CN112142725A - Organic electroluminescent material based on xanthone and application thereof in preparing OLED (organic light emitting diode) - Google Patents

Organic electroluminescent material based on xanthone and application thereof in preparing OLED (organic light emitting diode) Download PDF

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CN112142725A
CN112142725A CN202011048426.6A CN202011048426A CN112142725A CN 112142725 A CN112142725 A CN 112142725A CN 202011048426 A CN202011048426 A CN 202011048426A CN 112142725 A CN112142725 A CN 112142725A
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xanthone
organic electroluminescent
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唐本忠
赵祖金
陈金科
秦安军
胡蓉蓉
王志明
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of organic photoelectric materials, and discloses an organic electroluminescent material based on xanthone and application thereof in preparing an OLED (organic light emitting diode). The organic electroluminescent material based on the xanthone takes the xanthone as a core, and the two sides are connected with the same or different electron-donating groups, so that the obtained molecular structure is distorted, the molecular distance is larger in an aggregation state, and the organic electroluminescent material can have AIE and TADF characteristics at the same time; therefore, the material has the characteristics of high-efficiency solid-state luminescence, high-electric excitation exciton utilization rate and bipolarity. Based on the material, the non-doped organic electroluminescent device with high efficiency and low efficiency roll-off can be prepared, has wide application prospect in the field of organic electroluminescence, and is expected to be widely applied in the fields of flat panel display, solid state lighting and the like.

Description

Organic electroluminescent material based on xanthone and application thereof in preparing OLED (organic light emitting diode)
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic electroluminescent material based on xanthone and application thereof in preparing an OLED (organic light emitting diode).
Background
Organic electroluminescent devices, also called Organic Light Emitting Diodes (OLEDs), refer to devices based on organic light emitting materials that convert electrical energy into optical energy, wherein organic semiconductors and light emitting materials are driven by an electric field, and carriers are injected from both electrodes and are combined in a light emitting layer to cause light emission. The OLED device prepared by using the traditional fluorescent material has the exciton utilization rate of only 25 percent, and the rest 75 percent of triplet excitons return to the ground state in a non-radiative decay mode without emitting light, so that the device efficiency is very low (J.Mater.chem.2012,22, 23726-; OLEDs based on phosphorescent materials are capable of achieving 100% exciton utilization, but their practical application in electroluminescent devices is limited by the disadvantages of containing precious metals, poor stability, high manufacturing costs, etc. (j.appl.phys.2001,90,5048; eur.j.org.chem.2013,2013, 7653; phys.chem.chem.phys.2014,16,1719). Third generation organic light emitting materials, namely pure organic Thermally Activated Delayed Fluorescence (TADF) materials, developed by professor Adachi at kyushu university in 2012, can also fully utilize singlet and triplet excitons generated by electrical excitation, achieve 100% of exciton utilization rate, and simultaneously achieve high device efficiency, but the problem of efficiency roll-off is still serious, and the existing pure organic TADF materials are single in type, and meanwhile, the TADF materials are also affected by aggregation to cause luminescence quenching (ACQ) effect, so that the solid-state luminescence efficiency is not high, a complex doping technology is required to improve the technical problem, the preparation cost is increased, and a phase separation problem is also caused to reduce the service life of the device (chem.commun.2012 and 48,11392; org.electron.2016,29, 160; adv.sci.2016,3,1600080; angelw.chem., int.ed. 53,6402; adv.funct.mater.2016,26,7929; adv.2017.2014 29,1604856, 201425.201425).
In 2001, the inventors discovered a novel phenomenon: in the dispersed state, some luminescent molecules emit no light or very weak light, but when the molecules are aggregated, the intensity of the light emitted from the molecules is significantly increased, which is called "aggregation-induced emission" (AIE), which is a phenomenon completely opposite to the conventional ACQ phenomenon. Since then, more and more AIE materials covering the full visible color and high efficiency solid state light emission have been developed. Based on the materials, researchers have prepared undoped OLEDs with relatively high efficiency and simple device structures, and the efficiency roll-off degree is small, but the materials can only utilize singlet excitons to emit light, so that the device efficiency still has a great space for improvement. Therefore, the novel aggregation-induced delayed fluorescence (AIDF) luminescent material developed by organically combining the TADF and AIE effects not only has high solid-state quantum efficiency and 100% exciton utilization rate, but also can be used for preparing high-efficiency undoped devices, and based on the luminescent material, the OLEDs with simple structure, high efficiency, low roll-off and long service life are expected to be prepared.
Disclosure of Invention
To overcome the above-mentioned drawbacks and disadvantages of the prior art, it is a primary object of the present invention to provide a class of xanthone-based organic electroluminescent materials having both Thermally Activated Delayed Fluorescence (TADF) and Aggregation Induced Emission (AIE) properties.
The invention also aims to provide application of the organic electroluminescent material based on the xanthone in the field of organic electroluminescence.
The purpose of the invention is realized by the following scheme:
a xanthone-based organic electroluminescent material has the following structure:
Figure BDA0002708753360000021
wherein when Ar is1And Ar2When attached at positions 2 and 7, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to u, Ar1And Ar2Are identical or different radicals;
when Ar is1And Ar2When attached at positions 3 and 6, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to s, Ar1And Ar2Are the same group;
when Ar is1And Ar2When attached at positions 3 and 6, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to v, Ar1And Ar2Are different groups;
Figure BDA0002708753360000031
preferably, the organic electroluminescent material based on xanthone has the following structural formula
Figure BDA0002708753360000041
The application of the organic electroluminescent material based on xanthone in preparing OLED.
Preferably, the xanthone-based organic electroluminescent material functions as a light-emitting layer of an OLED in a doped or undoped manner.
