CN111777646A - Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device - Google Patents

Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device Download PDF

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CN111777646A
CN111777646A CN202010736486.0A CN202010736486A CN111777646A CN 111777646 A CN111777646 A CN 111777646A CN 202010736486 A CN202010736486 A CN 202010736486A CN 111777646 A CN111777646 A CN 111777646A
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李明
李小龙
李建行
仲维明
魏忠义
谢星冰
马晓宇
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Olide Shanghai Photoelectric Material Technology Co ltd
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

The invention discloses an organic phosphorus luminescent material, a preparation method thereof and an organic electroluminescent device, wherein the organic phosphorus luminescent material has a structural general formula

Description

Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic phosphorus luminescent material, a preparation method thereof and an organic electroluminescent device.
Background
Organic electroluminescence was discovered as early as the beginning of the 20 th century. In 1947, professor Dengqingyun, which is a national institute of America, hong Kong, discovered organic light emitting diodes, namely OLEDs in laboratories, and thus developed research on OLEDs, in 1987, professor Dengqingyun and Van Slyke adopted an ultrathin film technology, and a double-layer organic electroluminescent device was fabricated using a transparent conductive film as an anode, Alq3 as a light emitting layer, triarylamine as a hole transport layer, and Mg/Ag alloy as a cathode. In 1990, Burroughes et al discovered OLED using conjugated polymer PPV as light emitting layer, and thus the heat of OLED research has been raised worldwide.
The Organic Light Emitting Device (OLED) is composed of a cathode, an anode and organic layers inserted between the cathode and the anode, namely the device is composed of a transparent ITO anode, a hole injection layer (ETL), a Hole Transport Layer (HTL), a light Emitting Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and the cathode, and 1-2 organic layers can be omitted as required. The OLED has the action mechanism that voltage is formed between two electrodes, electrons are injected from a cathode on one side, holes are injected from an anode on the other side, the electrons and the holes are recombined in a light-emitting layer to form an excited state, the excited state returns to a stable ground state, and the device emits light.
And the light emitting material of the organic light emitting diode is mainly a phosphorescent light emitting material. The independent light emission of three primary colors of red, blue and green is the most adopted color mode at present, and the technical key point is to improve the color purity and efficiency of the luminescent material. Therefore, in recent years, research into organic phosphorescent materials has been conducted, and the most of them is a metal iridium complex.
As the light emitting material, excitons are formed by recombination of electrons and holes injected from each electrode. Singlet excitons emit fluorescence and triplet excitons emit phosphorescence. The singlet excitons emitted have a formation probability of 25%, while the triplet excitons emitting phosphorescence have a formation probability of 75%. Thus, triplet excitons provide greater luminous efficiency than singlet excitons. Among such phosphorescent materials, organic phosphorescent materials may have greater luminous efficiency than fluorescent materials. Therefore, organic phosphorescent materials are being widely studied as an important factor for improving the efficiency of organic electroluminescent devices.
However, the organic phosphor luminescent materials disclosed so far have certain defects in luminescent efficiency and lifetime. Therefore, it is a technical problem to be solved to develop a material with high luminous efficiency and long lifetime.
Disclosure of Invention
In view of the above, the present invention provides a phosphorescent compound, a method for preparing the same, and an organic electroluminescent device, wherein the phosphorescent compound is applied to the electroluminescent device, and the organic electroluminescent device prepared by using the phosphorescent compound has high current efficiency, low driving voltage, and long phosphorescent lifetime.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic phosphorus luminescent material, the structure of which is shown in formula I:
Figure BDA0002605166240000021
wherein:
R1～R6each independently represents hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C30Alkyl of (2), substituted or unsubstituted C6-C30Aryl of (2), substituted or unsubstituted C3-C30Cycloalkyl of (a), substituted or unsubstituted C1-C30Alkoxy of (2), substituted or unsubstituted C1-C30Alkylamino of (a), substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C2-C30Alkynyl of (a), substituted or unsubstituted C2-C30A heterocyclic group of (a);
R1、R3represents a mono-, di-, tri-or tetra-substituent, R2Represents a mono-or di-substituent.
Wherein R is1、R2、R3Not capable of forming a cyclic group with the ring, or R1、R2、R3The substituents cannot form a cyclic group therebetween.
By adopting the technical scheme, a specific heterocyclic ligand can be formed, so that the wavelength of the compound is in an optimal range.
Preferably, said R is1～R6Each independently selected from hydrogen, deuterium atom, cyano, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C2-C10A heterocyclic group of (A), substituted or unsubstituted C6-C12Aryl group of (1).
