000071
Figure BDA0002294085900000081
Figure BDA0002294085900000091
Figure BDA0002294085900000101
the invention also provides a preparation method of the novel organic material.
When in formula I Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When all Ar is contained, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I as a raw material, and carrying out a coupling reaction with Ar to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294085900000102
when in formula I Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I' as a raw material, and sequentially reacting with Ar1、Ar2Carrying out coupling reaction to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294085900000103
when in formula II Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II as a raw material, and carrying out a coupling reaction with Ar to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294085900000104
Figure BDA0002294085900000111
when in formula II Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II 'as a raw material, and reacting the compound P-II' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294085900000112
when in formula III Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III as a raw material, and carrying out a coupling reaction with Ar to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294085900000113
when in formula III Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III 'as a raw material, and reacting the compound P-III' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294085900000114
the above steps can be carried out by a person skilled in the art by known and conventional means, such as selecting a suitable catalyst, solvent, determining a suitable reaction temperature, time, etc.
In the above process for preparing a compound represented by any one of the general formulae I to III, when Ar is Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, as a preferred embodiment of the present invention, the method comprises: and (2) taking xylene as a reaction solvent, cuprous chloride as a catalyst, potassium hydroxide as an alkali, controlling the temperature to be 75-85 ℃ under the protection of nitrogen, and performing a coupling reaction on the raw materials and Ar to obtain the target compound.
In the above process for preparing a compound represented by any one of the general formulae I to III, when Ar is Ar1、Ar2When the groups are different, as a preferred embodiment of the present invention, the method comprises: firstly, dimethylbenzene is used as a reaction solvent, cuprous chloride is used as a catalyst, potassium hydroxide is used as alkali, nitrogen is used for protection, the temperature is controlled to be 75-85 ℃, and the raw material and Ar are mixed1Coupling reaction is carried out to obtain an intermediate product; and then taking toluene as a solvent, palladium acetate and tri-tert-butylphosphine as catalysts, potassium tert-butoxide as an alkali, protecting with nitrogen, controlling the temperature to be 90-120 ℃, and reacting the intermediate product and Ar2Coupling reaction is carried out to obtain the target compound.
The starting materials for the solvents, catalysts, bases, etc., used in the present invention can be synthesized by published commercial routes or methods known in the art.
The invention also protects the application of the novel organic material in an organic electroluminescent device. Preferably, the novel organic material is used as a host material in the light emitting layer.
The invention also discloses an organic electroluminescent device, wherein a luminescent layer of the organic electroluminescent device contains the novel organic material. Specifically, the organic electroluminescent device protected by the invention sequentially comprises a transparent substrate, an anode layer, a hole transport layer, a luminescent layer with the novel organic material as a main material, an electron transport layer, an electron injection layer and a cathode layer from bottom to top.
The novel organic material provided by the invention is a novel compound which takes the forced occupied ton as the center and has a high T1 energy level, a narrow band gap and a shallow Highest Occupied Molecular Orbital (HOMO) energy level. The perixanthenoxanthene is easily sublimable, stable in air, and does not undergo oxidative decomposition. Has high thermal stability and high glass transition temperature in air. By introducing a group with larger steric hindrance, the luminescent material is not easy to crystallize and quench and has good film-forming property.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
According to some embodiments of the present invention, the preferred solvent for preparing the organic electroluminescent device according to the present invention is selected from toluene, DMF or a mixture of these solvents. The reagents are analytically pure reagents, and the intermediate is purchased from an online shopping mall or is custom-synthesized from outsourcing companies.
Example 1
Figure BDA0002294085900000121
Synthesis of (Compound II-1-4)
The synthetic route is as follows:
Figure BDA0002294085900000131
synthesis of Compound II-1-4
A1L three-necked flask was stirred with magnetic stirring and then replaced with nitrogen, and 40.07g (0.378mol) of sodium carbonate, 58.59g (purity 99%, 0.21mol) of phenanthro [9,10-d ] thiazol-2-ylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 60.36g of light yellow solid with purity of 99% and yield of 79%.
Product MS (m/e): 523; elemental analysis (C)50H24N2O2S2): theoretical value C: 80.19 percent; h: 3.23 percent; n: 3.74 percent; o: 4.27 percent; s: 8.56 percent; found value C: 80.18 percent；H：3.24％；N：3.74％；O：4.27％；S：8.56％。
Example 2
Figure BDA0002294085900000132
Synthesis of (Compound II-1-7)
The synthetic route is as follows:
Figure BDA0002294085900000133
synthesis of Compound II-1-7
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 65.94g (purity 99%, 0.21mol) of 4- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 66.26g of light yellow solid with purity of 99% and yield of 81%.
