CN111471043B - Organic luminescent material containing benzo [ c ] [1,2,5] thiadiazole derivative receptor structural unit and application thereof - Google Patents
Organic luminescent material containing benzo [ c ] [1,2,5] thiadiazole derivative receptor structural unit and application thereof Download PDFInfo
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Abstract
The invention provides an organic luminescent material based on a donor-acceptor structure of a benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group acceptor and a 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile acceptor and application thereof. The organic luminescent material is a system with separated acceptor and donor, wherein the acceptor is benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group or 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile, and the donor is carbazole and derivatives or benzoxazine and the like. The lowest unoccupied orbital (LUMO) in the material is located in an acceptor, and the highest occupied orbital (HOMO) is located in a donor, so that the molecular orbital level of the luminescent material can be effectively regulated and controlled through the electrical regulation of the acceptor structure and the donor. The luminous color of the material molecules can be conveniently adjusted by adjusting the structure of the luminous material or the electron donating capability of the donor. The organic luminescent material has the characteristic of easily-adjusted luminescent color, and can be used as a luminescent material for preparing OLED devices.
Description
Technical Field
The invention relates to the field of organic luminescent materials, in particular to a luminescent material containing benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group and 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile acceptor structural unit and application thereof.
Background
The OLED, i.e., an Organic Light-Emitting Diode (Organic Light-Emitting Diode) or an Organic Light-Emitting Device (Organic Light-Emitting Device), is a self-Emitting material without a backlight source; the display has the advantages of all solid state, wide visual angle, low temperature resistance, vivid color, low driving voltage, high response speed, high contrast and definition, ultra-thin, easy flexible display and the like, and can also use glass, flexible metal and plastic with low cost as substrates; in addition, the method has the advantages of high energy efficiency, low energy consumption, wide material source, simple production process, planar luminescence, large-area production and the like. As a new generation of lighting and display technology, OLEDs have been applied to products such as mobile phones, flat panels, cameras, televisions, computers, detection instruments, and the like, and have potential application prospects in the fields of aerospace, planar solid-state lighting, and the like.
The light emitting material is a core part of the OLED device, and the organic light emitting material can be roughly classified into a fluorescent material, a phosphorescent material, and a Thermally Activated Delayed Fluorescence (TADF) material according to the principle of light emission. Fluorescent materials are the first generation of OLED materials in the earliest applications, and are limited in that electron spin statistics can only utilize singlet excitons to emit light, and the internal quantum efficiency of the device can reach as high as 25%. In 1988, Forrest professor of Princeton university in America reports the phosphorescence electroluminescence phenomenon of the metal organic platinum complex at room temperature, and the quantum efficiency in the device can reach 100%. Although the metal organic phosphorescent material has been developed to a great extent so far, the iridium complex phosphorescent material for red and green light has been used in commercial electronic products, but the phosphorescent material is very expensive due to the use of rare and expensive noble metals, and the resource is extremely limited. And at present, the core patents related to the metal organic phosphorescent material are monopolized by companies in the United states and Europe. Thermally Activated Delayed Fluorescence (TADF) materials achieve 100% luminous efficiency through the inversion of triplet excitons, which is comparable to that of phosphorescent materials, and the use of noble metals can be avoided. Therefore, the development of a novel thermal activation delayed fluorescent material which can be used for an OLED device has very important significance for the development of the OLED industry in China.
Disclosure of Invention
The invention aims to provide a luminescent material containing benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group and 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile acceptor structural units, and the material can be used for OLED devices.
The invention adopts the following technical scheme:
an organic luminescent material containing a benzo [ c ] [1,2,5] thiadiazole derivative acceptor structural unit has a structural formula shown as a formula (I) or a formula (II):
in formula (I), the acceptor is benzo [ c ]][1,2,5]Thiadiazole-4-carboxaldehyde radical, R a1 Or R b1 Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (C) 3 -C 24 Cycloalkyl of (C) 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (A), C 1 -C 24 Aryl of, C 4 -C 24 Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m1 and n1 represent the number of substituents; wherein m1 is an integer of 0-2, and n1 is an integer of 0-4;
in the formula (II), the acceptor is 2- (benzo [ c ]][1,2,5]Thiadiazole-4-methylene) malononitrile, R a2 Or R b2 Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (C) 3 -C 24 Cycloalkyl of, C 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (2), C 1 -C 24 Aryl of, C 4 -C 24 Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or combinations thereof;
m2 and n2 represent the number of substituents; wherein m2 is an integer of 0-2, and n2 is an integer of 0-4;
donor D 1 Or D 2 Each independently is one of the following structures:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 And R 12 Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (1), C 3 -C 24 Cycloalkyl of (C) 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (A), C 1 -C 24 Aryl of, C 4 -C 24 Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o1, p1, q1, R1, s1, t1, u1, v1, w1, x1, y1 and z1 are each R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 And R 12 The number of (2); o1, p1, q1, r1, s1, t1, u1, v1, w1, x1, y1 and z1 are integers from 0 to 4.
