CN111039997A - Organic phosphorus luminescent material and preparation method and application thereof - Google Patents
Organic phosphorus luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic phosphorus luminescent material and a preparation method and application thereof, wherein the organic phosphorus luminescent material has a structural general formula as shown in the specification
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organophosphorus luminescent material of an iridium complex of metal with multiple nitrogen atoms in a heterocyclic structure, and a preparation method and application thereof.
Background
Organic electroluminescent devices have been attracting attention in the fields of new-generation large-area flat panel displays and semiconductor solid-state illumination light sources due to their advantages of self-emission, fast response, high luminance, flexibility, rollability, and the like. It is the most competitive technology in the third generation flat panel reality due to its potentially superior performance in the display technology field. Compared with traditional display devices such as a CRT (cathode ray tube), an LCD (liquid crystal display), a PDP (plasma display panel) and the like, the OLED has all the advantages of the existing display, has unique advantages, not only has high brightness, high contrast, high definition, wide visual angle, wide color gamut and the like to realize high-quality images, but also has the characteristics of ultra-thinness, ultra-lightness, low driving voltage, low power consumption, wide temperature and the like to meet the requirements of portable equipment on portability, power saving and outdoor operation; the OLED has the unique characteristics of self-luminescence, high luminous efficiency, short response time, transparency, flexibility and the like, and therefore, the OLED has a good development prospect.
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. However, the development of organic electroluminescent devices has been significantly lagged behind due to the limitation of materials. Further improvements are currently needed in terms of lifetime and production costs.
As the light emitting material, excitons are formed by recombination of electrons and holes injected from each electrode, in which 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. In such a phosphorescent material, the red phosphorescent material may have greater luminous efficiency than the fluorescent material. Therefore, as an important factor for improving the efficiency of the organic electroluminescent device, red phosphorescent materials are being widely studied.
However, the luminescent materials disclosed at present have the disadvantages of high synthesis price, high synthesis process requirement, high purification requirement in the synthesis process, short service life, low efficiency and the like. Therefore, the development of a material with high luminous efficiency and long lifetime is a technical problem to be solved.
Disclosure of Invention
In view of the above, the present invention provides an organic phosphorus luminescent material, and a preparation method and an application thereof, and the organic phosphorus luminescent material provided by the present invention can improve the luminescent efficiency of an organic electroluminescent device and prolong the service life of the device as a luminescent material of the organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic phosphorus luminescent material, wherein the structure of the organic phosphorus luminescent material is shown as formula I:
wherein:
R1～R6each independently represents hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino radical, substituted or unsubstituted C2-C60Alkylene, substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C4-C60Heterocyclyl, substituted or unsubstituted C8-C60Condensed ring radical, substituted or unsubstituted C5-C60Spiro ring radical, R1～R6The same or different;
R1～R6in any position of the ring, R1～R4The number of substituents is 0 to 4, R5The number of substituents is 0 to 1, R6The number of the substituents is 0 to 2.
Preferably, said R is1～R6Each independently represents hydrogen, a deuterium atom, a substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C3-C20Alkoxy, substituted or unsubstituted C4-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C10-C20Condensed ring radical, R1～R6The same or different.
Preferably, said substituted or unsubstituted C1-C20The alkyl group includes any of methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl.
Preferably, said substituted or unsubstituted C6-C20The aryl group comprises any one of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene and fluorene.
Preferably, said substituted or unsubstituted C3-C20The cycloalkyl group includes any one of cyclopropyl, cyclopentyl, cyclohexyl and adamantylamine.
Preferably, said substituted or unsubstituted C4-C20The heterocyclic group includes an aromatic or non-aromatic cyclic group containing at least one heteroatom selected from the group consisting of O, S, N, P, B, Si and a combination of one or more of Se.
Preferably, said R is1～R6Independently of each other and between the ringsThe substituents forming the condensed ring/aromatic heterocycle and not forming the condensed ring or the aromatic heterocycle represent hydrogen, deuterium atom, substituted or unsubstituted C3-C60Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C20Cycloalkyl of (a), substituted or unsubstituted C4-C60A heterocyclic group of, substituted or unsubstituted C10-C20Condensed ring group of, substituted or unsubstituted C5-C60The spiro ring group of (1).
Preferably, said R is1～R6Each independently forms a condensed ring/aromatic heterocycle with other adjacent substituent on the ring, and the substituent not forming the condensed ring or the aromatic heterocycle represents hydrogen, deuterium atom, substituted or unsubstituted C3-C60Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C20Cycloalkyl of (a), substituted or unsubstituted C4-C60A heterocyclic group of, substituted or unsubstituted C10-C20Condensed ring group of, substituted or unsubstituted C5-C60The spiro ring group of (1).
