CN112321645A - Acridine compound and light-emitting device - Google Patents
Acridine compound and light-emitting device Download PDFInfo
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- CN112321645A CN112321645A CN201911399298.7A CN201911399298A CN112321645A CN 112321645 A CN112321645 A CN 112321645A CN 201911399298 A CN201911399298 A CN 201911399298A CN 112321645 A CN112321645 A CN 112321645A
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- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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Abstract
The invention relates to an acridine compound and application thereof. The structural formula of the acridine compound is shown as a formula (I):
wherein Ar is selected from: substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; r1、R2Each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; x is selected from oxygen or sulfur. The acridine compound provided by the invention has good electron transport performance and hole transport performance, so that the acridine compound can be used as a material of a hole transport layer and an electron transport layer; and the acridine compound has higher triplet state energy levelThe product is a good bipolar host material, and the host material used as the luminescent layer can enable more energy of excitons to be transmitted to a luminophor, thereby improving the luminous efficiency of the luminescent device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an acridine compound and a luminescent device.
Background
A conventional oled (organic Light Emitting diode) is a sandwich-like structure, and is an electroluminescent device composed of a cathode, an anode and an organic functional layer between the electrodes. The OLED light-emitting device is a current-type device, electrons are injected through an electron injection layer and are transported through an electron transport layer, holes are injected through a hole injection layer and are transported through a hole transport layer, and the electrons and the holes are combined in a light-emitting layer and emit light, namely OLED electroluminescence. In recent years, organic electroluminescent devices (TADF-OLEDs) based on a thermally activated delayed fluorescence mechanism have attracted extensive research interest and become the next generation of optoelectronic devices.
However, the performance of the current TADF-OLEDs is still to be improved.
Disclosure of Invention
Based on this, it is an object of the present invention to provide an acridine compound having a relatively high triplet energy level and having good hole transporting and electron transporting properties.
The specific technical scheme is as follows:
an acridine compound, the structural formula of which is shown in formula (I):
wherein Ar is selected from: substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
R1、R2each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
x is selected from: oxygen or sulfur.
Another object of the present invention is to provide a light emitting device, comprising: and the functional layer is formed by materials comprising the acridine compound.
Compared with the prior art, the invention has the following beneficial effects:
the molecular structure of the acridine compound provided by the invention is taking acridine-spiro-phosphoxyheteroanthracene or acridine-spiro-phosphothioanthracene as a nucleus. Because a spiro structure is adopted as a bridge between the donor (acridine) and the acceptor (phosphoxyheteroanthracene or phosphothioanthracene), the plane of the acridine unit and the plane of the hexatomic ring containing phosphoxy or the hexatomic ring containing phosphothioanthracene are constructed in a cross-perpendicular mode, the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) energy levels can be well separated, and the spiro structure can break pi conjugation, so that the acridine compound has a high triplet energy level.
Meanwhile, due to the existence of phosphorus oxy or phosphorus sulfur, the material has good electron transport performance; the acridine compound has good hole transport performance due to the existence of the acridine unit, so the acridine compound can be used as a material of a hole transport layer or an electron transport layer; and the acridine compound becomes a good bipolar host material due to the high triplet state energy level, and the host material used as the luminescent layer can transmit more energy of excitons to a luminous body, so that the luminous efficiency of the luminescent device is improved.
Drawings
Fig. 1 is a structural view of a light emitting device according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings, which illustrate embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the compounds of the present invention, when any variable (e.g., R1, R2, etc.) occurs more than one time in any constituent, its definition in each occurrence is independent of its definition at every other occurrence. Also, combinations of substituents and variables are permissible only if such combinations result in stable compounds. It is to be understood that substituents and substituted forms of the compounds of the present invention may be selected by one of ordinary skill in the art to provide compounds that are chemically stable and that can be readily synthesized by techniques in the art and methods set forth herein from readily available starting materials. If a substituent is itself substituted with more than one group, it is understood that these groups may be on the same carbon atom or on different carbon atoms, so long as the structure is stable.