By adopting the technical scheme, the wavelength characteristics of the compound are more obvious, and the prepared device has better effect and longer service life.
Preferably, the alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
Preferably, the cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylcyclopentyl, 3,4, 5-trimethylcyclohexyl.
Preferably, said R is1～R6The hydrogen atom in the group or substituent group of (a) is deuterated.
Preferably, the specific structural formula of the organic phosphorus luminescent material shown in chemical formula I is:
Figure BDA0002605166240000041
Figure BDA0002605166240000051
Figure BDA0002605166240000061
Figure BDA0002605166240000071
Figure BDA0002605166240000081
some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of the groups and the substituted groups and substituted positions thereof, which is not described in detail herein.
The invention also provides a preparation method of the organic phosphorus luminescent material, which comprises the following steps:
s1, under the protection of nitrogen, reacting the compound with the structure of the formula (II) with iridium trichloride in a mixed solution of ethylene glycol ethyl ether and ultrapure water, and after the reaction is finished, carrying out post-treatment to obtain a compound with the structure of the formula (IV);
s2, under the protection of nitrogen, reacting the compound with the structure of the formula (IV) with the compound with the structure of the formula (III) in an ethylene glycol ether solvent, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure of the formula (I);
Figure BDA0002605166240000091
by adopting the technical scheme, the obtained product has high purity and simple steps through a simple synthesis method.
Preferably, in step S1, the molar ratio of the compound with the structure of the formula (II) to the iridium trichloride is (2.2-2.8): 1.
By adopting the technical scheme, the reaction can be carried out more smoothly and the product purity is better by optimizing the reaction molar ratio.
Preferably, in step S1, the solvent is preferably a mixed solution of ethylene glycol ethyl ether and ultrapure water, and the ratio of the ethylene glycol ethyl ether to the ultrapure water is 3: 1; the dosage of the solvent is 10-50 times of that of iridium trichloride.
By adopting the technical scheme, the reaction can be carried out more smoothly and the product purity is better by optimizing the reaction molar ratio.
Preferably, in step S1, the reaction time is 24 to 30 hours.
By adopting the technical scheme, the reaction can be carried out more smoothly by optimizing the reaction time, and the product purity is better.
Preferably, in step S2, the molar ratio of the compound with the structure of formula (IV) to the compound with the structure of formula (III) is 1 (2.5-8).
By adopting the technical scheme, the reaction can be carried out more smoothly and the product purity is better by optimizing the reaction molar ratio.
Preferably, in step S2, the base used in the reaction is anhydrous potassium carbonate or anhydrous sodium carbonate, the solvent is preferably ethylene glycol ethyl ether, and the amount of the solvent is 10-30 times of that of formula (iv).
By adopting the technical scheme, the reaction can be carried out more smoothly and the product purity is better by optimizing the reaction molar ratio.
Preferably, in step S2, the reaction time is 10 to 30 hours, preferably 20 to 24 hours.
By adopting the technical scheme, the reaction can be carried out more smoothly by optimizing the reaction time, and the product purity is better.
Preferably, in step S1, the post-processing procedure is: and cooling to room temperature, separating out a precipitate, performing vacuum filtration, sequentially leaching with absolute ethyl alcohol and petroleum ether, and drying to obtain the bridged ligand compound shown in the formula B.
By adopting the technical scheme, the reaction steps are simple, the operation is simple and convenient, and the expected effect is achieved by optimizing the post-reaction treatment process.
Preferably, in step S2, the post-processing procedure is: cooling to room temperature, carrying out vacuum filtration, leaching a filter cake with ethanol, drying under-0.1 Mpa at 50 ℃, passing through a silica gel column, and spin-drying the obtained filtrate to obtain the organophosphorus luminescent material shown in the formula G.
By adopting the technical scheme, the reaction steps are simple, the operation is simple and convenient, and the expected effect is achieved by optimizing the post-reaction treatment process.
The invention further provides the application of the organic phosphorus luminescent material in an organic electroluminescent device.
The invention also provides an organic electroluminescent device containing the organic phosphorus luminescent material.
An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer, the organic layer being located between the first electrode and the second electrode; the organic layer comprises at least one; and at least one of the organic layers comprises the organic phosphorus luminescent material according to any one of claims 1 to 4; the organic phosphorus luminescent material exists in the organic layer in a single form or mixed with other substances.
Preferably, the organic layer at least comprises one or a combination of more of a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport technologies, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer having both electron transport and electron injection technologies.
Preferably, the organic electroluminescent device comprises a light-emitting layer containing the organic phosphorus light-emitting material.