Preferably, said R is1～R6The group or substituent group in which the hydrogen atom is deuterated.
Preferably, the specific structural formula of the organic phosphorus luminescent material is as follows:
the invention also provides a preparation method of the organic phosphorus luminescent material, which comprises the following steps:
s1, reacting the compound with the structure of the formula II with iridium trichloride under the protection of inert gas, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure of the formula III;
s2, under the protection of inert gas, reacting the compound with the structure shown in the formula III with silver trifluoromethanesulfonate and methanol, and after the reaction is finished, carrying out post-treatment to obtain a compound with the structure shown in the formula IV;
s3, under the protection of inert gas and at the temperature of 85-95 ℃, carrying out reflux reaction on the compound with the structure of the formula IV and the compound with the structure of the formula V in absolute ethyl alcohol for 20-30h, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure of the formula I;
the synthetic route is as follows:
preferably, in the step S1, the reaction molar ratio of the compound with the structure of formula II to the iridium trichloride is (2.2-3): 1.
Further, in the step S1, the compound having the structure of formula II and iridium trichloride are dissolved in a mixed solvent of ethylene glycol ethyl ether and water, wherein a volume ratio of ethylene glycol ethyl ether to water is (2-5): 1, the reaction temperature is 115-125 ℃, and the reaction time is 20-30 hours.
In step S1, the post-processing procedure is as follows: and cooling to room temperature after the reaction is finished, separating out a precipitate, carrying out suction filtration on the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence to obtain a yellow powder bridged ligand compound shown in formula III.
Preferably, in the step S2, the reaction molar ratio of the compound with the structure of formula III to silver trifluoromethanesulfonate is 1 (2.2-3.5).
Further, in step S2, the compound having the structure of formula III is reacted with silver trifluoromethanesulfonate and methanol in dichloromethane, wherein the volume ratio of methanol to dichloromethane is 1: (2-5) the reaction temperature is 20-30 ℃, and the reaction time is 24-48 hours.
In step S2, the post-processing procedure is as follows: and cooling the reaction liquid to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain the compound of the iridium complex intermediate formula IV as yellow powder.
Preferably, in the step S3, the reaction molar ratio of the compound with the structure of formula IV to the compound with the structure of formula V is 1 (1.5-3.5).
Further, in step S3, the post-processing procedure is: and (3) carrying out suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, carrying out silica gel column chromatography, and concentrating the filtrate to precipitate a solid to obtain a final yellow compound, namely the target compound of the formula I.
The invention also provides an application of the organic phosphorus luminescent material in preparing an organic electroluminescent device.
The invention also provides an organic electroluminescent device which comprises a substrate, and an anode layer, a hole transport layer, an organic luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially evaporated on the substrate, wherein the organic luminescent layer comprises a main material and a doping material, and the doping material is the organic phosphorus luminescent material.
Preferably, the weight ratio of the host substance to the doping material is 90: 10-99.5: 0.5.
Preferably, the thickness of the organic light emitting layer is 25 to 35 nm.
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 and the preparation method and application thereof provided by the invention have the following beneficial effects:
(1) the organic phosphorus luminescent material provided by the invention has the advantages that the specific heterocyclic complex is selected, the wavelength of the compound is adjusted, and the obtained organic metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life is long.
(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 formula I-1 comprises the following steps:
s1, weighing formula II-1 (50mmol, 7.75g), IrC1 under the protection of nitrogen3·3H2O (20mmo1, 7.05g) is put into a reaction system, 210mL of mixed solution of ethylene glycol ethyl ether and 70m1 of purified water is added, the mixture is refluxed for 24 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 to obtain yellow powder of the bridged ligand III-1(5.36g, the yield is 50%).
S2, weighing the intermediate compound III-1(5 mmol, 5.36g), adding silver trifluoromethanesulfonate (15mmol, 3.86g), adding 100ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, concentrating the filtrate of column chromatography (short column) until solid is separated out, and obtaining yellow powder of the iridium complex intermediate compound IV-1 (6.55g, 92% yield).