The aryl groups described herein can be a single ring (monocyclic) or multiple rings (bicyclic, or more) fused together or covalently linked. The alkyl group includes straight-chain alkyl, alkyl containing branched chain, cycloalkyl and alkoxy. The heteroaryl group is an aryl group containing one or more heteroatoms.
An acridine compound, the structural formula of which is shown in formula (I):
wherein Ar is selected from: substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
R1、R2each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; x is selected from: oxygen or sulfur.
In one embodiment, Ar is selected from: substituted or unsubstituted aryl or heteroaryl having 6 to 60 ring atoms;
R1、R2each independently selected from: H. a substituted or unsubstituted alkyl group having 3 to 50C atoms, or a substituted or unsubstituted aryl or heteroaryl group having 6 to 60 ring atoms;
wherein the heteroatom in the heteroaryl group is nitrogen, oxygen or sulfur;
the substituents in the substituted alkyl group, the substituents in the substituted aryl group, and the substituents in the substituted heteroaryl group are each independently selected from: deuterium groups, alkyl groups, aryl groups, nitro groups, cyano groups, arylamine groups, halogens, hydroxyl groups, carboxyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkoxycarbonyl groups, perfluoroalkyl groups, perfluoroalkoxy groups, aralkyl groups, silyl groups, siloxane groups, or thioalkoxy groups.
In one embodiment, aryl is selected from: phenyl, biphenyl, triphenyl, benzo, naphthyl, anthryl, benzonaphthyl, phenanthryl, fluorenyl, pyrenyl, chrysenyl, perylenyl, or azulenyl.
In one embodiment, the heteroaryl is selected from: dibenzothienyl, dibenzofuryl, furyl, thienyl, benzofuryl, benzothienyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, oxadiazolyl, indolyl, benzimidazolyl, indazolyl, indolizinyl, benzoxazolyl, isoxazolyl, benzothiazolyl, quinolyl, isoquinolyl, o-diaza-naphthyl, quinazolinyl, quinoxalinyl, naphthyl, phthalidyl, pteridinyl, xanthinyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, dibenzoselenophenyl, benzoselenophenyl, benzofuropyridylpyrazolyl, indolocarbazolyl, pyridylindolyl, pyrrolydipyridoindolyl, Furan bipyridyl, benzothiophene furopyridinyl, thienobipyridyl, benzoselenophenopyridine, or selenophene bipyridyl.
In one embodiment, the alkyl group is selected from: methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl or isohexyl.
In one embodiment, R1、R2Each independently selected from: H. carbazolyl, benzocarbazolyl, benzopyrolyl, pyridyl, pyrazinyl, benzophenazinyl, benzothiazinyl, benzosilazinyl, spirofluorenyl or benzazedinyl.
In one embodimentAr is selected from:
wherein R is3Is selected from H or
R1、R2Each independently selected from: h or
In one embodiment, the acridine compound is selected from:
the acridine compound provided by the invention also has good film-forming property and thermal stability, higher glass transition temperature and proper HOMO and LUMO energy levels, is used for preparing a light-emitting device, and can effectively improve the efficiency and stability of the light-emitting device.
The invention also provides application of any one of the acridine compounds in preparation of a light-emitting device.
Further, the light emitting device may be an organic electroluminescent device (TADF-OLEDs) based on a thermally activated delayed fluorescence mechanism. Similar to phosphorescent OLEDs, most of the light-emitting layers of TADF-OLEDs adopt a host-guest mixed structure in which TADF emitters are dispersed as guests within a host material as a substrate, and the concentration of the guest material in the host material is relatively low in order to reduce concentration quenching and triplet-triplet annihilation. A suitable high-performance host material is therefore particularly important for a high-performance stable TADF-OLED.