Further, the organic luminescent material is a compound shown in formulas (III) and (IV):
wherein, in the formula (III), R a3 Or R b3 Each independently of the others is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (C) 3 -C 24 Cycloalkyl of, C 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (A), C 1 -C 24 Aryl of, C 4 -C 24 Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m3 and n3 represent the number of substituents; wherein m3 is an integer of 0-2, n3 is an integer of 0-4;
in the formula (IV), R a4 Or R b4 Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (C) 3 -C 24 Cycloalkyl of, C 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (2), C 1 -C 24 Aryl of (C) 4 -C 24 Aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m4 and n4 represent the number of substituents; wherein m4 is an integer of 0-2, and n4 is an integer of 0-4;
said donor D 3 Or D 4 Each independently is one of the following structures:
wherein R is 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 '、R 7 '、R 8 '、R 9 '、R 10 '、R 11 ' and R 12 ' independently of one another are hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Alkoxy group of (C) 3 -C 24 Cycloalkyl of, C 1 -C 24 Ether of (C) 1 -C 24 Heterocyclic group of (2), C 1 -C 24 Aryl of (C) 4 -C 24 Aryloxy, halogen, silicon, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o2, p2, q2, R2, s2, t2, u2, v2, w2, x2, y2 and z2 are each R 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 '、R 7 '、R 8 '、R 9 '、R 10 '、R 11 ' and R 12 ' number; o2, p2, q2, r2, s2, t2, u2, v2, w2, x2, y2 and z2 are integers from 0 to 4.
Further, the organic light-emitting material is one of the following materials:
further, the organic luminescent material based on the donor-acceptor structure of the benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group acceptor and the 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile acceptor is as follows:
the invention also provides an application of the luminescent material based on the benzo [ c ] [1,2,5] thiadiazole-4-aldehyde group and the 2- (benzo [ c ] [1,2,5] thiadiazole-4-methylene) malononitrile acceptor structural unit as a luminescent layer of an organic electroluminescent device.
Compared with the prior art, the invention has the beneficial effects that:
(1) the molecular orbital energy level of the luminescent material can be effectively regulated and controlled through the electrical regulation of the acceptor structure and the donor.
(2) The luminous color of the material molecules can be conveniently adjusted by adjusting the structure of the luminous material or the electron donating capability of the donor.
(3) Luminescent materials based on novel acceptor structures can be successfully applied to the preparation of OLED devices.
Drawings
FIG. 1 is a comparison of HOMO and LUMO orbital distributions of BTC-1, BTC-2, BTC-3, and BTC-4 calculated by Density Functional Theory (DFT).
FIG. 2 is a comparison of HOMO and LUMO orbital distributions of BTN-1, BTN-2, BTN-3, and BTN-4 calculated by Density Functional Theory (DFT).
FIG. 3(a) is an absorption spectrum of luminescent materials BTC-1, BTC-2, BTC-3, and BTC-4 in a toluene solution at room temperature; (b) the absorption spectra of the luminescent materials BTN-1, BTN-2, BTN-3 and BTN-4 in toluene solution at room temperature.
FIG. 4(c) is an emission spectrum of the luminescent materials BTC-1, BTC-2, BTC-3 and BTC-4 in a toluene solution at room temperature; (d) the emission spectra of the luminescent materials BTN-1, BTN-2 and BTN-3 in toluene solution at room temperature.
FIG. 5 is a comparison of the emission spectra of the light-emitting material BTC-1 at room temperature in various environments. Wherein HEX is n-hexane; TOL is toluene; EA is ethyl acetate; THF is tetrahydrofuran; DCM is dichloromethane.
Fig. 6 is a comparison of the emission spectra of the light-emitting material BTC-2 at room temperature in various environments. Wherein HEX is n-hexane; TOL is toluene; EA is ethyl acetate; THF is tetrahydrofuran; DCM is dichloromethane.
FIG. 7 is a graph showing emission spectra of thin films of the light-emitting materials BTC-1, BTC-2 and BTC-3.
FIG. 8 is a graph of the electroluminescence spectra of the luminescent materials CBP or mCBP as luminescent host respectively doped with BTC-3 with different concentrations.
Fig. 9 is a device current density-voltage-luminous intensity curve of the light emitting material CBP or mCBP as the light emitting host under different concentrations of BTC-3 doping, respectively.
FIG. 10 is the device electroluminescence spectrum of the luminescent material mCBP as the luminescent host under the doping of the guest BTC-1, BTC-2 and BTC-3 respectively.
Fig. 11 is a device current density-voltage-luminescence intensity curve of the light-emitting material mCBP as a light-emitting host under doping of the guest BTC-1, BTC-2 and BTC-3, respectively.
Fig. 12 is a schematic view of the structure of the fabricated device and the molecular structure of a part of the material.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
Unless otherwise indicated, all commercial reagents involved in the following experiments were purchased and used directly without further purification. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are both in deuterated chloroform (CDCl) 3 ) Measured in solution, hydrogen spectra were 400 or 500For the carbon spectrum of the NMR spectrometer, a NMR spectrometer with 100 or 126 MHz was used, and the chemical shifts were based on Tetramethylsilane (TMS) or residual solvent. With deuterated chloroform (CDCl) 3 ) As solvent, the hydrogen spectrum and carbon spectrum are respectively expressed in TMS (delta. 0.00ppm) and CDCl 3 (δ 77.00ppm) as an internal standard. The following abbreviations (or combinations) are used to interpret the hydrogen spectral peaks: s is singlet, d is doublet, t is triplet, q is quartet, p is quintet, m is multiplet, br is broad. The high resolution mass spectrum is measured on an LTQ FT Ultra mass spectrometer of Sammer Feishel technologies, Inc., and the sample ionization mode is electrospray ionization.