The invention takes xanthone as a core, and the two sides are connected with the same or different electron-donating groups, so that the obtained molecular structure is distorted, the molecular distance is larger in an aggregation state, and the intermolecular is effectively weakenedInteraction, slowing down the exciton annihilation process caused by Dexter energy transfer, achieves intense luminescence in the aggregate state. In addition, the electron-donating (D) -electron-withdrawing (A) and twisted molecular structure are beneficial to separating the highest occupied orbital (HOMO) from the lowest unoccupied orbital (LUMO), so that the molecules have smaller singlet-triplet energy level difference (delta E)ST) The full utilization of triplet excitons is realized through a reverse system cross-over (RISC) process, so that 100% of Internal Quantum Efficiency (IQE) is obtained, and the obtained material can have AIE and TADF characteristics at the same time; therefore, the material has the characteristics of high-efficiency solid-state luminescence, high-electric excitation exciton utilization rate and bipolarity. Based on the material, the non-doped organic electroluminescent device with high efficiency and low efficiency roll-off can be prepared, has wide application prospect in the field of organic electroluminescence, and is expected to be widely applied in the fields of flat panel display, solid state lighting and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention synthesizes a novel organic electroluminescent material based on xanthone, and the material has AIE and TADF characteristics.
(2) The organic electroluminescent material based on xanthone has the advantages of simple synthesis method, easily obtained raw materials, higher yield, stable structure of the obtained material and simple storage.
(3) The organic electroluminescent material based on xanthone has excellent electroluminescent performance and can be widely applied to the fields of organic electroluminescence and the like.
Drawings
FIG. 1 is a L-V-J diagram of undoped OLEDs produced on the basis of the xanthone-based organic electroluminescent material obtained in example 1.
FIG. 2 is a graph showing the efficiency of undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 1 as a function of luminance.
FIG. 3 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 2.
FIG. 4 is a graph of efficiency as a function of brightness for doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 2.
FIG. 5 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 3.
FIG. 6 is a graph of efficiency as a function of brightness for doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 3.
FIG. 7 is a L-V-J plot of undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 4.
FIG. 8 is a graph showing the efficiency of undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 4 as a function of luminance.
FIG. 9 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 5.
FIG. 10 is a graph of efficiency as a function of brightness for doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 5.
FIG. 11 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 6.
FIG. 12 is a graph of efficiency as a function of brightness for doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 6.
FIG. 13 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 7.
FIG. 14 is a graph of efficiency as a function of brightness for doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 7.
FIG. 15 is a L-V-J plot of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 12.
FIG. 16 is a graph showing the efficiency of doped and undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 12 as a function of luminance.
FIG. 17 is a graph showing the efficiency of doped and undoped OLEDs produced based on the xanthone-based organic electroluminescent material obtained in example 14 as a function of luminance.
FIG. 18 is a L-V-J plot of undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 15.
FIG. 19 is a graph showing the efficiency of undoped OLEDs prepared based on the xanthone-based organic electroluminescent material obtained in example 15 as a function of luminance.
FIG. 20 is a L-V-J graph of undoped OLEDs produced based on the xanthone-based organic electroluminescent material obtained in example 16.
FIG. 21 is a graph showing the efficiency of undoped OLEDs produced on the basis of the xanthone-based organic electroluminescent material obtained in example 16 as a function of luminance.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
The reagents used in the following examples are commercially available.
Example 1: preparation of xanthone-based organic electroluminescent materials (BPXZ-XT)
Figure BDA0002708753360000071
The synthetic route is as follows:
Figure BDA0002708753360000072
3, 6-dibromo-xanthone (0.177g,0.5mmol), phenoxazine (0.22g, 1.2mmol), sodium tert-butoxide (0.288g,3mmol) and palladium acetate (0.018g,0.08mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.016g,0.08mmol) was added under nitrogen protection, 20mL of toluene was added finally, and the mixture was heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BPXZ-XT with yield of 83%.
Example 2: preparation of organic electroluminescent material (BSAF-XT) based on xanthone
Figure BDA0002708753360000073
The synthetic route is as follows:
Figure BDA0002708753360000074
3, 6-dibromoxanthone (1.06g,3mmol), 10H-spiro [ [ pyridine-9, 9' -fluorene ] (2.38g,7.2mmol), sodium tert-butoxide (1.15g,12mmol), tris (dibenzylideneacetone) dipalladium (0.11g,0.12mmol) and tri-tert-butylphosphine tetrafluoroborate (0.14g,0.48mmol) were added to a reaction flask, the gas was purged three times, 50mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BSAF-XT with yield of 58%.
1H NMR(500MHz,CDCl3)8.78(d,J＝8.3Hz,2H),7.85–7.77(m,6H),7.65–7.59(m,2H),7.47–7.37(m,8H),7.32–7.27(m,4H),7.00–6.92(m,4H),6.66–6.60(m,4H),6.49–6.41(m,8H).13C NMR(126MHz,CDCl3)158.02,156.28,147.79,140.50,139.30,129.99,128.45,128.13,127.74,127.55,127.39,125.73,125.25,121.87,121.35,121.10,120.00,114.54,56.73.HRMS(C63H38N2O2):m/z 854.2937[M+,calcd 854.2933].
Example 3: preparation of xanthone-based organic electroluminescent materials (BDPAC-XT)
Figure BDA0002708753360000081
The synthetic route is as follows:
Figure BDA0002708753360000082
3, 6-dibromoxanthone (1.06g,3mmol), 9, 10-dihydro-9, 9-diphenylacridine (2.4g,7.2mmol), sodium tert-butoxide (1.15g,12mmol), tris (dibenzylideneacetone) dipalladium (0.11g,0.12mmol) and tri-tert-butylphosphine tetrafluoroborate (0.14g,0.48mmol) were added to a reaction flask, the gas was purged three times, 50mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BDPAC-XT with yield of 85%.