S3, weighing the intermediate IV-1 (9mmol, 6.41g), adding the ligand V-1 (27mmol, 7.99g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, performing suction filtration, washing with alcohol, and drying. Using dichloromethane as solvent, performing silica gel column chromatography, concentrating the filtrate, and precipitating solid to obtain final yellow compound formula I-1) with HPLC purity of more than 99%, wherein the mass spectrum and element analysis results of the compound formula I-1 are as follows:
mass spectrum calculated 796.18, test value 796.13;
elemental analysis calculated as C63.38; h is 3.42; 24.15 parts of Ir; n is 7.04; o is 2.01; test value C: 63.39; h is 3.43; 24.14 parts of Ir; n is 7.02; o is 2.02.
Example 2
The synthesis of I-32 comprises the following steps:
s1, weighing formula II-32 (48mmol, 8.79g) IrC1 under the protection of nitrogen3·3H2O (20mmo1, 7.05g) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 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 to obtain yellow powder of the bridged ligand III-32 (5.68g, the yield is 48%).
S2, weighing the intermediate compound IV-32 (4.5mmol, 5.33g), adding silver trifluoromethanesulfonate (14mmol, 3.6g), adding 100ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain yellow powder of the intermediate compound IV-32 (6.36g, 92% yield).
S3, weighing the intermediate IV-32 (8mmol, 6.15g), adding the ligand V-32 (24mmol, 7.44g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, performing suction filtration, washing with alcohol, and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride as a solvent to concentrate the solid to precipitate out to give the final yellow compound of formula I-32 (1.73g, 25% yield) having an HPLC purity of more than 99%, and the results of mass spectrometry and elemental analysis of the compound of formula I-32 were as follows:
mass spectrum calculated 866.26, test value 866.22;
elemental analysis calculated as C: 65.18; h is 4.31; 22.19 parts of Ir; n is 6.47; o is 1.85; test value C: 65.19; h is 4.30; 22.18 parts of Ir; n is 6.46; o is 1.87.
Example 3
The synthesis of formula I-76, comprising the following steps:
s1, weighing formula II-76 (60mmol, 10.15g), IrC1 under the protection of nitrogen3·3H2O (20mmo1, 7.05g) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 purified water is added, the mixture is refluxed for 24 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 to obtain yellow powder of a bridging ligand III-76 (5.64g, the yield is 50%).
S2, weighing the intermediate III-76 (5mmol, 5.64g), adding silver trifluoromethanesulfonate (14mmol, 3.6g), adding 100ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is precipitated. The iridium complex intermediate of formula IV-76 (6.66g, 90%) was obtained as a yellow powder.
S3, weighing the intermediate IV-76 (9mmol, 6.66g), adding the ligand V-76 (22.5mmol, 7.29g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride and toluene as solvents to concentrate the solid to give a final yellow compound of formula I-76 (1.76g, 23% yield) having an HPLC purity of more than 99%, and the results of mass spectrometry and elemental analysis of the compound of formula I-76 were as follows:
mass spectrum calculated 852.24; test value 852.28;
elemental analysis, calculated value is C: 64.85; h is 4.14; 22.56 parts of Ir; n is 6.58; o is 1.88; test value C: 64.87; h is 4.15; 22.55 parts of Ir; n is 6.57; o is 1.87.
Example 4
The synthesis of formula I-110 comprises the following steps:
s1, weighing formula II-110 (50mmol, 10.56g), IrC13·3H2Adding O (20mmo1, 7.05g) into a reaction system, adding a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand III-110 (6.48g, 50% yield) was obtained as a yellow powder.
S2, weighing the intermediate III-110 (5mmol, 6.48g), adding silver trifluoromethanesulfonate (15mmol, 3.86g), adding 100ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula IV-110 was obtained as a yellow powder (7.66g, 93% yield).
S3, weighing the intermediate IV-110 (9mmol, 6g), adding the ligand V-110 (27mmol, 9.13g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The filtrate was subjected to silica gel column chromatography using toluene as a solvent to concentrate the solid to precipitate out to give the final yellow compound of formula I-110 (1.88g, 22% yield) having an HPLC purity of more than 99%, and the results of mass spectrometry and elemental analysis of the compound of formula I-110 were as follows:
mass spectrum calculated 950.35; test value 950.3;
elemental analysis calculated as C: 66.99; h is 5.20; ir of 20.23; n is 5.90; o is 1.68; the test value is C: 66.98; h is 5.21; ir of 20.23; n is 5.91; o is 1.67.
Example 5
The synthesis of formula I-140 comprises the following steps:
s1, weighing formula II-140 (60mmol, 10.32g) IrC1 under the protection of nitrogen3·3H2O (20mmo1, 7.05g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, the mixture is refluxed for 24 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 III-140 was obtained as a yellow powder (5.89g, 50% yield).