Preferably, the light-emitting layer includes a host material and a dopant material, the host material includes a fluorescent host and a phosphorescent host, and the dopant material is the above-mentioned organic phosphorus light-emitting material.
Preferably, the mass ratio of the host material to the dopant material is (90:10) - (99.5: 0.5).
The invention further provides application of the organic electroluminescent device in an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
According to the technical scheme, compared with the prior art, the organic phosphorus luminescent material, the preparation method thereof and the organic electroluminescent device provided by the invention have the following beneficial effects:
(1) the invention provides an organic phosphorus luminescent material with a novel structure, and an organic electroluminescent device prepared by using the organic phosphorus luminescent material has higher current efficiency, low driving voltage and longer phosphorescence service life.
(2) The preparation method of the organic phosphorus luminescent material provided by the invention has the advantages of simple and efficient process and high purity of the prepared product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, 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
The synthesis of the compound of formula I-2 comprises the following specific steps:
Figure BDA0002605166240000121
s1, weighing ligand II-2 (12.57g, 46mmol) IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 210m1 ethylene glycol ethyl ether and 70m1 pure water is added, the mixture is refluxed for 25 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand IV-2 was obtained as a dark red powder in a mass of 8.19g with a yield of 53%.
S2, weighing the bridging ligand IV-2 (7.72g, 5mmol), adding anhydrous potassium carbonate (6.9g, 50mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-2 (2.00g, 20mmol) under nitrogen, refluxing for 24 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, and concentrating and precipitating a solid from the filtrate to finally obtain the organic phosphorus luminescent material shown in the formula I-1, wherein the mass of the organic phosphorus luminescent material is 3.93 g. The yield was 47% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 835.98; the test value was 835.62.
Elemental analysis:
calculated value is C: 61.78; h is 4.22; 22.99 parts of Ir; n is 3.35; o is 7.66.
Test value C: 61.77; h is 4.20; 22.98 parts of Ir; n is 3.37; o is 7.68.
Example 2
The synthesis of compounds of formula I-56 is specifically carried out by the following steps:
Figure BDA0002605166240000131
s1, weighing ligand II-56 (14.96g, 50mmol) IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 pure water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridging ligand IV-56 was obtained as a dark red powder in a mass of 10.05g with a yield of 61%.
S2, weighing the bridging ligand IV-56 (9.89g, 6mmol), adding anhydrous potassium carbonate (8.28g, 60mmol), adding 130ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-56 (5.04g, 24mmol) under nitrogen, refluxing for 22 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Using dichloromethane and toluene as solvents, carrying out chromatography by using a neutral alumina column, and concentrating and precipitating a solid from the filtrate to finally obtain the organophosphorus luminescent material shown in the formula I-31, wherein the mass of the organophosphorus luminescent material is 5.63 g. The yield was 47% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 997.89 test 997.77.
Elemental analysis:
calculated value is C: 51.76; h is 2.63; f is 17.13; 19.26 parts of Ir; n is 2.81; o is 6.41.
Test value C: 51.77; h is 2.65; f, 17.14; 19.24 parts of Ir; 2.80 of N; o is 6.40.
Example 3
The synthesis of compounds of formula I-105 is described in the following specific synthetic procedures:
Figure BDA0002605166240000141
s1, weighing ligand II-105 (16.24g, 52mmol) IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, mixed solution of 420m1 ethylene glycol ethyl ether and 140m1 purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridging ligand IV-105 was obtained as a dark red powder with a mass of 8.84g and a yield of 52%.
S2, weighing the bridging ligand IV-105 (8.50g, 5mmol), adding anhydrous potassium carbonate (6.9g, 50mmol), adding 170ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-105 (3.39g, 15mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organophosphorus luminescent material shown in the formula I-56, wherein the mass of the organophosphorus luminescent material is 4.68 g. The yield was 45% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1039.99; the test value was 1039.47.
Elemental analysis:
calculated value is C54.28; h is 2.91; f is 12.79; 18.48 parts of Ir; n is 5.39; o is 6.15.
Test value is C: 54.26; h is 2.90; f is 12.78; 18.49 parts of Ir; n is 5.39; o is 6.18.
Example 4
The synthesis of compounds of formula I-128 is specifically performed as follows:
Figure BDA0002605166240000151
s1, weighing ligand II-128 (21.99g, 54mmol) IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, mixed solution of 390m1 ethylene glycol ethyl ether and 130m1 pure water is added, reflux is carried out for 28 hours under the protection of nitrogen, then cooling is carried out to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand IV-128 obtained was 13.31g in the form of a dark red powder, with a yield of 64%.