1H NMR(500MHz,CD2Cl2)8.36(d,J＝8.4Hz,2H),7.30–7.20(m,12H),7.19(d,J＝1.9Hz,2H),7.16–7.06(m,6H),7.02–6.90(m,16H),6.69–6.63(m,4H).13C NMR(126MHz,CD2Cl2)176.68,158.83,148.84,147.21,142.76,133.51,131.62,131.41,129.93,128.98,128.26,127.79,126.14,122.76,121.83,118.86,117.11,58.37.HRMS(C63H42N2O2):m/z 858.3236[M+,calcd 858.3246]
Example 4: preparation of xanthone-based organic electroluminescent materials (BTMAC-XT)
Figure BDA0002708753360000083
The synthetic route is as follows:
Figure BDA0002708753360000084
3, 6-dibromo-xanthone (1.06g,3mmol), 9, 10-dihydro-3, 6,9, 9-tetramethylacridine (1.7g,7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were added to a reaction flask, the gas was evacuated three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen, 50mL of toluene was finally added, heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BTMAC-XT with yield of 48%.
1H NMR(500MHz,CD2Cl2)8.37(d,J＝8.6Hz,2H),7.41–7.29(m,8H),6.92–6.90(m,4H),6.66(d,J＝8.2Hz,4H),2.32(s,12H),1.59(s,12H).13C NMR(126MHz,CD2Cl2)175.45,158.34,149.53,138.64,135.54,132.43,129.02,127.18,126.10,121.73,119.45,118.32,113.49,54.27,54.05,53.83,53.62,53.40,37.08,29.95,21.06。
Example 5: preparation of organic electroluminescent materials (BSNO-XT) based on xanthone
Figure BDA0002708753360000091
The synthetic route is as follows:
Figure BDA0002708753360000092
3, 6-dibromoxanthone (1.06g,3mmol), 10H-spiro [ acridine-9, 9' -xanthene ] (2.5g,7.2mmol), sodium tert-butoxide (1.15g,12mmol), tris (dibenzylideneacetone) dipalladium (0.11g,0.12mmol) and tri-tert-butylphosphine tetrafluoroborate (0.14g,0.48mmol) were added to a reaction flask, the gas was purged three times, 50mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BSNO-XT with yield of 96%.
1H NMR(500MHz,CDCl3)8.76(d,J＝8.3Hz,2H),7.74(d,J＝1.8Hz,2H),7.59–7.53(m,2H),7.24–7.14(m,12H),7.02–6.95(m,4H),6.96–6.88(m,8H),6.78–6.71(m,4H),6.38–6.32(m,4H).13C NMR(126MHz,CDCl3)175.96,158.00,148.52,147.68,138.37,132.63,131.81,131.17,130.10,129.95,127.75,127.69,127.10,123.72,121.94,121.59,121.31,116.07,113.94,44.69.HRMS(C63H38N2O4):m/z 886.2837[M+,calcd 886.2832]。
Example 6: preparation of xanthone-based organic electroluminescent materials (BDMCz-XT)
Figure BDA0002708753360000093
The synthetic route is as follows:
Figure BDA0002708753360000101
3, 6-dibromo-xanthone (0.106g,0.3mmol), 1, 8-dimethylcarbazole (0.14g,0.72mmol), sodium tert-butoxide (0.115g,1.2mmol), tris (dibenzylideneacetone) dipalladium (0.011g,0.012mmol) and tri-tert-butylphosphine tetrafluoroborate (0.014g,0.048mmol) were added to a reaction flask, and gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, powdering, and passing through column to obtain final product BDMCz-XT with 86% yield.
1H NMR(500MHz,CD2Cl2)8.44(d,J＝8.3Hz,2H),8.02–7.96(m,4H),7.63–7.55(m,4H),7.14–7.17(m,4H),7.08(d,J＝7.3Hz,4H),1.95(s,12H).13C NMR(126MHz,CD2Cl2)177.17,157.12,149.84,141.89,130.44,129.16,127.96,125.58,123.34,122.88,122.27,121.73,119.31,20.85.
Example 7: preparation of xanthone-based organic electroluminescent materials (Cz-XT-DMAC)
Figure BDA0002708753360000102
The synthetic route is as follows:
Figure BDA0002708753360000103
(1) 3, 6-dibromoxanthone (0.318g,0.9mmol), carbazole (0.05g,0.3mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 24%.
(2) Intermediate 2(0.44g,1mmol), 9, 10-dihydro-9, 9-dimethylacridine (0.25g,1.2mmol), sodium tert-butoxide (0.288g,3mmol) and palladium acetate (0.018g,0.08mmol) were charged into a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.016g,0.08mmol) was added under nitrogen, 20mL of toluene was added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Cz-XT-DMAC with yield of 98%.
1H NMR(400MHz,CD2Cl2)8.58–8.52(m,2H),8.17(d,J＝7.8,Hz,2H),7.82–7.30(m,12H),7.14–6.96(m,4H),6.67–6.56(m,2H),1.67(s,6H).
Example 8: preparation of organic electroluminescent materials based on xanthones (Cz-XT-PXZ)
Figure BDA0002708753360000111
The synthetic route is as follows:
Figure BDA0002708753360000112
(1) 3, 6-dibromoxanthone (0.318g,0.9mmol), carbazole (0.05g,0.3mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 24%.
(2) Intermediate 2(0.22g,0.5mmol), phenoxazine (0.137g,0.75mmol), sodium tert-butoxide (0.144g,1.5mmol) and palladium acetate (0.009g,0.04mmol) were added to the reaction flask, the gas was evacuated three times, tri-tert-butylphosphine (0.008g,0.04mmol) was added under nitrogen protection, 20mL of toluene was added finally, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Cz-XT-PXZ with yield of 88%.
1H NMR(400MHz,CD2Cl2)8.59–8.52(m,2H),8.17(d,J＝7.6Hz,2H),7.90–7.27(m,10H),6.86–6.59(m,6H),6.21–6.05(m,2H).
Example 9: preparation of organic electroluminescent materials (Cz-XT-DPAC) based on xanthones
Figure BDA0002708753360000113
The synthetic route is as follows:
Figure BDA0002708753360000114
(1) 3, 6-dibromoxanthone (0.318g,0.9mmol), carbazole (0.05g,0.3mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 24%.
(2) Intermediate 2(0.132g,0.3mmol), 9, 10-dihydro-9, 9-diphenylacridine (0.15g,0.45mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were charged into a reaction flask, purged three times, 20mL of toluene were added, heated to 120 ℃ and reacted at this temperature for 6 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Cz-XT-DPAC with yield of 82%.