In general, the main materials for preparing TADF-OLEDs need to satisfy the following requirements: a higher triplet energy level than the TADF material is required to prevent energy transfer from guest to host; the host material needs to have the appropriate lowest unoccupied orbital Level (LUMO) and highest occupied orbital level (HOMO) relative to the adjacent transport layer to facilitate carrier injection; bipolar carrier transport properties; and good thermal stability and morphology stability to ensure good device stability.
The molecular structure of the acridine compound provided by the invention takes acridine-spiro-phosphoxyheteroanthracene or acridine-spiro-phosphothioanthracene as a nucleus. A spiro structure is adopted as a bridge between a donor (acridine) and an acceptor (phosphoxyheteroanthracene or phosphothioanthracene), a plane where an acridine unit is located and a plane where a six-membered ring containing a phosphoxy group or a six-membered ring containing a phosphothioanthracene are located are constructed in a cross-perpendicular mode, so that the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) energy levels can be well separated, and the spiro structure can break pi conjugation, therefore, the acridine compound has a high triplet state energy level, so that the acridine compound becomes a good bipolar host material and is used as a host material of a light-emitting layer, and the energy of excitons is more transmitted to a light-emitting body.
The acridine compound provided by the invention also has good film-forming property and thermal stability, higher glass transition temperature and proper HOMO and LUMO energy levels.
In conclusion, the acridine compound is used as a main material of a light-emitting layer to prepare a light-emitting device, so that the efficiency and stability of the light-emitting device can be effectively improved.
Furthermore, the acridine compound provided by the invention has good electron transport performance due to the existence of phosphorus oxy or phosphorus thio; due to the existence of the acridine unit, the acridine compound has good hole transport performance, so that the acridine compound can be used as a material of a hole transport layer or an electron transport layer to prepare a light-emitting device.
The invention also provides a light-emitting device which comprises a functional layer, wherein the material for forming the functional layer comprises the acridine compound.
In an embodiment, the functional layer of the light emitting device includes at least one of a light emitting layer, a hole transport layer, and an electron transport layer. More specifically, the acridine compound can be used as a host material in a light-emitting layer.
Further, the light emitting device includes a first electrode, a hole injection layer formed on the first electrode, a hole transport layer formed on the hole injection layer, a light emitting layer formed on the hole transport layer, an electron transport layer formed on the light emitting layer, an electron injection layer formed on the electron transport layer, and a second electrode formed on the electron injection layer.
The invention also provides a display device which comprises the light-emitting device.
It is understood that the display device may be a device for displaying such as a mobile phone, a computer, a tablet, a television, or the like.
The present invention will be described in further detail with reference to specific examples.
Synthesis of precursor 1:
mixing the raw materials
(10mmol) and
(50mol) mixing, reacting for 12h at 120 ℃ to obtain the raw materials
After consumption, the reaction solution is cooled, concentrated and dissolved in DMF, excess NaH (20mmol) is added, after reaction is carried out for 30min at 0 ℃, ammonium chloride aqueous solution is added to stop the reaction, a precursor 1 is obtained by filtration, and recrystallization purification is carried out on the precursor 1, wherein the yield is 80%.
Synthesis of precursor 1-1:
mixing the raw materials
(10mmol)，
(50mol) mixing, reacting for 12h at 120 ℃ to obtain the raw materials
After consumption, cooling the reaction solution, concentrating and dissolving in DMF, adding excessive NaH (20mmol), reacting at 0 ℃ for 30min, adding ammonium chloride aqueous solution to terminate the reaction, filtering to obtain a precursor 1-1, and recrystallizing and purifying the precursor 1-1 with the yield of 78%.
And (3) synthesizing a precursor 2-5:
precursor 1(10mmol) was dissolved in 50mL of glacial acetic acid, heated to reflux, and 1.2-fold molar equivalent of liquid bromine (12mmol) was added and reacted overnight. Extraction with dichloromethane, washing with water, drying, removal of the solvent under reduced pressure and separation by silica gel chromatography and HPLC gave 2 as a white solid in 30% yield, respectively.