Product MS (m/e): 818; elemental analysis (C)58H34N4O2): theoretical value C: 85.07 percent; h: 4.18 percent; n: 6.84 percent; o: 3.91 percent; found value C: 85.06 percent; h: 4.19 percent; n: 6.84 percent; o: 3.91 percent.
Example 3
Figure BDA0002294085900000141
Synthesis of (Compound II-1-12)
The synthetic route is as follows:
Figure BDA0002294085900000142
synthesis of Compound II-1-12
A1 liter three-necked flask was charged with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 17.93g (purity: 99%, 0.11mol) of benzo [ d ] oxazol-2-ylboronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 31.52g of light yellow solid with purity of 99% and yield of 79%.
Product MS (m/e): 399; elemental analysis (C)27H13NO3): theoretical value C: 81.19 percent; h: 3.28 percent; n: 3.51 percent; o: 12.02 percent; found value C: 81.18 percent; h: 3.29 percent; n: 3.51 percent; o: 12.02 percent.
Example 4
Figure BDA0002294085900000151
Synthesis of (Compound II-1-18)
The synthetic route is as follows:
Figure BDA0002294085900000152
synthesis of Compound II-1-18
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 60.27g (purity 99%, 0.21mol) of 6-phenylpyridin-3-yl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 47.04g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 588; elemental analysis (C)42H24N2O2): theoretical value C: 85.70 percent; h: 4.11 percent; n: 4.76 percent; o: 5.44 percent; found value C: 85.69 percent; h: 4.12 percent; n: 4.76 percent; o: 5.44 percent.
Example 5
Figure BDA0002294085900000153
Synthesis of (Compound II-1-26)
The synthetic route is as follows:
Figure BDA0002294085900000161
synthesis of Compound II-1-26
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 30.36g (purity 99%, 0.11mol) of 3, 5-bis (pyridin-3-yl) phenyl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, filtering to obtain 39.94g of light yellow solid with purity of 99% and yield of 78%.
Product MS (m/e): 512; elemental analysis (C)36H20N2O2): theoretical value C: 84.36 percent; h: 3.93 percent; n: 5.47%; o: 6.24 percent; found value C: 84.35 percent; h: 3.94 percent; n: 5.47%; o: 6.24 percent.
Example 6
Figure BDA0002294085900000162
Synthesis of (Compound I-34)
The synthetic route is as follows:
Figure BDA0002294085900000163
synthesis of Compound II-1-34-1
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.378mol) of sodium carbonate, 19.69g (purity 99%, 0.11mol) of benzo [ d ] thiazol-2-ylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 44g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled between 75 and 90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, and repeatedly boiling and washing filter cake with DMF for several times to obtain 24.11g light yellow solid with purity of 99% and yield of 49%.
Synthesis of Compound II-1-34
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.378mol) of sodium carbonate, 26.18g (purity 99%, 0.11mol) of (1-phenyl-1H-benzo [ d ] imidazol-2-yl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution of 49.2g of Compound II-1-34-1 (purity 99%, 0.1mol) and 100ml of toluene was added dropwise thereto, and the temperature was controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, and repeatedly boiling and washing the filter cake with DMF for several times to obtain 71.45g of light yellow solid with purity of 99% and yield of 78%.
Product MS (m/e): 607; elemental analysis (C)40H21N3O2S): theoretical value C: 79.06 percent; h: 3.48 percent; n: 6.91 percent; o: 5.27 percent; s: 5.28 percent; found value C: 79.05 percent; h: 3.49 percent; n: 6.91 percent; o: 5.27 percent; s: 5.28 percent.
According to the technical schemes of the examples 1 to 6, the compounds shown in II-1-1 to II-1-62 can be synthesized only by simply replacing the corresponding raw materials without changing any substantial operation.