Example 10: preparation of organic electroluminescent materials (Cz-XT-SAF) based on xanthone
Figure BDA0002708753360000121
The synthetic route is as follows:
Figure BDA0002708753360000122
(1) 3, 6-dibromoxanthone (0.318g,0.9mmol), carbazole (0.05g,0.3mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 24%.
(2) Intermediate 2(0.132g,0.3mmol), 10H-spiro [ pyridine-9, 9' -fluorene ] (0.149g,0.45mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were charged into a reaction flask, purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 6 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Cz-XT-SAF with yield of 72%.
Example 11: preparation of organic electroluminescent materials (Cz-XT-SNO) based on xanthone
Figure BDA0002708753360000131
The synthetic route is as follows:
Figure BDA0002708753360000132
(1) 3, 6-dibromoxanthone (0.318g,0.9mmol), carbazole (0.05g,0.3mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 24%.
(2) Intermediate 2(0.132g,0.3mmol), 10H-spiro [ acridine-9, 9' -xanthene ] (0.156g,0.45mmol), sodium tert-butoxide (0.057g,0.6mmol), tris (dibenzylideneacetone) dipalladium (0.006g,0.006mmol) and tri-tert-butylphosphine tetrafluoroborate (0.007g,0.024mmol) were charged into a reaction flask, purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 6 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Cz-XT-SNO with yield of 85%.
Example 12: preparation of xanthone-based organic electroluminescent materials (DMCz-XT-DMAC)
Figure BDA0002708753360000133
The synthetic route is as follows:
Figure BDA0002708753360000134
(1) 3, 6-dibromoxanthone (1.4g,4.0mmol), 1, 8-dimethylcarbazole (0.195g,1mmol), sodium tert-butoxide (0.192g,2mmol), tris (dibenzylideneacetone) dipalladium (0.018g,0.02mmol) and tri-tert-butylphosphine tetrafluoroborate (0.023g,0.08mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 10%.
(2) Intermediate 2(0.7g,1.5mmol), 9, 10-dihydro-9, 9-dimethylacridine (0.376g,1.8mmol), sodium tert-butoxide (0.432g,4.5mmol) and palladium acetate (0.027g,0.12mmol) were charged to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.024g,0.12mmol) was added under nitrogen, 20mL of toluene was added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product DMCz-XT-DMAC with yield of 57%.
1H NMR(500MHz,CD2CL2)8.52(d,J＝8.5Hz,1H),8.43(d,J＝8.3Hz,1H),8.02–7.95(m,2H),7.69(d,J＝1.9Hz,1H),7.58–7.56(m,1H),7.54–7.49(m,3H),7.44–7.42(m,1H),7.19–7.16(t,2H),7.12–7.08(m,2H),7.06–7.01(m,4H),6.62–6.60(m,2H),1.97(s,6H),1.65(s,6H).13C NMR(126MHz,CD2CL2)176.03,158.51,156.11,148.99,148.62,140.95,140.70,133.71,129.54,128.05,127.02,126.78,125.68,124.63,124.60,122.59,122.55,122.01,121.27,120.78,120.63,118.40,117.04,116.81,36.85,30.53,19.91.
Example 13: preparation of organic electroluminescent materials (t-BuCz-XT-DMAC) based on xanthones
Figure BDA0002708753360000141
The synthetic route is as follows:
Figure BDA0002708753360000142
(1) 3, 6-dibromoxanthone (0.708g,2mmol), 3, 6-di-tert-butylcarbazole (0.279g,1mmol), sodium tert-butoxide (0.192g,2mmol), tris (dibenzylideneacetone) dipalladium (0.018g,0.02mmol) and tri-tert-butylphosphine tetrafluoroborate (0.023g,0.08mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 3 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain intermediate 2 with yield of 5%.
(2) Intermediate 2(0.276g,0.5mmol), 9, 10-dihydro-9, 9-dimethylacridine (0.125g,0.6mmol), sodium tert-butoxide (0.144g,1.5mmol) and palladium acetate (0.009g,0.04mmol) were added to the reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.008g,0.04mmol) was added under nitrogen, 20mL of toluene was added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through a column to obtain the final product t-BuCz-XT-DMAC with a yield of 68%.
Example 14: preparation of xanthone-based organic electroluminescent materials (BTMCz-XT)
Figure BDA0002708753360000151
The synthetic route is as follows:
Figure BDA0002708753360000152
3, 6-dibromo-xanthone (1.06g,3mmol), 1,3,6, 8-tetramethylcarbazole (1.6g,7.2mmol), sodium tert-butoxide (1.15g,12mmol), tris (dibenzylideneacetone) dipalladium (0.11g,0.12mmol) and tri-tert-butylphosphine tetrafluoroborate (0.14g,0.48mmol) were added to a reaction flask, and the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BTMCz-XT with yield of 78%.
1H NMR(500MHz,CD2Cl2)8.41(d,J＝8.3Hz,2H),7.74(d,J＝1.7Hz,4H),7.62(d,J＝1.8Hz,2H),7.51–7.53(m,2H),6.92(d,J＝1.6Hz,4H),2.45(s,12H),1.92(s,12H).13C NMR(126MHz,CD2Cl2)176.31,156.29,149.40,139.92,130.80,130.16,128.10,127.00,124.91,122.26,121.69,121.17,118.16,21.19,19.82.
Example 15: preparation of xanthone-based organic electroluminescent materials (BDFDMCz-XT)
Figure BDA0002708753360000153
The synthetic route is as follows:
Figure BDA0002708753360000154
3, 6-dibromo-xanthone (1.06g,3mmol), 3, 6-difluoro-1, 8-dimethylcarbazole (1.52g,6.6mmol), sodium tert-butoxide (1.15g,12mmol), tris (dibenzylideneacetone) dipalladium (0.11g,0.12mmol) and tri-tert-butylphosphine tetrafluoroborate (0.14g,0.48mmol) were added to a reaction flask, the gas was purged three times, 20mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through a column to obtain the final product BDFDMCz-XT with the yield of 87%.