Example 1: the synthesis route of the luminescent material BTN-1 is as follows:
synthesis of intermediate 1: 3-methyl-1, 2-phenylenediamine (30.53g,249.87mmol,1.0 equiv.), triethylamine (138.92mL,999.47mmol,4.0 equiv.), and methylene chloride (300mL) were added sequentially to a dry three-necked flask equipped with magnetic stirring and placed in an ice bath. The mixture was stirred for more than 1 hour, after which thionyl chloride (36.25mL,499.74mmol,2.0 equiv.) and dichloromethane (100mL) were slowly added dropwise, the mixture was stirred at that temperature for 1 hour, then the mixture was placed in an oil bath, stirred at 40 ℃ for 20 hours, and the reaction was monitored by thin layer chromatography until the reaction was complete. The reaction was stopped and the resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with ethyl acetate. The combined organic phases were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate 10: 1-4: 1) to obtain 33.40g of a colorless liquid with a yield of 89%.
Synthesis of intermediate 2: intermediate 1(32.06g,213.43mmol,1.0 equiv.), hydrogen bromide solution (200mL, 48% aq.) and bromine water (11.48mL,224.10mmol,1.05 equiv.) were added sequentially to a dry three-necked flask equipped with magnetic stirring, the mixture was placed in an oil bath and the reaction stirred at 120 ℃. After 24 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and neutralized with saturated sodium bicarbonate solution. The mixture was extracted three times with ethyl acetate. The combined organic phases were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate 20: 1-5: 1) to give 42.05g of a white solid in 86% yield.
And (3) synthesis of an intermediate 3: intermediate 2(25.34g,110.62mmol,1.0 equiv.), N-bromosuccinimide (59.07g,331.88mmol,3.0 equiv.), and chlorobenzene (250mL) were added sequentially to a dry three-necked flask equipped with magnetic stirring and placed in an oil bath and stirred at 60 ℃ for 20 minutes. Benzoyl peroxide (5.36g,22.13mmol,0.2 eq.) was then added and the mixture placed in an oil bath and heated to 100 ℃ for reaction. After 24 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic phases were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate: 100: 1-10: 1) to obtain 32.10g of a pale yellow solid with a yield of 75%.
Synthesis of Br-CHO: intermediate 3(30.74g,79.45mmol,1.0 equiv.) and formic acid (100mL) were added sequentially to a dry three-necked flask equipped with magnetic stirring and placed in an oil bath and heated to 120 ℃. After 24 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature, quenched with water and stirred for 1 hour. The resulting mixture was concentrated in vacuo and the residue was washed three times with water and finally dried in a vacuum oven to give 15.45g of a brown solid compound in 80% yield. 1 H NMR(500MHz,CDCl 3 ),δ8.06(d,J＝9.5Hz,1H),8.10(d,J＝9.5Hz,1H),10.76(s,1H)。 13 C NMR(125MHz，CDCl 3 ),δ121.7,126.7,131.5,131.9,152.1,153.8,188.0。HRMS(m/z,FAB+)：C 7 H 3 79 BrN 2 OS calculated 241.9149, found 241.9149, C 7 H 3 81 BrN 2 OS calculated 243.9129, found 243.9137.
Synthesis of intermediate 1-Br: carbazole (8.39g,50.17mmol,1.0 equivalent), 1-bromo-4-iodobenzene (15.61g,55.19mmol,1.1 equivalent), cuprous iodide (955.6mg,5.02mmol,0.1 equivalent), L-proline (1.16g,10.03mmol,0.2 equivalent), and potassium carbonate (13.87g,100.35mmol,2.0 equivalent) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then dimethyl sulfoxide (100mL) was added under nitrogen blanket, the mixture was placed in an oil bath and heated to 100 ℃ for reaction. After 36 hours, the reaction was monitored by thin layer chromatography until completion. The resulting mixture was cooled to room temperature and diluted with dichloromethane. The mixture was washed three times with brine and extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether) to obtain 9.70g of a white solid with a yield of 60%.
Synthesis of intermediate 1-B: 1-Br (4.99g,15.49mmol,1.0 eq.) was added to a dry three-necked flask equipped with magnetic stirring. Nitrogen was purged three times, then tetrahydrofuran (100mL) was added under nitrogen blanket, and after the mixture was cooled to-78 deg.C, n-butyllithium (9.68mL,15.49mmol,1.0 eq, 1.6mol/L in hexane) was added slowly dropwise and stirred at that temperature for 1 hour. The mixture was then warmed to room temperature and 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane (3.16mL,15.49mmol,1.0 eq) was added to the flask under nitrogen and after stirring for 12 hours, monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and quenched with saturated ammonium chloride solution. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 3:1) to give 4.52g of a white solid in a yield of 79%.