Preparation of device examples
(1) Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm;
Figure BDA0002294085900000171
(3) evaporating and plating a layer of NPB (nitrogen-phosphorus) on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
Figure BDA0002294085900000181
(4) the compound II-4-1 provided in example 1 was further vapor-deposited as a host material on the hole transport layer at a rate of 0.1nm/s, Ir (piq)2acac is used as a doping material (namely a luminescent material), the doping concentration is 10%, an organic luminescent layer of the device is formed, and the total film thickness of the organic luminescent layer obtained by evaporation is 30 nm;
Figure BDA0002294085900000182
(5) continuously evaporating a layer of compound BPhen on the organic light-emitting layer to be used as an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
Figure BDA0002294085900000183
(6) continuously evaporating a layer of LiF on the electron transport layer to be used as an electron injection layer of the device, wherein the thickness of the evaporated film is 0.5 nm;
(7) continuously evaporating a layer of Al on the electron injection layer to be used as a cathode of the device, wherein the thickness of the evaporated film is 150 nm; the OLED device provided by the invention is obtained and is marked as OLED-1.
According to the same steps, replacing the compound II-4-1 in the step (4) with the compound prepared in the embodiment 2-6 of the invention to obtain the devices OLED-2-OLED-6 provided by the invention.
According to the same procedure as above, compound II-4-1 in step (4) was replaced with comparative compound 1 (structure shown below), to give comparative device OLED-7.
Figure BDA0002294085900000184
The results of the performance tests of the obtained devices OLED-1 to OLED-7 are shown in Table 1.
Table 1: performance test results of OLED-1 to OLED-7
Figure BDA0002294085900000191
From the above results, it can be seen that the current efficiency of the devices OLED-1 to OLED-6 prepared by using the organic material provided by the present invention is higher, and the operating voltage is significantly lower than that of the device OLED-7 using the comparative compound 1 as the organic light emitting host material under the same brightness condition.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (7)

1. A novel organic material having a structure represented by general formula II-1':
Figure FDA0003001046460000011
ar is1、Ar2Each independently represents the group or represents a H atom, Ar1、Ar2May be the same or different, and Ar1、Ar2Not H atoms at the same time;
Figure FDA0003001046460000012
2. the organic material of claim 1, wherein Ar is Ar1、Ar2Each independently selected from the group consisting of:
Figure FDA0003001046460000021
3. the organic material of claim 1, wherein the compound is selected from the following specific structures:
Figure FDA0003001046460000022
Figure FDA0003001046460000031
Figure FDA0003001046460000041
Figure FDA0003001046460000051
Figure FDA0003001046460000061
4. use of the novel organic material of any one of claims 1 to 3 in an organic electroluminescent device.
5. Use according to claim 4, wherein the novel organic material is used as host material in the light-emitting layer.
6. An organic electroluminescent device characterized in that a light-emitting layer contains the novel organic material according to any one of claims 1 to 3.
7. An organic electroluminescent device, comprising a transparent substrate, an anode layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode layer, wherein the luminescent layer, the electron transport layer, the electron injection layer and the cathode layer are made of the novel organic material according to any one of claims 1 to 3.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101490208A (en) * 2006-07-28 2009-07-22 默克专利有限公司 Novel materials for organic electroluminescent devices
US20160133857A1 (en) * 2014-11-10 2016-05-12 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN107083529A (en) * 2017-03-01 2017-08-22 南京理工大学 A kind of precursor molecule coupling control method
JPWO2018186462A1 (en) * 2017-04-07 2020-02-27 コニカミノルタ株式会社 Fluorescent compound, organic material composition, luminescent film, organic electroluminescent device material, and organic electroluminescent device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101490208A (en) * 2006-07-28 2009-07-22 默克专利有限公司 Novel materials for organic electroluminescent devices
US20160133857A1 (en) * 2014-11-10 2016-05-12 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN107083529A (en) * 2017-03-01 2017-08-22 南京理工大学 A kind of precursor molecule coupling control method
JPWO2018186462A1 (en) * 2017-04-07 2020-02-27 コニカミノルタ株式会社 Fluorescent compound, organic material composition, luminescent film, organic electroluminescent device material, and organic electroluminescent device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Axially Chiral peri-Xanthenoxanthenes as a Circularly Polarized Luminophore;Kazuto Takaishi,et al.,;《J. Am. Chem. Soc.》;20190719;第141卷;第11852-11857页 *
Near-infrared excition of the peri-xanthenoxanthene radical cation drives energy-demanding hole transfer reactions;Joseph A.Christensen,et al.,;《J.Phys.Chem.C》;20180925;第122卷;第23364-23370页 *

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