S2, weighing the bridging ligand IV-128 (12.48g, 6mmol), adding anhydrous potassium carbonate (8.28g, 60mmol), adding 250ml ethylene glycol ethyl ether into the system, displacing nitrogen for three times, adding the formula III-128 (6.31g, 30mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, and concentrating the filtrate to precipitate solid, thereby finally obtaining the organophosphorus luminescent material shown in the formula I-128, wherein the mass of the organophosphorus luminescent material is 5.68 g. The yield was 39% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 1213.78; the test value was 1213.62.
Elemental analysis:
calculated value is C: 42.55; h is 1.16; f, 32.87; 15.84 parts of Ir; 2.31 of N; o is 5.27.
Test value C42.56; h is 1.17; f, 32.89; 15.82 parts of Ir; 2.32 of N; o is 5.24.
Example 5
The synthesis of compounds of formula I-136 is specifically performed as follows:
Figure BDA0002605166240000161
s1, weighing the formula II-136 (13.67g, 50mmol) IrC1 under the protection of nitrogen3·3H2O (7.05g, 20mmo1) is put into a reaction system, mixed solution of 450m1 ethylene glycol ethyl ether and 150m1 pure water is added, reflux is carried out for 28 hours under the protection of nitrogen, then cooling is carried out to room temperature, and precipitate is separated outFiltering the precipitate, washing with water, absolute ethyl alcohol and petroleum ether in sequence, and drying. The mass of the bridged ligand IV-136 was 8.96g, which was obtained as a dark red powder, in 58% yield.
S2, weighing the bridging ligand IV-136 (8.50g, 5.5mmol), adding anhydrous potassium carbonate (7.59g, 55mmol), adding 150ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula III-136 (4.10g, 16.5mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. And (3) taking dichloromethane as a solvent, carrying out chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the organic phosphorus luminescent material shown in the formula I-136, wherein the mass of the organic phosphorus luminescent material is 3.90 g. The yield was 36% and the HPLC purity was greater than 99.5%.
Mass spectrum calculated 984.18; the test value was 984.24.
Elemental analysis:
calculated value is C is 62.24; h, 5.02; f is 3.86; 19.53 parts of Ir; 2.85 of N; o is 6.50.
The test value is C: 62.26; h is 5.04; f is 3.87; 19.51 parts of Ir; 2.83 of N; o is 6.50.
Examples 6 to 20
The target compounds of examples 6 to 20 can be synthesized by the synthesis method of example 1 by replacing the corresponding reactants, and the specific structural chemical formulas and the results of MS (i.e., mass spectrum) are shown in table 1.
TABLE 1 chemical formulas of target compounds of examples 6 to 20 and MS results
Figure BDA0002605166240000171
Figure BDA0002605166240000181
Example 21
The embodiment provides an organic electroluminescent device, which comprises a substrate, an anode layer arranged on the substrate, a hole injection layer arranged on the anode layer, a hole transport layer arranged on the hole injection layer, an organic light emitting layer arranged on the hole transport layer, an electron transport layer arranged on the organic light emitting layer, an electron injection layer arranged on the electron transport layer and a cathode layer arranged on the electron injection layer.
The preparation method of the organic electroluminescent device comprises the following steps:
coating with a thickness of
Figure BDA0002605166240000188
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water and ultrasonic cleaning is carried out for 10 minutes, after the cleaning by distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and drying, the ITO glass substrate is transferred into a plasma cleaning machine, the ITO glass substrate is cleaned for 5 minutes and sent into an evaporation machine, the standard pressure is set to be 1 × 10-6 torr under the vacuum condition, and then CuPc is applied to the ITO glass substrate
Figure BDA0002605166240000182
NPB
Figure BDA0002605166240000183
CBP + formula I-1 (5%)
Figure BDA0002605166240000184
Alq3
Figure BDA0002605166240000185
LiF
Figure BDA0002605166240000186
And Al
Figure BDA0002605166240000187
The layers of organic substance are formed in sequence to prepare the organic electroluminescent device of the corresponding compound.
By referring to the above-mentioned method, formula I-1 is replaced with the compounds of formula I-2, formula I-10, formula I-20, formula I-29, formula I-45, formula I-56, formula I-66, formula I-79, formula I-84, formula I-90, formula I-98, formula I-105, formula I-108, formula I-114, formula I-119, formula I-124, formula I-128, formula I-130, formula I-136, respectively, to prepare the organic electroluminescent device of the corresponding compound.
Comparative example 1
An organic electroluminescent device was fabricated in the same manner as in example 21, except that the compound I-1 as the dopant of the organic light-emitting layer was replaced with the compound (btp)2Ir (acac), the resulting organic electroluminescent device.