BTC-1 synthesis: 1-B (1.33g,3.61mmol,1.2 equivalents), Br-CHO (730.3mg,3.00mmol,1.0 equivalents), tetrakis (triphenylphosphine) palladium (104.1mg,0.09mmol,0.03 equivalents) and potassium carbonate (1.04g,7.51mmol,2.5 equivalents) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then toluene (36mL), ethanol (12mL) and water (12mL) were added under nitrogen, and the mixture was placed in an oil bath and heated to 90 deg.C. The reaction was monitored by thin layer chromatography until completion and stopped after 18 hours. The resulting mixture was cooled to room temperature and quenched with water. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:1.5) to give 779.6mg of a yellow solid in a yield of 64%. 1 H NMR(500MHz,CDCl 3 ),δ7.32-7.35(m,2H),7.44–7.47(m,2H),7.57(d,J＝8.2Hz,2H),7.81(dt,J＝8.5,2.2Hz,2H),8.02(d,J＝7.3Hz,1H),8.18(dt,J＝7.8,0.9Hz,2H),8.28(dt,J＝8.5,2.3Hz,2H),8.38(d,J＝7.3Hz,1H),10.84(s,1H)。 13 C NMR(125MHz,CDCl 3 ),δ109.99,120.48,120.57,123.79,126.24,126.73,127.23,127.33,131.23,132.65,135.26,139.16,139.41,140.65,153.94,154.01,189.08。
Synthesis of BTN-1: BTC-1(614.3mg,1.51mmol,1.0 equiv.), malononitrile (300.2mg,4.54mmol,3.0 equiv.), sodium acetate (618.5mg,4.54mmol,3.0 equiv.), anhydrous sodium sulfate (1.29g,9.09mmol,6.0 equiv.), and toluene (30mL) were added sequentially to a three-necked flask equipped with magnetic stirring. The mixture was placed in an oil bath and the reaction was stirred at 90 ℃. After 18 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and a sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:1) to give 680.2mg of an orange-yellow solid in a yield of 99%. 1 H NMR(500MHz,CDCl 3 ),δ7.32–7.35(m,2H),7.44–7.47(m,2H),7.57(d,J＝8.2Hz,2H),7.83(dt,J＝8.6,2.2Hz,2H),8.03(d,J＝7.7Hz,1H),8.17(dt,J＝7.7,1.0Hz,2H),8.30(dt,J＝8.6,2.2Hz,2H),8.86(dd,J＝7.7,0.6Hz,1H),8.90(s,1H)。
Example 2: the synthesis route of the luminescent material BTN-2 is as follows:
synthesis of 2-Br: 3, 6-di-tert-butylcarbazole (3.19g,11.41mmol,1.0 equiv.), 1-bromo-4-iodobenzene (3.55g,12.55mmol,1.1 equiv.), cuprous iodide (217.2mg,1.14mmol,0.1 equiv.), L-proline (262.6mg,2.28mmol,0.2 equiv.), and potassium carbonate (2.63g,22.81mmol,2.0 equiv.) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then dimethyl sulfoxide (60mL) was added under nitrogen blanket, the mixture was placed in an oil bath and heated to 100 ℃ for reaction. After 36 hours, the reaction was monitored by thin layer chromatography until completion. The resulting mixture was cooled to room temperature and diluted with dichloromethane. The mixture was washed three times with brine and extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether) to obtain 3.32g of a white solid in a yield of 67%.
2-B Synthesis: 2-Br (2.01g,4.63mmol,1.0 equiv.) was added to a dry three-necked flask equipped with magnetic stirring. After purging with nitrogen three times, tetrahydrofuran (50mL) was added under nitrogen, and the mixture was cooled to-78 deg.C and n-butyllithium (2.89mL,4.63mmol,1.0 eq, 1.6mol/L in hexane) was added slowly dropwise and stirred at this temperature for 1 hour. The mixture was then warmed to room temperature and 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane (0.94mL,4.63mmol,1.0 eq) was added to the flask under nitrogen blanket and after stirring for 12 h, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and quenched with saturated ammonium chloride solution. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and a sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 4:1) to obtain 1.96g of a white solid in a yield of 88%.
Synthesis of BTC-2: 2-B (1.72g,3.57mmol,1.2 equivalents), Br-CHO (722.2mg,2.97mmol,1.0 equivalents), tetrakis (triphenylphosphine) palladium (103.0mg,0.09mmol,0.03 equivalents) and potassium carbonate (1.03g,7.43mmol,2.5 equivalents) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then toluene (36mL), ethanol (12mL) and water (12mL) were added under nitrogen, and the mixture was placed inHeated to 90 ℃ in an oil bath. The reaction was monitored by thin layer chromatography until completion and stopped after 18 hours. The resulting mixture was cooled to room temperature and quenched with water. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:1.5) to give 676.8mg of a yellow solid in a yield of 44%. 1 H NMR(500MHz,CDCl 3 ),δ1.48(s,18H),7.48–7.52(m,4H),7.80(dd,J＝6.5,1.9Hz,2H),8.01(d,J＝7.3Hz,1H),8.16(s,2H),8.26(dt,J＝8.5,2.2Hz,2H),8.37(d,J＝7.3Hz,1H),10.84(s,1H)。
Synthesis of BTN-2: BTC-2(518.2mg,1.00mmol,1.0 equiv.), malononitrile (198.4mg,3.00mmol,3.0 equiv.), sodium acetate (408.7mg,3.00mmol,3.0 equiv.), anhydrous sodium sulfate (853.1mg,6.01mmol,6.0 equiv.), and toluene (20mL) were added sequentially to a three-necked flask equipped with magnetic stirring. The mixture was placed in an oil bath and the reaction was stirred at 90 ℃. After 18 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and a sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1.5:1) to give 368.1mg of a brown solid in a yield of 65%. 1 H NMR(500MHz,CDCl 3 ),δ1.48(s,18H),7.48–7.52(m,4H),7.82(dd,J＝6.6,1.9Hz,2H),8.03(d,J＝7.7Hz,1H),8.16(s,2H),8.28(dt,J＝8.6,2.2Hz,2H),8.86(d,J＝7.7Hz,1H),8.89(s,1H)。 13 C NMR(125MHz,CDCl 3 ),δ32.14,34.93,83.84,109.47,113.00,113.78,116.54,122.89,123.90,123.93,126.73,127.54,130.79,131.18,134.07,138.86,139.53,140.13,143.61,152.92,153.06,154.49。
Example 3: the synthesis route of the luminescent material BTN-3 is as follows:
synthesis of 3-Br: 3, 6-Diphenylcarbazole (3.33g,10.42mmol,1.0 equivalent), 1-bromo-4-iodobenzene (3.24g,11.46mmol,1.1 equivalent), cuprous iodide (39.7mg,0.21mmol,0.02 equivalent), and sodium tert-butoxide (2.00g,20.81mmol,2.0 equivalents) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then 1, 2-trans-cyclohexanediamine (0.13mL,1.04mmol,0.1 equiv.) and 1, 4-dioxane (100mL) were added under nitrogen, the mixture was placed in an oil bath and the reaction was stirred at 100 ℃. The reaction was monitored by thin layer chromatography until the reaction was complete and stopped after 48 hours. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure and the sample was purified by silica gel column chromatography (eluent: petroleum ether) to give 4.20g of a white solid in 85% yield.