Precursor 1(10mmol) was dissolved in 50mL of glacial acetic acid, heated to reflux, and 2.2-fold molar equivalent of liquid bromine (22mmol) was added and reacted overnight. Extraction with dichloromethane, washing with water, drying, removal of the solvent under reduced pressure and separation by silica gel chromatography and HPLC gave 3 as a white solid in 32% yield, respectively.
Precursor 2(1.5mmol), amine compound
(1.75mmol)，CuI(0.15g)，K2CO3(0.28g), 18-crown-6 (0.05g) was dissolved in N, N-Dimethylpropylurea (DMPU), heated at 180 ℃ overnight, extracted with dichloromethane, dried, extracted, and passed through a column to give compound 4 in 80% yield.
Precursor 3(1.5mmol), amine compound
(3.5mmol)，CuI(0.23g)，K2CO3(0.55g), 18-crown-6 (0.1g) was dissolved in N, N-Dimethylpropylurea (DMPU), heated at 180 ℃ overnight, extracted with dichloromethane, dried, extracted, and subjected to column chromatography to give compound 5 in 80% yield.
Synthesis of compound M1:
reacting triphenyl phosphine bromide
(20mmol) was dissolved in 60ml of anhydrous THF, cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, incubated for 1 hour, 1(19mmol) was dissolved in 30ml of THF, added dropwise to the reaction system overnight, extracted with dichloromethane, dried, and chromatographed on silica gel to give a white solid. And directly adding the obtained white solid into glacial acetic acid, heating and refluxing, adding 15ml of concentrated hydrochloric acid to generate solid precipitate, and performing suction filtration to obtain a white solid product 6 with the yield of 52%.
The solid product 6(2.4mmol) was dissolved in 50mL of dichloromethane, and 6mL (about 1.2 times molar equivalent) of hydrogen peroxide was slowly added dropwise to the reaction solution, followed by reaction overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M1 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS37H26NOP, detection value [ M +]+531.17, calculate value 531.59.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):7.77(d,4H),7.54-7.51(m,5H),7.41-7.38(m,4H),7.24-7.14(m,8H),7.08(m,2H),7.00-6.95(m,3H)。
Synthesis of compound M2:
reacting triphenyl phosphine bromide
(20mmol) was dissolved in 60ml of anhydrous THF, cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, incubated for 1 hour and the mixture was cooled
(19mmol) was dissolved in 30ml THF, added dropwise to the reaction system overnight, extracted with dichloromethane, dried, and chromatographed on silica gel to give a white solid. And directly adding the obtained white solid into glacial acetic acid, heating and refluxing, adding 15ml of concentrated hydrochloric acid to generate solid precipitate, and performing suction filtration to obtain a white solid product 7 with the yield of 52%.
The solid product 7(2.4mmol) was dissolved in 50mL of dichloromethane, and 6mL (about 1.2 times molar equivalent) of hydrogen peroxide was slowly added dropwise to the reaction solution, followed by reaction overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M2 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS49H33N2OP, detection value [ M +]+696.15, calculate value 696.79.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,1H),8.19(d,1H),7.94(d,1H),7.77(m,4H),7.58-7.41(m,9H),7.38-7.35(m,3H),7.20-7.14(m,10H),7.04(d,1H),6.95(t,1H)。
Synthesis of compound M3:
reacting triphenyl phosphine bromide
(20mmol) was dissolved in 60ml of anhydrous THF, cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, the temperature was maintained for 1 hour, precursor 4(19mmol) was dissolved in 30ml of THF and added dropwise to the reaction system overnight. Extraction with dichloromethane, drying and chromatography on silica gel column gave a white solid. Adding the obtained white solid into glacial acetic acid, heating and refluxing, adding 15ml concentrated hydrochloric acid to obtain solidThe precipitate was filtered off with suction to give the product 8 as a white solid in 52% yield.