Wherein the compounds used in the embodiments of the present invention are copper (II) phthalocyanine (CuPc), NPB, (btp)2Ir(acac)，Alq3And the structural formula of CBP, as follows:
Figure BDA0002605166240000191
to further illustrate the luminescence properties of the novel iridium complex as a phosphorescent material, the devices obtained in example 21 and comparative example 1 were tested for their luminescence properties, and the results of driving voltage, luminescence brightness, and luminescence efficiency were evaluated using a KEITHLEY model 2400 source measuring unit, a CS-2000 spectroradiometer, and are shown in table 2.
Table 2 test results of organic electroluminescent devices in example 21 and comparative example 1
Figure BDA0002605166240000192
Figure BDA0002605166240000201
As shown in the table, the compound of the present invention has a lower voltage and a significantly improved current efficiency under the same current. The compound obtained by the invention is used as a luminescent layer of an organic electroluminescent device, and the invention provides the organic electroluminescent device with longer service life compared with the prior material.
It will be apparent to those skilled in the art that many modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. It is therefore contemplated that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. An organic phosphorus luminescent material, wherein the structure of the organic phosphorus luminescent material is shown as formula I:
Figure FDA0002605166230000011
wherein:
R1～R6each independently represents hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C30Alkyl of (2), substituted or unsubstituted C6-C30Aryl of (2), substituted or unsubstituted C3-C30Cycloalkyl of (a), substituted or unsubstituted C1-C30Alkoxy of (2), substituted or unsubstituted C1-C30Alkylamino of (a), substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C2-C30Alkynyl of (a), substituted or unsubstituted C2-C30A heterocyclic group of (a);
R1、R3represents a mono-, di-, tri-or tetra-substituent, R2Represents a mono-or di-substituent.
2. The organic phosphorus luminescent material as claimed in claim 1, wherein R is1～R6Each independently selected from hydrogen, deuterium atom, cyano, substituted or unsubstitutedC1-C10Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C2-C10A heterocyclic group of (A), substituted or unsubstituted C6-C12Aryl group of (1).
3. An organophosphorus light-emitting material according to claim 1, wherein said alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
4. An organophosphorus light-emitting material according to claim 1, wherein said cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylcyclopentyl, 3,4, 5-trimethylcyclohexyl.
5. The organic phosphorus luminescent material according to any one of claims 1 to 4, wherein R is1～R6The hydrogen atom in the group or substituent group of (a) is deuterated.
6. A method for preparing the organic phosphorus luminescent material according to any one of claims 1 to 5, comprising the following steps:
s1, under the protection of nitrogen, reacting the compound with the structure of the formula (II) with iridium trichloride in a mixed solution of ethylene glycol ethyl ether and ultrapure water, and after the reaction is finished, carrying out post-treatment to obtain a compound with the structure of the formula (IV);
s2, under the protection of nitrogen, reacting the compound with the structure of the formula (IV) with the compound with the structure of the formula (III) in an ethylene glycol ether solvent, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure of the formula (I);
Figure FDA0002605166230000021
7. the method for preparing organophosphorus luminescent material according to claim 6, wherein the molar ratio of the compound having the structure of formula (II) to iridium trichloride is (2.2-2.8): 1.
8. The method for preparing an organophosphorus luminescent material according to claim 6, wherein the molar ratio of the compound having the structure of formula (IV) to the compound having the structure of formula (III) is 1 (2.5-8).
9. Use of the organic phosphorus luminescent material according to any one of claims 1 to 5, wherein the organic phosphorus luminescent material is used in an organic electroluminescent device.
10. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer, the organic layer being located between the first electrode and the second electrode; the organic layer comprises at least one; and at least one of the organic layers comprises the organic phosphorus luminescent material of any one of claims 1 to 5; the organic phosphorus luminescent material exists in the organic layer in a single form or mixed with other substances.
CN202010736486.0A 2020-07-28 2020-07-28 Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device Withdrawn CN111777646A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105837641A (en) * 2016-05-07 2016-08-10 吉林奥来德光电材料股份有限公司 Synthesizing and application of novel iridium metal complex phosphorescent material
CN108912175A (en) * 2018-06-05 2018-11-30 长春海谱润斯科技有限公司 A kind of metal iridium complex and its organic luminescent device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105837641A (en) * 2016-05-07 2016-08-10 吉林奥来德光电材料股份有限公司 Synthesizing and application of novel iridium metal complex phosphorescent material
CN108912175A (en) * 2018-06-05 2018-11-30 长春海谱润斯科技有限公司 A kind of metal iridium complex and its organic luminescent device

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