1H NMR(500MHz,CD2Cl2)8.46(d,J＝8.4Hz,2H),7.67(d,J＝1.9Hz,2H),7.60–7.54(m,6H),6.93–6.90(m,4H),1.96(s,12H).13C NMR(126MHz,CD2Cl2)177.02,159.75,157.86,157.17,149.30,139.45,128.98,128.31,126.03,126.00,125.95,125.92,125.20,125.13,123.52,122.17,119.49,118.52,118.32,104.76,104.57,20.76.
Example 16: preparation of xanthone-based organic electroluminescent materials (BDClDMAC-XT)
Figure BDA0002708753360000161
The synthetic route is as follows:
Figure BDA0002708753360000162
3, 6-dibromo-xanthone (1.06g,3mmol), 9, 10-dihydro-3, 6-dichloro-9, 9-dimethylacridine (2g,7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were added to a reaction flask, the gas was evacuated three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen, 50mL of toluene was finally added, heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BDClDMAC-XT with yield of 49%.
1H NMR(500MHz,CD2Cl2)8.58(d,J＝8.5Hz,2H),7.53(d,J＝1.9Hz,2H),7.45(d,J＝2.4Hz,4H),7.40–7.37(m,2H),7.01–6.99(m,4H),6.39(d,J＝8.8Hz,4H),1.66(s,12H).13C NMR(126MHz,CD2Cl2)175.81,158.33,147.59,139.43,139.17,133.26,130.05,127.22,126.84,126.13,125.85,121.78,119.42,116.76,37.03,30.71.
Example 17: preparation of xanthone-based organic electroluminescent materials (BClDMAC-XT)
Figure BDA0002708753360000163
The synthetic route is as follows:
Figure BDA0002708753360000171
3, 6-dibromo-xanthone (1.06g,3mmol), 9, 10-dihydro-3, chloro-9, 9-dimethylacridine (1.75g,7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were charged into a reaction flask, the gas was evacuated three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen, 50mL of toluene was finally added, heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BClDMAC-XT with yield of 64%.
Example 18: preparation of xanthone-based organic electroluminescent materials (BINSB-XT)
Figure BDA0002708753360000172
The synthetic route is as follows:
Figure BDA0002708753360000173
3, 6-dibromo-xanthone (1.06g,3mmol), iminostilbene (1.74g,9mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.10g,0.48mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen protection, 50mL of toluene was finally added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BINSB-XT with yield of 63%.
1H NMR(500MHz,CD2Cl2)7.76(d,J＝8.9Hz,2H),7.57–7.45(m,12H),7.43–7.40(m,4H),6.86(s,4H),6.24–6.22(m,2H),5.97(d,J＝2.4Hz,2H).13C NMR(126MHz,CD2Cl2)174.64,157.82,154.13,142.05,136.15,130.86,130.74,130.43,129.91,128.16,127.22,114.10,109.54,98.35.
Example 19: preparation of xanthone-based organic electroluminescent materials (BINDB-XT)
Figure BDA0002708753360000174
The synthetic route is as follows:
Figure BDA0002708753360000181
3, 6-dibromo-xanthone (1.06g,3mmol), iminodibenzyl (1.76g,9mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen protection, 50mL of toluene was added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BINDB-XT with yield of 57%.
1H NMR(500MHz,CD2Cl2)8.00–7.93(m,2H),7.42–7.38(m,4H),7.34–7.23(m,12H),6.58–6.55(m,2H),6.31(d,J＝2.4Hz,2H),2.99(s,8H).13C NMR(126MHz,CD2Cl2)174.43,158.34,154.40,142.75,138.26,131.61,129.45,128.39,127.84,127.80,113.28,110.42,98.83,30.90.
Example 20: preparation of xanthone-based organic electroluminescent materials (BaDMAC-XT)
Figure BDA0002708753360000182
The synthetic route is as follows:
Figure BDA0002708753360000183
3, 6-dibromo-xanthone (1.06g,3mmol), adamantane acridine (2.17g,7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen protection, 50mL of toluene was finally added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BaDMAC-XT with yield of 25%.
Example 21: preparation of organic electroluminescent material (Bt-BuDMAC-XT) based on xanthone
Figure BDA0002708753360000184
The synthetic route is as follows:
Figure BDA0002708753360000191
3, 6-dibromo-xanthone (1.06g,3mmol), 9, 10-dihydro-3, 6-di-tert-butyl-9, 9-dimethylacridine (2.3g,7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.1g,0.48mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen protection, 50mL of toluene was finally added, and the mixture was heated to 120 ℃ and reacted at this temperature for 5 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product Bt-BuDMAC-XT with yield of 82%
Example 22: preparation of xanthone-based organic electroluminescent materials (BSMCz-XT)
Figure BDA0002708753360000192
The synthetic route is as follows:
Figure BDA0002708753360000193
3, 6-dibromoxanthone (1.77g,5mmol), 1, -methylcarbazole (2.17g,12mmol), sodium tert-butoxide (2.88g,30mmol), tris (dibenzylideneacetone) dipalladium (0.733g,0.8mmol) and tri-tert-butylphosphine tetrafluoroborate (0.232g,0.8mmol) were added to a reaction flask, the gas was purged three times, 50mL of toluene was added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain the final product BSMCz-XT with yield of 69%.
Example 23: preparation of xanthone-based organic electroluminescent materials (BPTZ-XT)
Figure BDA0002708753360000194
The synthetic route is as follows:
Figure BDA0002708753360000195
3, 6-dibromo-xanthone (1.06g,3mmol), phenothiazine (1.43g, 7.2mmol), sodium tert-butoxide (1.73g,18mmol) and palladium acetate (0.107g,0.48mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.097g,0.48mmol) was added under nitrogen protection, 20mL of toluene was added, and the mixture was heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product BPTZ-XT with yield of 23%.