3-B Synthesis: 3-Br (3.31g,6.98mmol,1.0 equiv.), Bipinacol boronate (3.19g,12.57mmol,1.8 equiv), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (153.2mg,0.21mmol,0.03 equiv.) and potassium acetate (2.05g,20.93mmol,3.0 equiv.) were added sequentially to a dry three-necked flask equipped with magnetic stirring. Nitrogen was purged three times, then dimethyl sulfoxide (60mL) was added under nitrogen blanket, the mixture was placed in an oil bath and the reaction stirred at 90 ℃. After 24 hours, the reaction was monitored by thin layer chromatography until the reaction was complete. The resulting mixture was cooled to room temperature and diluted with dichloromethane. The mixture was washed three times with brine and extracted three times with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and filtered, the filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 2:1) to obtain 2.33g of a white solid in a yield of 64%.
Synthesis of BTC-3: 3-B (1.87g,3.59mmol,1.2 equivalents), Br-CHO (727.5mg,2.99mmol,1.0 equivalents), tetrakis (triphenylphosphine) palladium (103.8mg,0.09mmol,0.03 equivalents), potassium carbonate (1.03g,7.48mmol,2.5 equivalents) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then toluene (36mL), ethanol (12mL) and water (12mL) were added under nitrogen, and the mixture was placed in an oil bath and heated to 90 ℃. Monitoring by thin layer chromatography until the reaction is complete, 24 hoursThe reaction was then stopped. The resulting mixture was cooled to room temperature and quenched with water. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:4) to give 918.0mg of an orange solid in a yield of 55%. 1 H NMR(500MHz,CDCl 3 ),δ7.35–7.39(m,2H),7.49–7.52(m,4H),7.64(d,J＝8.5Hz,2H),7.72(dd,J＝8.5,1.8Hz,2H),7.74(d,J＝0.9Hz,2H),7.76(d,J＝1.2Hz,2H),7.86(dt,J＝8.5,2.3,2H),8.03(d,J＝7.2Hz,1H),8.31(dt,J＝9.1,2.3Hz,2H),8.39(d,J＝7.3Hz,1H),8.43(d,J＝1.4Hz,2H),10.85(s,1H)。 13 C NMR(125MHz,CDCl 3 ),δ110.42,119.13,124.49,125.98,126.78,126.89,127.09,127.38,127.47,128.99,131.34,132.64,134.23,135.40,139.07,139.35,140.57,141.88,154.03,189.07。
Synthesis of BTN-3: BTC-3(555.0mg,1.00mmol,1.0 equiv.), malononitrile (197.2mg,2.99mmol,3.0 equiv.), sodium acetate (406.3mg,2.99mmol,3.0 equiv.), anhydrous sodium sulfate (848.2g,5.97mmol,6.0 equiv.), and toluene (25mL) were added sequentially to a three-necked flask equipped with magnetic stirring. The mixture was placed in an oil bath and the reaction was stirred at 90 ℃. The reaction was monitored by thin layer chromatography until completion and stopped after 24 hours. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:4) to give 403.9mg of a red solid with a yield of 67%. 1 H NMR(500MHz,CDCl 3 ),δ7.36–7.39(m,2H),7.49–7.52(m,4H),7.65(d,J＝8.6Hz,2H),7.72(dd,J＝8.6,1.8Hz,2H),7.74(d,J＝1.2Hz,2H),7.76(d,J＝1.4Hz,2H),7.88(dt,J＝8.5,2.2Hz,2H),8.05(d,J＝7.7Hz,1H),8.33(dt,J＝8.6,2.3Hz,2H),8.43(d,J＝1.6Hz,2H),8.87(dd,J＝7.6,0.8Hz,1H),8.90(s,1H)。
Example 4: the synthesis route of the luminescent material BTN-4 is as follows:
synthesis of 4-Br: phenoxazine (3.66g,19.98mmol,1.0 equiv.), 1-bromo-4-iodobenzene (6.22g,21.97mmol,1.1 equiv.), cuprous iodide (76.1mg,0.40mmol,0.02 equiv.), and sodium tert-butoxide (3.84g,39.95mmol,2.0 equiv.) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen was purged three times, then 1, 2-trans-cyclohexanediamine (0.25mL,2.00mmol,0.1 equiv.) and 1, 4-dioxane (80mL) were added under nitrogen, the mixture was placed in an oil bath and the reaction was stirred at 90 ℃. The reaction was monitored by thin layer chromatography until the reaction was complete and stopped after 48 hours. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether) to give 2.77g of a white solid in 41% yield.