S2, weighing the intermediate III-140 (5mmol, 5.89g), adding silver trifluoromethanesulfonate (15mmol, 3.86g), adding 100mL of dichloromethane into the system, adding 40mL of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula IV-140 was obtained as a yellow powder (6.78g, 91% yield).
S3, weighing the intermediate IV-140 (9mmol, 6.72g), adding the ligand V-140 (27mmol, 9.45g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, performing suction filtration, washing with alcohol, and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride as a solvent to concentrate the solid to precipitate out to give a final yellow compound of formula I-140 (1.59g, 20% yield) having an HPLC purity of more than 99%, and the results of mass spectrometry and elemental analysis of the compound of formula I-140 were as follows:
mass spectrum calculated 886.30; test value 886.39;
elemental analysis calculated as C: 65.06; h is 5.12; 21.69 parts of Ir; n is 6.32; o is 1.81; test value C: 65.04; h is 5.10; 21.69 parts of Ir; n is 6.35; o is 1.82.
Example 6
The synthesis of formula I-176 is carried out by the following steps:
s1, weighing formula II-176 (60mmol, 11.35g), IrC13·3H2Adding O (20mmo1, 7.05g) into a reaction system, adding a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. The bridged ligand III-176 (6.04g, 50% yield) was obtained as a yellow powder.
S2, weighing the intermediate III-176 (5mmol, 6.04g), adding silver trifluoromethanesulfonate (15mmol, 3.86g), adding 100ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula IV-176 was obtained as a yellow powder (7.41g, 95% yield).
S3, weighing the intermediate IV-176 (9.5mmol, 7.41g), adding the ligand V-176 (28.5mmol, 9.41g), adding 120ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The filtrate was subjected to silica gel column chromatography using methylene chloride as a solvent to concentrate the solid to precipitate out to give the final yellow compound of formula I-176 (2.3g, 27% yield) having an HPLC purity of more than 99%, and the results of mass spectrometry and elemental analysis of the compound of formula I-176 were as follows:
mass spectrum: calculated value 898.39; test value 898.33;
elemental analysis: calculated value is C64.19; h is 6.39; 21.40 parts of Ir; n is 6.24; o is 1.78; the test value is C: 64.17; h is 6.37; 21.42 parts of Ir; n is 6.25; o is 1.79.
Examples 7 to 22
The target compounds of examples 7 to 22 were synthesized according to the synthesis method of example 1 by replacing the corresponding reactants, and the specific structures, product masses, yields, and results of FD-MS (mass spectrometry) are shown in table 1.
TABLE 1 details of structures, product masses, yields and FD-MS results for the target compounds of examples 7 to 22
Example 23
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 air barrier layer arranged on the organic light emitting layer, an electron transport layer arranged on the air barrier 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
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. Firstly, evaporating N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl-1, 4-diamine ('2-TNATA') 60nm on an ITO (anode), then evaporating NPB60nm, a host substance 4, 4'-N, N' -biphenyl dicarbazole ('CBP') and a doping substance compound formula I-1 in a mixed manner for 30nm, wherein the weight ratio of the CBP to the compound formula I-1 is 90:10, the thickness of a hole blocking layer ('BAlq') is 10nm, and an electron transport layer 'Alq' is evaporated340nm thick evaporated electron injection layer LiFThe organic electroluminescent device is prepared in a mode of 0.2nm and 150nm of evaporated cathode Al.
By substituting formula I-1 with formula I-3, formula I-13, formula I-27, formula I-32, formula I-34, formula I-45, formula I-56, formula I-62, formula I-76, formula I-87, formula I-94, formula I-102, formula I-110, formula I-117, formula I-128, formula I-137, formula I-140, formula I-159, formula I-162, formula I-182, respectively, with the above-mentioned method, an organic electroluminescent device of the corresponding compound was prepared.
Comparative example 1
An organic electroluminescent device was fabricated in the same manner as in example 23, except that the dopant species of the organic light-emitting layer, the compound of formula I-1, was replaced with the compound Ir (ppy)3The resulting organic electroluminescent device, Compound Ir (ppy)3The structural formula of (A) is as follows:
to further illustrate the luminescence properties of the novel iridium complex as a phosphorescent material, the devices obtained in example 23 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 23 and comparative example 1
As can be seen from Table 2, the light-emitting luminance was 5000cd/cm2Compared with the comparative example 1, the driving voltage of the device provided by the invention is 3.0-4.0V, which is only about half of that of the comparative example 1, the efficiency (80.1-85.1) is 3-4 times that of the comparative example 1, and the service life (728-782) is as long as that of the comparative example 113 to 14 times of comparative example 1, it can be seen that an organic electroluminescent device prepared using the compound of the present invention as a dopant material for a light emitting layer and a comparative compound Ir (ppy)3Compared with the organic electroluminescent device prepared by the doped material of the luminescent layer, the driving electricity is obviously reduced, and the luminous efficiency and the service life are obviously improved.