1H NMR(400MHz,CDCl3)8.12(d,J＝8.9Hz,2H),7.46–7.44(m,4H),7.40–7.30(m,8H),7.23–7.19(m,4H),7.02–6.99(m,2H),6.89(d,J＝2.3Hz,2H).
Example 24: preparation of xanthone-based organic electroluminescent material (m-BDMAC-XT)
Figure BDA0002708753360000201
The synthetic route is as follows:
Figure BDA0002708753360000202
2, 7-dibromo-xanthone (0.177g,0.5mmol), 9, 10-dihydro-9, 9-dimethylacridine (0.25g,1.2mmol), sodium tert-butoxide (0.288g,3mmol) and palladium acetate (0.018g,0.08mmol) were added to a reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.016g,0.08mmol) was added under nitrogen protection, 20mL of toluene was finally added, and the mixture was heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product m-BDMAC-XT with yield of 94%.
Example 25: preparation of organic electroluminescent materials (m-BPXZ-XT) based on xanthone
Figure BDA0002708753360000203
The synthetic route is as follows:
Figure BDA0002708753360000204
2, 7-dibromo-xanthone (0.354g,1mmol), phenoxazine (0.44g, 2.4mmol), sodium tert-butoxide (0.576g,6mmol) and palladium acetate (0.036g,0.16mmol) were added to the reaction flask, the gas was purged three times, tri-tert-butylphosphine (0.032g,0.16mmol) was added under nitrogen protection, 20mL of toluene was finally added, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain final product m-BPXZ-XT with yield of 52%.
Example 26: preparation of xanthone-based organic electroluminescent material (m-BPhDMAC-XT)
Figure BDA0002708753360000211
The synthetic route is as follows:
Figure BDA0002708753360000212
2, 7-dibromo-xanthone (0.106g,0.3mmol), 9-dimethyl-10- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -9, 10-dihydroacridine (0.296g, 0.72mmol), potassium carbonate (0.166g,1.2mmol) and tetrakistriphenylphosphine palladium (0.035g,0.03mmol) were added to a reaction flask, purged three times, 20mL of toluene was added under nitrogen protection, heated to 120 ℃ and reacted at this temperature for 8 hours. Extracting with dichloromethane and water, concentrating, making powder, and passing through column to obtain the final product m-BPhDMAC-XT with a yield of 35%.
Example 27: OLEDs device performance of xanthone-based organic electroluminescent materials (BPXZ-XT)
The organic electroluminescent material BPXZ-XT based on xanthone prepared in the example 1 is used as a non-doped device prepared from a luminescent material, and the performance of the device is tested and characterized as shown in the figure 1-2.
The device structure is as follows: ITO/HATCN (5nm)/TAPC (30nm)/TcTa (5nm)/BPXZ-XT (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (undoped structure).
FIG. 1 is a L-V-J graph of an OLEDs device based on the material obtained in example 1, from which it can be seen that the maximum luminance of the BPXZ-XT based undoped device is high and the threshold voltage is low, 55030cd/m2And 2.9V. FIG. 2 is a graph of the efficiency as a function of brightness for an undoped device based on the material obtained in example 1, as can be seen from the graphThe maximum current efficiency and power of the non-doped device of BPXZ-XT are respectively 26.47cd/A and 23.9lm W-1BPXZ-XT based undoped devices have a maximum external quantum efficiency of 8.92% when the luminance is 1000cd/m2The external quantum efficiency was maintained at 8.89%.
Example 28: OLEDs device performance of xanthone-based organic electroluminescent materials (BSAF-XT)
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material BSAF-XT (thin film fluorescence quantum yield 59.9%) prepared in example 2 as a luminescent material, and device performances of the doped devices and the undoped devices are tested and characterized, and the results are shown in FIGS. 3-4.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/20 wt% emitter PPF (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/emitter (30nm)/TPBi (50nm)/LiF (1nm)/Al (undoped structure).
FIG. 3 is a L-V-J graph of OLEDs based on the material obtained in example 2, from which it can be seen that the maximum luminance is high and the threshold voltage is low for the doped and undoped devices based on BSAF-XT, 74452cd/m respectively23.5V and 39218cd/m2And 3.3V. FIG. 4 is a graph of the efficiency of doped and undoped devices based on the material obtained in example 2 as a function of luminance, from which it can be seen that the maximum current efficiency and power efficiency of the doped and undoped devices based on BSAF-XT are 86.1cd/A, 59.9lm W-1And 48.0cd/A, 42.5lm W-1The maximum external quantum efficiency of the doped and undoped devices based on BSAF-XT is 26.7% and 15.4%, respectively, when the luminance is 1000cd/m2The external quantum efficiency was maintained at 23.2% and 14.5%, respectively.
Example 29: OLEDs device performance of organic electroluminescent material BDPAC-XT based on xanthone
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material BDPAC-XT (thin film fluorescence quantum yield: 94.4%) prepared in example 3 as a luminescent material, and the devices are tested and characterized, and the results are shown in FIGS. 5-6.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/20 wt% emitter PPF (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/emitter (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (undoped structure).
FIG. 5 is a L-V-J plot of OLEDs based on the material obtained in example 3, from which it can be seen that the maximum luminance is high and the actuation voltage is low for the BDPAC-XT based doped and undoped devices, 42291cd/m respectively23.3V and 18448cd/m2And 3.5V. FIG. 6 is a graph of the efficiency of doped and undoped devices based on the material obtained in example 3 as a function of luminance, from which it can be seen that the maximum current efficiency and power efficiency of the BDPAC-XT based doped and undoped devices are 79.0cd/A, 60.2lm W-1And 54.9cd/A, 41.5lm W-1(ii) a The maximum external quantum efficiency of the BDPAC-XT based doped and undoped devices is 26.5 percent and 20.8 percent respectively when the brightness is 1000cd/m2The external quantum efficiency was maintained at 25.6% and 17.5%, respectively.