The solid product 8(2.4mmol) was dissolved in 50mL of dichloromethane. 6ml (about 1.2 times molar equivalent) of hydrogen peroxide was slowly added dropwise to the reaction solution, and reacted overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M3 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS49H33N2OP, detection value [ M +]+696.22, calculate value 696.79.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,1H),8.19(d,1H),7.94(d,1H),7.77-7.74(m,5H),7.59-7.50(m,8H),7.41-7.31(m,6H),7.24-7.14(m,7H),7.08-6.95(m,4H)。
Synthesis of compound M4:
reacting triphenyl phosphine bromide
(20mmol) was dissolved in 60ml of anhydrous THF, cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, the temperature was maintained for 1 hour, precursor 5(19mmol) was dissolved in 30ml of THF and added dropwise to the reaction system overnight. Extraction with dichloromethane, drying and chromatography on silica gel column gave a white solid. And directly adding the obtained white solid into glacial acetic acid, heating and refluxing, adding 15ml of concentrated hydrochloric acid to generate solid precipitate, and performing suction filtration to obtain a white solid product 9 with the yield of 52%.
The solid product 9(2.4mmol) was dissolved in 50mL of dichloromethane, and 6mL of hydrogen peroxide (about 1.2 times molar equivalent) was slowly added dropwise to the reaction solution and reacted overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M4 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS61H40N3OP, detection value [ M +]+961.23, calculate value 961.98.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,2H),8.19(d,2H),7.94(d,2H),7.77-7.74(m,6H),7.59-7.50(m,11H),7.41-7.31(m,8H),7.24-7.16(m,6H),7.08-7.00(m,3H)。
Synthesis of compound M5:
the solid product 6(2.4mmol) was dissolved in 50mL of methylene chloride, and 1.2-fold molar equivalent of sulfur was added to the reaction solution to react overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M5 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS37H26NP, detection value [ M +]+547.15, calculate value 547.66.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):7.31-7.24(m,9H),7.23-7.08(m,14H),7.00-6.95(m,3H)。
Synthesis of compound M6:
the solid product 7(2.4mmol) was dissolved in 50mL of methylene chloride, and 1.2-fold molar equivalent of sulfur was added to the reaction solution to react overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M6 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS49H33N2P, detection value [ M +]+712.19, calculate value 712.85.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,1H),8.19(d,1H),7.94(d,1H),7.58(d,1H),7.50-7.45(m,2H),7.35-7.14(m,24H),7.04(d,1H),6.95(m,2H)。
Synthesis of compound M7:
the solid product 8 (2.4)mmol) was dissolved in 50mL of methylene chloride, and 1.2-fold molar equivalent of sulfur was added to the reaction solution to react overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M7 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS49H33N2PS, detection value [ M +]+712.25, calculate value 712.85.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,1H),8.19(d,1H),7.94(d,1H),7.74(s,1H),7.59(m,2H),7.50(t,1H),7.35-7.16(m,21H),7.14(d,1H),7.08(d,2H),7.00-6.95(m,2H)。
Synthesis of compound M8:
the solid product 9(2.4mmol) was dissolved in 50mL of methylene chloride, and 1.2-fold molar equivalent of sulfur was added to the reaction solution to react overnight. Extraction with dichloromethane, washing with water, drying and removal of the solvent under reduced pressure gave M8 as a solid in 93% yield. The compound, formula C, was identified using HPLC-MS61H40N3PS, detection value [ M +]+877.18, calculate value 878.05.