4-B Synthesis: 4-Br (2.36g,6.98mmol,1.0 equiv.), Bipinacolboronic acid ester (3.19g,12.56mmol,1.8 equiv.), [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (153.1mg,0.21mmol,0.03 equiv.), and potassium acetate (2.05g,20.94mmol,3.0 equiv.) were added sequentially to a dry three-necked flask equipped with magnetic stirring. Nitrogen was purged three times, then dimethyl sulfoxide (60mL) was added under nitrogen blanket, the mixture was placed in an oil bath and the reaction stirred at 90 ℃. The reaction was monitored by thin layer chromatography until completion and stopped after 24 hours. The resulting mixture was cooled to room temperature and diluted with dichloromethane. The mixture was washed three times with brine and extracted three times with dichloromethane. The combined organic layer was dried over anhydrous sodium sulfate and filtered, the filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 5:1) to obtain 1.21g of a white solid in a yield of 45%.
Synthesis of BTC-4: 4-B (1.04g,2.71mmol,1.2 equivalents), Br-CHO (548.4mg,2.26mmol,1.0 equivalents), tetrakis (triphenylphosphine) palladium (78.2mg,0.07mmol,0.03 equivalents), potassium carbonate (779.5mg,5.64mmol,2.5 equivalents) were added sequentially to a dry three-necked flask equipped with magnetic stirring. The nitrogen is pumped for three times, and then toluene (30mL) and ethane are added under the protection of nitrogenAlcohol (10mL) and water (10mL) and the mixture was heated to 90 ℃ in an oil bath. After 24 hours, the reaction was monitored by thin layer chromatography until completion. The resulting mixture was cooled to room temperature and quenched with water. The mixture was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:3) to give 561.0mg of a deep red solid in a yield of 59%. 1 H NMR(500MHz,CDCl 3 ),δ6.08(dd,J＝7.9,1.5Hz,2H),6.63(td,J＝7.3,1.8Hz,2H),6.68(td,J＝7.8,1.6Hz,2H),6.73(dd,J＝7.8,1.7Hz,2H),7.57(dt,J＝8.5,2.2Hz,2H),7.99(d,J＝7.3Hz,1H),8.25(dt,J＝8.5,2.3Hz,2H),10.84(s,1H)。 13 C NMR(125MHz,CDCl 3 ),δ113.50,115.68,121.76,123.39,126.83,127.56,131.43,132.32,134.10,136.55,139.15,140.35,144.07,153.89,189.01。
Synthesis of BTN-4: BTC-4(614.3mg,1.51mmol,1.0 equiv.), malononitrile (199.2mg,3.02mmol,3.0 equiv.), sodium acetate (410.4mg,3.02mmol,3.0 equiv.), anhydrous sodium sulfate (856.6mg,6.03mmol,6.0 equiv.), and toluene (20mL) were added sequentially to a three-necked flask equipped with magnetic stirring. The mixture was placed in an oil bath and the reaction was stirred at 90 ℃. After 24 hours, the reaction was monitored by thin layer chromatography until completion. The resulting mixture was cooled to room temperature and quenched by addition of water. The mixture was extracted three times with dichloromethane. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1:3) to give 387.0mg of a dark green solid, yield 82%. 1 HNMR(500MHz,CDCl 3 ),δ6.07(dd,J＝7.9,1.5Hz,2H),6.63(td,J＝7.4,1.7Hz,2H),6.69(td,J＝7.8,1.5Hz,2H),6.73(dd,J＝7.8,1.7Hz,2H),7.58(dt,J＝8.5,2.2Hz,2H),8.00(d,J＝7.7Hz,1H),8.27(dt,J＝8.5,2.3Hz,2H),8.84(dd,J＝7.7,0.8Hz,2H),8.89(s,1H)。 13 C NMR(125MHz,CDCl 3 ),δ84.30,112.89,113.54,113.66,115.79,121.86,123.25,123.44,127.89,130.66,131.53,132.34,134.08,136.04,139.16,140.88,144.13,152.85,152.98,154.41。
Electrochemical, photophysical testing, theoretical calculations, and device data elucidation
Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV) characterizations were performed using a CH1760E electrochemical analyzer. The oxidation potential and reduction potential were measured using 0.1mol/L tetra-N-butylammonium hexafluorophosphate as the electrolyte and anhydrous N, N-dimethylformamide as the solvent, and the solution was bubbled with nitrogen for 15min before the test. Silver, platinum and glassy carbon are respectively used as a pseudo reference electrode, a counter electrode and a working electrode. The scan rate was 300 mV/s. With ferrocene ion pairs (CP) 2 Fe/Cp 2 Fe + ) And (5) making an internal standard. And measuring the oxidation-reduction potential by differential pulse voltammetry. Redox reversibility was measured by cyclic voltammetry. The process is considered reversible if the magnitudes of the peak anodic current and the peak cathodic current are equal at a scan speed of 100mV/s or less; if the magnitudes of the peak anode current and the peak cathode current are not equal, but the return sweep is not zero, then the process is considered to be quasi-reversible; otherwise the process is not reversible. Containing benzo [ c ]][1,2,5]The electrochemical properties and energy comparison of each energy level of the luminescent material with the structural unit of the thiadiazole derivative are shown in the following table.