Example 30: OLEDs device performance of organic electroluminescent material BTMAC-XT based on xanthone
The organic electroluminescent material BTMAC-XT based on xanthone prepared in the example 4 is used as a non-doped device prepared from a luminescent material, and the performance of the device is tested and characterized as shown in the figure 7-8.
The device structure is as follows: ITO/HATCN (5nm)/TAPC (20nm)/TCTA (5nm)/emitter (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (undoped structure).
FIG. 7 is a L-V-J graph of an OLEDs device based on the material obtained in example 4, from which it can be seen that the maximum luminance of the BTMAC-XT based undoped device is high and the threshold voltage is low, 34501cd/m2And 2.7V. FIG. 8 is a graph of efficiency as a function of luminance for an undoped device based on the material obtained in example 4, from which it can be seen that the maximum current efficiency and power of the BTMAC-XT based undoped device are 69.2cd/A and 67.9lm W, respectively-1Most preferably BTMAC-XT based undoped devicesHigh external quantum efficiency of 19.5%, when the brightness is 1000cd/m2The external quantum efficiency was maintained at 18.0%.
Example 31: OLEDs device performance of xanthone-based organic electroluminescent materials (BSNO-XT)
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material BSNO-XT (thin film fluorescence quantum yield: 64.4%) prepared in example 5 as a luminescent material, and device performances of the doped devices and the undoped devices are tested and characterized, and the results are shown in fig. 9-10.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/20 wt% emitter PPF (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/emitter (30nm)/TPBi (50nm)/LiF (1nm)/Al (undoped structure).
FIG. 9 is a L-V-J plot of OLEDs based on the material obtained in example 5, from which it can be seen that the maximum luminance is high and the threshold voltage is low for the BSNO-XT based doped and undoped devices, 59805cd/m respectively23.7V and 24093cd/m24.3V. FIG. 10 is a graph of the efficiency of doped and undoped devices based on the material obtained in example 5 as a function of luminance, from which it can be seen that the maximum current efficiency and power efficiency of the doped and undoped devices based on BSNO-XT are 84.8cd/A, 70.1lm W, respectively-1And 25.5cd/A, 17.6lm W-1The maximum external quantum efficiency of the doped and undoped devices based on BSNO-XT is 26.1% and 8.7%, respectively, when the brightness is 1000cd/m2The external quantum efficiency was maintained at 21.4% and 8.0%, respectively.
Example 32: OLEDs device performance of xanthone-based organic electroluminescent materials (BDMCz-XT)
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material BDMCz-XT prepared in the embodiment 6 as a luminescent material, and the device performance is tested and characterized, and the result is shown in FIGS. 11-12.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)20 wt% emitter PPF (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/emitter (20nm)/TmPyPB (60nm)/LiF (1nm)/Al (undoped structure).
FIG. 11 is a L-V-J plot of OLEDs based on the material obtained in example 6, from which it can be seen that the maximum luminance is high and the threshold voltage is low for the doped and undoped devices based on BDMCz-XT, 18362cd/m respectively23.6V and 1152cd/m2And 3.1V. FIG. 12 is a graph of the efficiency of doped and undoped devices based on the material obtained in example 6 as a function of luminance, from which it can be seen that the maximum current efficiency and power efficiency of the doped and undoped devices based on BDMCz-XT are 49.7cd/A, 41.1lm W/A, respectively-1And 13.3cd/A, 13.0lm W-1BDMCz-XT based doped and undoped devices have maximum external quantum efficiencies of 21.3% and 4.7%, respectively, when the luminance is 1000cd/m2The external quantum efficiency was maintained at 18.2% and 0.9%, respectively.
Example 33: OLEDs device performance of xanthone-based organic electroluminescent materials (Cz-XT-DMAC)
Doped devices and undoped devices are prepared by using the organic electroluminescent material Cz-XT-DMAC based on xanthone prepared in the embodiment 7 as a luminescent material, and the device performance is tested and characterized, and the result is shown in FIGS. 13-14.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)20 wt% emitter PPF (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/emitter (20nm)/PPF (10nm)/TPBi (50nm)/LiF (1nm)/Al (undoped structure).
FIG. 13 is a L-V-J plot of OLEDs based on the material obtained in example 7, from which it can be seen that doped and undoped devices based on Cz-XT-DMAC have high maximum luminance and low actuation voltage 69466cd/m, respectively23.6V and 45619cd/m2And 3.1V. FIG. 14 is a graph of the efficiency as a function of luminance for doped and undoped devices based on the material obtained in example 7, from which it can be seen that the maximum current efficiency and power efficiency scores for doped and undoped devices based on Cz-XT-DMAC89.2cd/A, 77.8lm W respectively-1And 43.1cd/A, 32.5lm W-1The maximum external quantum efficiencies of doped and undoped devices based on Cz-XT-DMAC are 27.1% and 13.3%, respectively, when the luminance is 1000cd/m2The external quantum efficiency was maintained at 21.4% and 13.1%, respectively.
Example 34: OLEDs device performance of xanthone-based organic electroluminescent materials (DMCz-XT-DMAC)
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material DMCz-XT-DMAC prepared in example 12 as a luminescent material, and the device performance is tested and characterized, and the result is shown in FIGS. 15-16.
The device structure is as follows: ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/30 wt% emitter mCP (20nm) (30nm)/TPBi (50nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/NPB (30nm)/mCP (10nm)/emitter (30nm)/TPBi (50nm)/LiF (1nm)/Al (undoped structure).
FIG. 15 is a L-V-J plot of OLEDs based on the material obtained in example 12, from which it can be seen that the maximum luminance is high and the actuation voltage is low for the doped and undoped devices based on DMCz-XT-DMAC, 81127cd/m respectively23.6V and 63912cd/m2And 2.7V. FIG. 16 is a graph of the efficiency of doped and undoped devices based on the material obtained in example 7 as a function of luminance, from which it can be seen that the maximum current efficiency and power efficiency of the doped and undoped devices based on DMCz-XT-DMAC are 50.3cd/A, 33.5lm W-1And 63.5cd/A, 52.5lm W-1The maximum external quantum efficiencies of the doped and undoped devices based on DMCz-XT-DMAC are 15.4% and 18.8%, respectively, when the luminance is 1000cd/m2The external quantum efficiency was maintained at 14.8% and 18.3%, respectively.