1HNMR(500MHz,CDCl3),δ(TMS,ppm):8.55(d,2H),8.19(d,2H),7.94(d,2H),7.74(s,2H),7.59(m,4H),7.50(t,1H),7.35-7.16(m,23H),7.08-6.95(m,2H)。
The triplet energy levels of compounds M1-M8 were tested according to the conventional method, and the test results are shown in Table 1:
TABLE 1
| Compound (I) | Triplet state energy level ET(eV) |
| M1 | 2.98 |
| M2 | 2.99 |
| M3 | 2.99 |
| M4 | 2.97 |
| M5 | 2.96 |
| M6 | 2.97 |
| M7 | 2.97 |
| M8 | 2.96 |
As can be seen from table 1, the acridine compound provided by the present invention has a higher triplet level, is a good bipolar host material, and is used as a host material of a light-emitting layer, such that more energy of excitons is transmitted to a light-emitting body.
Light emitting device example
As shown in fig. 1, the light emitting device has a structure of: a first electrode, a hole injection layer formed on the first electrode, a hole transport layer formed on the hole injection layer, a light emitting layer formed on the hole transport layer, an electron transport layer formed on the light emitting layer, an electron injection layer formed on the electron transport layer, a second electrode on the electron injection layer; wherein the material for forming at least one of the light-emitting layer, the hole-transporting layer and the electron-transporting layer comprises the acridine compound.
The specific structure and raw materials of the light-emitting device are as follows:
ITO/HAT-CN (10nm)/TAPC (30nm)/TCTA (10nm)/M: FIrpic (40nm),7 wt%, (40nm)/TmPyPB (30nm)/LiF (1nm)/Al (120 nm); the device takes ITO as a first electrode, HAT-CN as a Hole Injection Layer (HIL), TAPC as a Hole Transport Layer (HTL), TCTA as a second layer hole transport layer material, M is an acridine compound and is used as a host material of a light-emitting layer, FIrpic is used as a light-emitting layer guest material (EML), TmPyPB is used as an electron transport layer material (ETL), LiF is used as an electron injection layer material (EIL), and Al is used as a second electrode.
The structure of the material concerned is as follows:
the preparation method of the light-emitting device comprises the following steps:
(1) firstly, the ITO substrate is cleaned according to the following sequence: 5% KOH solution is processed by ultrasonic treatment for 15min, pure water is processed by ultrasonic treatment for 15min, isopropanol is processed by ultrasonic treatment for 15min, and drying is carried out in an oven for 1 h.
(2) The substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment.
(3) Then, evaporation film forming is carried out: sequentially preparing a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a second electrode; firstly, vacuumizing to 10-7Torr, then slowly increase the current value, slowly increase the rate to
And opening the baffle for evaporation after the speed is stable.
(4) And finally, carrying out UV curing packaging, and baking for 30min at 80 ℃.
Examples 1 to 8
The compounds M1-M8 are respectively used as main materials of the luminescent layer, and the luminescent devices 1-8 are prepared according to the structure, the raw materials and the preparation method of the luminescent device.
Device performance test equipment and method:
the prepared light-emitting devices 1-8 are subjected to an IV-L test system to measure the light-emitting performance of the devices, the model of the machine of the test system is an F-star CS2000A instrument, and the device performance is shown in Table 2:
TABLE 2
| Device numbering | Maximum external quantum efficiency [% ]] |
| 1 | 18.2％ |
| 2 | 19.1％ |
| 3 | 19.5％ |
| 4 | 17％ |
| 5 | 15％ |
| 6 | 15.5％ |
| 7 | 14.3％ |
| 8 | 13.7％ |
As is clear from the data in table 2, the acridine compound of the present invention as a host material of a light-emitting layer improves the light-emitting efficiency of the device.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The acridine compound is characterized by having a structural formula shown as a formula (I):
wherein Ar is selected from: substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
R1、R2each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
x is selected from: oxygen or sulfur.