Table one: luminescent material containing benzo [ c ] [1,2,5] thiadiazole derivative structural unit has electrochemical property and energy comparison of individual energy level
| Luminescent material | E Oxidation by oxygen [V] | E Reduction of [V] | HOMO a [eV] | LUMO b [eV] |
| BTN-1 | 1.06 | -0.58 | -5.86 | -4.22 |
| BTN-2 | 1.08 | -0.60 | -5.88 | -4.20 |
| BTN-3 | 1.27 | -0.60 | -6.07 | -4.20 |
| BTN-4 | 1.38 | -0.68 | -6.18 | -4.12 |
Note: a HOMO＝-(E oxidation by oxygen +4.8)eV。 b LUMO＝-(E Reduction of +4.8)eV。
Fig. 1-2 are theoretical calculations of the luminescent material using the tivan software package in the gas phase using the LACVP and B3LYP functionals. Optimization of ground state (S) using Density Functional Theory (DFT) 0 ) The geometry of the molecule. As can be seen from FIG. 1, the lowest unoccupied orbital (LUMO) of the luminescent materials BTC-1, BTC-2, BTC-3 and BTC-4 is located at the benzo [ c ] acceptor][1,2,5]Thiadiazole-4-aldehyde moiety, as shown in figure 2, wherein the LUMO of BTN-1, BTN-2, BTN-3 and BTN-4 is in receptor 2- (benzo [ c ]][1,2,5]Thiadiazole-4-methylene) malononitrile moiety; and the eight Highest Occupied Molecular Orbitals (HOMO) are all in the donor carbazole positionThe oxazole and the derivative or the benzoxazine part form an acceptor-donor separation system, so that charge transfer in excited molecules can be realized, and further radiation transition luminescence can be realized.
As shown in the table I, the reduction potentials of the luminescent materials BTN-1, BTN-2, BTN-3 and BTN-4 are close (-0.58 to-0.68V), and the oxidation potentials are greatly different (1.06 to 1.38V). BTN-1, BTN-2, and BTN-3 have similar LUMO orbital levels (-4.20eV to-4.22 eV), but have large differences in HOMO orbital levels (-5.86eV to-6.07 eV); this result is also supported by the Density Functional Theory (DFT) calculation (fig. 2). The power supply capacity of a donor is changed under the condition that the acceptor structure is kept unchanged, the LUMO orbital distribution of the three materials is very similar, but the HOMO orbital distribution is very different; it is demonstrated that the molecular orbital level of the luminescent material can be effectively adjusted by adjusting the molecular structure thereof.
In addition, the absorption spectra were measured on an Agilent 8453 UV-Vis spectrometer, all samples being toluene (chromatographic grade) dilute solutions (10) -5 -10 -6 M), as shown in fig. 3; FIGS. 4-7 are graphs showing the results of steady state emission spectroscopy measurements using a Horiba Jobin Yvon FluoroLog-3 spectrometer, where FIG. 7 is a graph of the measurements for thin film samples, each being a 10 wt% luminescent doped DEPEO film. The structure of DEPEO is shown by the following formula:
the photophysical property data of the luminescent material containing the structural unit of the benzo [ c ] [1,2,5] thiadiazole derivative are shown in the following table II.
Table two: photophysical property of luminescent material containing benzo [ c ] [1,2,5] thiadiazole derivative structural unit
| Luminescent material | BTC-1 | BTC-2 | BTC-3 | BTC-4 | BTN-1 | BTN-2 | BTN-3 |
| Peak/nm | 476 | 547 | 542 | 553 | 579 | 607 | 603 |
| Color of light emission | Blue light | Green light | Green light | Green light | Yellow light | Orange light | Orange light |
| Quantum efficiency of solution (toluene) | 69.5％ | 43.9％ | 26.1％ | 0.87％ | 42.3％ | 24.0％ | 24.4％ |
| Film quantum efficiency (DPEPO) | 28.7％ | 15.6％ | 15.9％ | 4.4％ | 26.3％ | 6.2％ | 2.3％ |
Note: peak refers to the strongest emission Peak of the emission spectrum of the luminescent material in toluene solution at room temperature.
As can be seen from FIGS. 3-6 and Table II, one is: the luminescent color of the material is easy to adjust: the luminous color of the material molecule can be effectively adjusted by adjusting the receptor unit or adjusting the structure of the donor under the condition of keeping the receptor structure unchanged. The second step is as follows: the emission spectrum characteristics of the luminescent material in different solvents are consistent with the characteristics of intramolecular charge transfer, and the luminescent material is indicated to be a thermally induced delayed fluorescence material. And thirdly: the material molecules can emit strong light, and the light emission can respectively reach 69.5 percent and 28.7 percent in a toluene solution and a DPEPO film at room temperature.
Fig. 8 is a graph of electroluminescence spectra of the luminescent material CBP or mCBP as luminescent host doped with different concentrations of BTC-3, respectively, from which it can be seen that the luminescent material containing the structural unit of benzo [ c ] [1,2,5] thiadiazole derivative of the present invention can emit light strongly.
Further, the organic luminescent material provided by the invention is applied to a luminescent layer of an organic electroluminescent device. In an organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emits light. The complex of the present invention represented by the general formula (1) can be used as a light-emitting material for an excellent organic light-emitting device such as an organic photoluminescent device or an organic electroluminescent device. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed over a substrate. The organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. Fig. 12 shows a schematic structure of a specific organic light-emitting device. In fig. 12, the left device includes 7 layers from bottom to top, which sequentially represent a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, where the light emitting layer is a mixed layer of a guest material doped with a host material.