Example 35: OLEDs device performance of xanthone-based organic electroluminescent materials (BTMCz-XT)
Doped devices and undoped devices are prepared by using the xanthone-based organic electroluminescent material BTMCz-XT prepared in example 14 as a luminescent material, and the device performance is tested and characterized, and the result is shown in FIG. 17.
The device structure is as follows: ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/CBP 10 wt% emitter (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (doped structure);
ITO/HATCN (5nm)/TAPC (30nm)/TcTa (5nm)/emitter (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (undoped structure).
FIG. 17 is a graph of efficiency vs. luminance for OLEDs based on the material obtained in example 14, from which it can be seen that the maximum external quantum efficiencies of the BTMCz-XT based doped and undoped devices are 19.2% and 2.0%, respectively, when the luminance is 1000cd/m2The external quantum efficiency was maintained at 14.1% and 1.5%, respectively.
Example 36: OLEDs device performance of xanthone-based organic electroluminescent materials (BDFDMCz-XT)
The organic electroluminescent material BDFDMCz-XT based on xanthone prepared in the example 15 is used as a non-doped device prepared from a luminescent material, and the performance of the device is tested and characterized as shown in the figure 18-19.
The device structure is as follows: ITO/HATCN (5nm)/TAPC (30nm)/TcTa (5nm)/emitter (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (undoped structure).
FIG. 18 is a L-V-J graph of an OLEDs device based on the material obtained in example 15, from which it can be seen that the maximum luminance of the BDFDMCz-XT based undoped device is high and the threshold voltage is low, 1570cd/m2And 3.3V. FIG. 19 is a graph of the efficiency of an undoped device based on the material obtained in example 15 as a function of luminance, from which it can be seen that the maximum current efficiency and power of the undoped device based on BDFDMCz-XT are 15.6cd/A and 12.4lm W, respectively-1BDFDMCz-XT based undoped device has maximum external quantum efficiency of 5.0 percent and brightness of 1000cd/m2The external quantum efficiency was maintained at 2.7%.
Example 37: OLEDs device performance of xanthone-based organic electroluminescent materials (BDClDMAC-XT)
The organic electroluminescent material BDClDMAC-XT based on the xanthone prepared in the example 16 is used as a non-doped device prepared from a luminescent material, and the performance of the device is tested and the characterization result is shown in figures 20-21.
The device structure is as follows: ITO/HATCN (5nm)/TAPC (50nm)/TcTa (5nm)/emitter (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (undoped structure).
FIG. 20 is a L-V-J graph of an OLEDs device based on the material obtained in example 16, from which it can be seen that the maximum luminance of a non-doped device based on BDCDC-XT is high and the threshold voltage is low, 3663cd/m2And 3V. FIG. 21 is a graph of the efficiency as a function of luminance for an undoped device based on the material obtained in example 16, from which it can be seen that the maximum current efficiency and power of the undoped device based on BDClDMAC-XT are 27.2cd/A and 27.8lm W, respectively-1The maximum external quantum efficiency of the BDClDMAC-XT-based undoped device is 8.9 percent when the brightness is 1000cd/m2The external quantum efficiency was maintained at 4.0%.
The data show that the invention takes xanthone as the core, and connects the same or different electron-donating groups on two sides, so that AIE and TADF characteristics can be organically combined in one molecule, and the doped OLEDs prepared by taking the material as a luminescent layer have high efficiency and smaller efficiency roll-off degree; the non-doped OLEDs (organic light emitting diodes) device with a simple structure prepared based on the materials has lower starting voltage, higher efficiency and smaller efficiency roll-off degree. In a word, the material has wide application prospect in the field of organic electroluminescence.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (4)

1. An organic electroluminescent material based on xanthone is characterized by having the following structure:
Figure FDA0002708753350000011
wherein when Ar is1And Ar2When attached at positions 2 and 7, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to u, Ar1And Ar2Are identical or different radicals;
when Ar is1And Ar2When attached at positions 3 and 6, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to s, Ar1And Ar2Are the same group;
when Ar is1And Ar2When attached at positions 3 and 6, Ar1、Ar2Are respectively selected from one of the structures shown in the formulas a to v, Ar1And Ar2Are different groups;
Figure FDA0002708753350000012
2. the xanthone-based organic electroluminescent material of claim 1, wherein the xanthone-based organic electroluminescent material comprises one or more of the following compounds:
Figure FDA0002708753350000021
3. use of the xanthone-based organic electroluminescent material according to any one of claims 1 to 2 for the production of OLEDs.
4. Use according to claim 3, wherein the xanthone-based organic electroluminescent material is used as a light-emitting layer of an OLED in a doped or undoped manner.
CN202011048426.6A 2020-09-29 2020-09-29 Organic electroluminescent material based on xanthone and application thereof in preparing OLED (organic light emitting diode) Pending CN112142725A (en)

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CN105340101A (en) * 2013-07-03 2016-02-17 国立大学法人九州大学 Light-emitting material, long-persistent phosphor, organic light-emitting element and compound
CN105884830A (en) * 2016-05-11 2016-08-24 中节能万润股份有限公司 Bipolar OLED (organic light-emitting diode) phosphorescence main body material and luminescent device containing material
CN107312523A (en) * 2017-06-23 2017-11-03 中节能万润股份有限公司 A kind of electroluminescent organic material and its preparation method and application
CN108346756A (en) * 2017-01-24 2018-07-31 江苏三月光电科技有限公司 A kind of organic electroluminescence device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105340101A (en) * 2013-07-03 2016-02-17 国立大学法人九州大学 Light-emitting material, long-persistent phosphor, organic light-emitting element and compound
CN105884830A (en) * 2016-05-11 2016-08-24 中节能万润股份有限公司 Bipolar OLED (organic light-emitting diode) phosphorescence main body material and luminescent device containing material
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