2. The acridine compound of claim 1, wherein Ar is selected from the group consisting of: substituted or unsubstituted aryl or heteroaryl having 6 to 60 ring atoms;
the R is1、R2Are respectively and independentlySelected from: H. a substituted or unsubstituted alkyl group having 3 to 50C atoms, or a substituted or unsubstituted aryl or heteroaryl group having 6 to 60 ring atoms;
wherein the heteroatom in the heteroaryl group is nitrogen, oxygen or sulfur;
the substituents in the substituted alkyl group, the substituents in the substituted aryl group, and the substituents in the substituted heteroaryl group are each independently selected from: deuterium groups, alkyl groups, aryl groups, nitro groups, cyano groups, arylamine groups, halogens, hydroxyl groups, carboxyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkoxycarbonyl groups, perfluoroalkyl groups, perfluoroalkoxy groups, aralkyl groups, silyl groups, siloxane groups, or thioalkoxy groups.
3. The acridine compound of claim 2, wherein the aryl group is selected from: phenyl, biphenyl, triphenyl, benzo, naphthyl, anthryl, benzonaphthyl, phenanthryl, fluorenyl, pyrenyl, chrysenyl, perylenyl, or azulenyl.
4. The acridine compound of claim 2, wherein the heteroaryl group is selected from: dibenzothienyl, dibenzofuryl, furyl, thienyl, benzofuryl, benzothienyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, oxadiazolyl, indolyl, benzimidazolyl, indazolyl, indolizinyl, benzoxazolyl, isoxazolyl, benzothiazolyl, quinolyl, isoquinolyl, o-diaza-naphthyl, quinazolinyl, quinoxalinyl, naphthyl, phthalidyl, pteridinyl, xanthinyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, dibenzoselenophenyl, benzoselenophenyl, benzofuropyridylpyrazolyl, indolocarbazolyl, pyridylindolyl, pyrrolydipyridoindolyl, Furan bipyridyl, benzothiophene furopyridinyl, thienobipyridyl, benzoselenophenopyridine, or selenophene bipyridyl.
5. The acridine compound of claim 1, wherein the alkyl group is selected from: methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl or isohexyl.
6. The acridine compound of claim 5, wherein R is1、R2Each independently selected from: H. carbazolyl, benzocarbazolyl, benzopyrolyl, pyridyl, pyrazinyl, benzophenazinyl, benzothiazinyl, benzosilazinyl, spirofluorenyl or benzazedinyl.
7. The acridine compound according to any one of claims 1 to 6, wherein Ar is selected from the group consisting of:
wherein R is3Selected from: h or
The R is1、R2Each independently selected from: h or
8. The acridine compound of claim 1, wherein the acridine compound is selected from the group consisting of:
9. a light emitting device, comprising:
a functional layer, a material forming the functional layer comprising the acridine compound according to any one of claims 1 to 8.
10. The light-emitting device according to claim 9, wherein the functional layer of the light-emitting device comprises at least one of a light-emitting layer, a hole-transporting layer, and an electron-transporting layer.
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| CN113603724A (en) * | 2021-07-16 | 2021-11-05 | 武汉华星光电半导体显示技术有限公司 | Organic compound, preparation method thereof and light-emitting device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103946215A (en) * | 2011-11-17 | 2014-07-23 | 默克专利有限公司 | Spiro dihydroacridine derivatives and the use thereof as materials for organic electroluminescence devices |
| CN107709330A (en) * | 2015-11-17 | 2018-02-16 | 株式会社Lg化学 | Spiro-compound and the organic illuminating element for including it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103946215A (en) * | 2011-11-17 | 2014-07-23 | 默克专利有限公司 | Spiro dihydroacridine derivatives and the use thereof as materials for organic electroluminescence devices |
| CN107709330A (en) * | 2015-11-17 | 2018-02-16 | 株式会社Lg化学 | Spiro-compound and the organic illuminating element for including it |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603724A (en) * | 2021-07-16 | 2021-11-05 | 武汉华星光电半导体显示技术有限公司 | Organic compound, preparation method thereof and light-emitting device |
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