The compounds represented in the examples were applied to OLED devices as organic light emitting materials. The device structure of the luminescent material CBP or mCBP as a luminescent main body under different concentrations of BTC-3 doping is as follows: device 1: ITO/HATCN (10nm)/TAPC (65 nm)/CBP: BTC-3 (x%, 20nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al, x is 10%. Device 2: ITO/HATCN (10nm)/TAPC (65 nm)/CBP: BTC-3 (x%, 20nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al, and x is 20%. Device 3: ITO/HATCN (10nm)/TAPC (65 nm)/mCBP: BTC-3 (x%, 20nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al, and x is 10%. Device 4: ITO/HATCN (10nm)/TAPC (65 nm)/mCBP: BTC-3 (x%, 20nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al，x＝20％。
The device structure of the luminescent material mCBP as a luminescent host under the doping of the guest BTC-1, BTC-2 and BTC-3 is as follows: device 5: ITO/HATCN (10nm)/TAPC (40nm)/TCTA (10 nm)/mCBP: BTC-1 (x%, 30nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al, x is 10%. Device 6: ITO/HATCN (10nm)/TAPC (40nm)/TCTA (10 nm)/mCBP: BTC-2 (x%, 30nm)/PPT (4)0nm)/Li 2 CO 3 (1nm)/Al, and x is 10%. The device 7: ITO/HATCN (10nm)/TAPC (40nm)/TCTA (10 nm)/mCBP: BTC-3 (x%, 30nm)/PPT (40nm)/Li 2 CO 3 (1nm)/Al, and x is 10%. The molecular structure of the materials used in the above devices is as follows:
taking the diagram in fig. 12a as an example, ITO is a transparent anode; HAT-CN is a hole injection layer, TAPC is a hole transport layer, TCTA is an electron blocking layer, CBP is a host material, the compounds represented in examples 1 to 4 are guest materials, 10 to 20 wt.% are doping concentrations, 30nm or 20nm is the thickness of an emission layer, PPT is an electron transport layer, Li is a hole transporting layer 2 CO 3 Is an electron injection layer and Al is a cathode. The number in parentheses in nanometers (nm) is the thickness of the film.
The materials used to make the devices are subjected to a high vacuum (10) prior to use -5 -10 -6 Torr) for sublimation purification by gradient heating. Indium Tin Oxide (ITO) substrates used by the devices were sequentially sonicated in deionized water, acetone, and isopropanol. The anode electrode is indium tin oxide ITO, and the cathode is made of Li 2 CO 3 And Al. The device passes through the vacuum degree of less than 10 -7 And vacuum thermal evaporation is carried out under the pressure of Torr. After all devices are prepared, the glass cover and the epoxy resin are packaged in a nitrogen glove box, and a moisture absorbent is added into the package.
FIG. 9 is a graph of device current density-voltage-luminous intensity for devices 1-4, FIGS. 10 and 11 are a graph of electroluminescence spectra and a graph of current density-voltage-luminous intensity for devices 5-7, respectively, and it can be seen from the characterization of the performance data for the devices in FIG. 8, FIG. 9, FIG. 10, and FIG. 11 that the maximum luminous intensity of the OLED device doped with molecules of the luminescent material developed in the present application can exceed 10000cd/m 2 Indicating that the material molecule can be successfully used as the OLED luminescent material.
It should be noted that the structure is an example of an application of the light emitting material of the present invention, and does not constitute a limitation of the structure of the specific OLED device of the light emitting material of the present invention, and the light emitting material is not limited to the compounds shown in examples 1 to 4.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of practicing the invention, and that various changes in form and detail may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.
Claims (5)
1. An organic luminescent material containing a benzo [ c ] [1,2,5] thiadiazole derivative acceptor structural unit is characterized in that the structural formula is shown as a formula (I) or a formula (II):
in the formula (I), the acceptor is benzo [ 2 ]c][1,2,5]Thiadiazole-4-carbaldehyde group, R a1 Or R b1 Each independently is hydrogen;
m1 and n1 represent the number of substituents; wherein m1 is an integer of 0-2, n1 is an integer of 0-4;
in the formula (II), the acceptor is 2- (benzo [ 2 ], ]c][1,2,5]Thiadiazole-4-methylene) malononitrile, R a2 Or R b2 Each independently is hydrogen;
m2 and n2 represent the number of substituents; wherein m2 is an integer of 0-2, and n2 is an integer of 0-4;
donor D 1 Or D 2 Each independently is one of the following structures:
wherein R is 1 、R 2 、R 3 、R 4 Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Aryl of (a);
o1, p1, q1 and R1 are each R 1 、R 2 、R 3 、R 4 The number of (2); o1, p1, q1, r1 are integers from 0 to 4.
2. An organic light-emitting material according to claim 1, wherein: the organic luminescent material is a compound shown in formulas (III) and (IV):
wherein, in the formula (III), R a3 Or R b3 Each independently is hydrogen;
m3 and n3 represent the number of substituents; wherein m3 is an integer of 0-2, n3 is an integer of 0-4;
in the formula (IV), R a4 Or R b4 Each independently is hydrogen;
m4 and n4 represent the number of substituents; wherein m4 is an integer of 0-2, and n4 is an integer of 0-4;
said donor D 3 Or D 4 Each independently is one of the following structures:
wherein R is 1' 、R 2' 、R 3' 、R 4' Each independently is hydrogen or deuterium, C 1 -C 24 Alkyl of (C) 1 -C 24 Aryl of (a);
o2, p2, q2 and R2 are each R 1' 、R 2' 、R 3' 、R 4' The number of (2); o2, p2, q2, r2 are integers from 0 to 4.
3. An organic luminescent material containing a benzo [ c ] [1,2,5] thiadiazole derivative acceptor structural unit is characterized in that: the organic luminescent material is one of the following materials:
4. an organic luminescent material containing a benzo [ c ] [1,2,5] thiadiazole derivative acceptor structural unit is characterized in that: the organic luminescent material is:
5. use of the organic light emitting material containing benzo [ c ] [1,2,5] thiadiazole derivative acceptor structural unit according to any one of claims 1 to 4 in an organic electroluminescent device, wherein the organic light emitting material is used as a light emitting layer material.
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