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:
wherein:
R1～R6each independently represents hydrogen, deuterium atom, halogen, cyano, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphoryl, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstitutedC2-C60Alkylene, substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C4-C60Heterocyclyl, substituted or unsubstituted C10-C60Condensed ring radical, substituted or unsubstituted C5-C60Spiro ring radical, R1～R6The same or different;
R1～R6in any position of the ring, R1～R4The number of substituents is 0 to 4, R5The number of substituents is 0 to 1, R6The number of the substituents is 0 to 2.
2. The organic phosphorus luminescent material as claimed in claim 1, wherein R is1～R6Each independently represents hydrogen, a deuterium atom, a substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C3-C20Alkoxy, substituted or unsubstituted C4-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C10-C20Condensed ring radical, R1～R6The same or different.
3. The organic phosphorus luminescent material of claim 2, wherein the substituted or unsubstituted C is1-C20The alkyl group includes any of methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl.
4. The organic phosphorus luminescent material of claim 2, wherein the substituted or unsubstituted C is6-C20The aryl group comprises any one of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene and fluorene.
5. The organic phosphorus luminescent material of claim 2, wherein the substituted or unsubstituted C is3-C20The cycloalkyl group includes any one of cyclopropyl, cyclopentyl, cyclohexyl and adamantylamine.
6. The organic phosphorus luminescent material of claim 2, wherein the substituted or unsubstituted C is4-C20The heterocyclic group includes an aromatic or non-aromatic cyclic group containing at least one heteroatom selected from the group consisting of O, S, N, P, B, Si and a combination of one or more of Se.
7. The organic phosphorus luminescent material according to any one of claims 1 to 6, wherein R is1～R6Each independently forms a condensed ring/aromatic heterocyclic ring with the ring, and the substituent group not forming the condensed ring or the aromatic heterocyclic ring represents hydrogen, a deuterium atom, a substituted or unsubstituted C3-C60Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C20Cycloalkyl of (a), substituted or unsubstituted C4-C60A heterocyclic group of, substituted or unsubstituted C10-C20Condensed ring group of, substituted or unsubstituted C5-C60The spiro ring group of (1).
8. A method for preparing the organic phosphorus luminescent material according to any one of claims 1 to 7, comprising the following steps:
s1, reacting the compound with the structure of the formula II with iridium trichloride under the protection of inert gas, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure of the formula III;
s2, under the protection of inert gas, reacting the compound with the structure shown in the formula III with silver trifluoromethanesulfonate and methanol, and after the reaction is finished, carrying out post-treatment to obtain a compound with the structure shown in the formula IV;
s3, under the protection of inert gas and at the temperature of 85-95 ℃, carrying out reflux reaction on the compound with the structure shown in the formula IV and the compound with the structure shown in the formula V in a single solvent of absolute ethyl alcohol or ethylene glycol ethyl ether for 20-30h, and after the reaction is finished, carrying out post-treatment to obtain the compound with the structure shown in the formula I;
the synthetic route is as follows:
9. an organic electroluminescent device, comprising a substrate, and an anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, an organic light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer which are sequentially evaporated on the substrate, wherein the organic light emitting layer comprises a host material and a doping material, and the doping material is the organic phosphorus light emitting material according to any one of claims 1 to 7.
10. Use of an organic electroluminescent device according to claim 9 in an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
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| CN102449107A (en) * | 2009-04-06 | 2012-05-09 | 通用显示公司 | Metal complex comprising novel ligand structures |
| US20180097185A1 (en) * | 2016-06-20 | 2018-04-05 | Universal Display Corporation | Organic electroluminescent materials and devices |
| WO2019143153A1 (en) * | 2018-01-17 | 2019-07-25 | 주식회사 엘지화학 | Novel compound and organic light emitting device using same |
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| CN102449107A (en) * | 2009-04-06 | 2012-05-09 | 通用显示公司 | Metal complex comprising novel ligand structures |
| US20180097185A1 (en) * | 2016-06-20 | 2018-04-05 | Universal Display Corporation | Organic electroluminescent materials and devices |
| WO2019143153A1 (en) * | 2018-01-17 | 2019-07-25 | 주식회사 엘지화학 | Novel compound and organic light emitting device using same |
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