CN109336784B - Soluble branch-substituted anthracene-based deep blue light material and preparation and application thereof - Google Patents
Soluble branch-substituted anthracene-based deep blue light material and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of blue light electroluminescent materials, and discloses a soluble branch-substituted anthracene-based deep blue light material, and preparation and application thereof. The structural formula of the anthracene-based deep blue light material is shown in formula I, and R is one of the electric absorption structural units. The invention also discloses a preparation method of the anthracene-based deep blue light material. The soluble branch-substituted anthracene-based deep blue light material has the characteristics of good solubility, thermal stability, film morphology stability, easiness in synthesis and purification and the like; and in the non-doped electroluminescent device, high luminous efficiency and low efficiency roll-off are shown, and the method has important application prospect.
Description
Technical Field
The invention belongs to the technical field of blue light electroluminescent materials, relates to an organic molecule blue light electroluminescent material, and particularly relates to a soluble branch substituted anthracene-based deep blue light material, and a preparation method and application thereof. The anthracene-based deep blue light material is applied to an electroluminescent device.
Background
Organic Light Emitting Diodes (OLEDs) are leading to the development of information display and illumination technologies due to their advantages of self-luminescence, flexibility, low power consumption, and the like. Compared with green light and red light materials, the blue light electroluminescent material with high efficiency and high stability is designed, and has important significance for OLED display, especially OLED illumination.
The blue light emitting material may be classified into a conventional blue light emitting material, a blue light emitting phosphor material, a TADF (thermally activated delayed fluorescence) type blue light emitting material, and a TTA (triplet-triplet annihilation) type blue light emitting material. However, the traditional blue light fluorescent material can only utilize singlet excitons, and the electroluminescent internal quantum efficiency is generally only 25%; for blue phosphorescent materials and TADF type blue materials, the electroluminescent internal quantum efficiency can reach 100%, but the longer triplet exciton lifetime and the high triplet energy level thereof are not favorable for obtaining highly stable and highly efficient OLED devices. In contrast, the TTA type blue fluorescent material, i.e. two triplet excitons, are recombined to form a singlet state, so the electroluminescent internal quantum efficiency can reach 62.5%, which is far more than 25% of that of the classical fluorescent material. At high current density, the increase of the density of the triplet excitons promotes the probability of mutual collision and recombination of the triplet excitons, and the roll-off of the device efficiency can be reduced. In addition, the triplet state energy level is lower, and a high-stability deep blue electroluminescent device is favorably obtained. Therefore, the design and synthesis of TTA type fluorescent materials have important theoretical and practical significance.
Although an electron anthracene unit can be conveniently used to construct a TTA type light emitting material. The existing TTA type luminescent material has relatively insufficient electron injection and transmission performance, or the solid state luminous efficiency, the blue light color purity, the solubility and the like are still to be improved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a soluble branch-substituted anthracene-based deep blue light material. The soluble branch-substituted anthracene-based deep blue light material disclosed by the invention takes a phenyl-bridged dianthracene group as a core, adopts a soluble branch-substituted aryl end group, and introduces an electron-withdrawing or electron-deficient end group, so that the problem that the existing anthracene-based blue light material is easy to quench luminescence in a solid state is solved, the electron injection and transmission are promoted, the blue light material is favorable for reducing the high current density and reducing the efficiency roll-off, the solubility of the luminescent material is improved, and the synthesis and purification are facilitated. Meanwhile, the anthracene-based blue light material has high luminous efficiency, good stability and film forming property.
The invention also aims to provide a preparation method of the soluble branch substituted anthracene-based deep blue light material.
The invention further aims to provide application of the soluble branch substituted anthracene-based deep blue light material. The anthracene-based deep blue light material is applied to electroluminescent devices, particularly non-doped devices. The anthracene-based deep blue light material can be used for a light-emitting layer of a light-emitting diode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a soluble branch-substituted anthracene-based deep blue light material has a structural formula of formula I:
r is one of the following electricity absorption structural units:
the soluble branch-substituted anthracene-based deep blue light material preferably has more than one of the following chemical structures:
the preparation method of the soluble branch-substituted anthracene-based deep blue light material comprises the following steps:
(1) preparation of 9- (4-bromophenyl) -10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracene: reacting 9-bromo-10- (3, 5-bis (4-tert-butylphenyl) phenyl) anthracene with 4-bromobenzeneboronic acid in an organic solvent under the action of a catalytic system, and performing subsequent treatment to obtain a bromo-containing anthryl compound;
(2) preparation of 2- (4- (10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan: reacting the bromine-containing anthracene-based compound in the step (1) with bis-pinacol borate in an organic solvent under the action of a catalytic system, and performing subsequent treatment to obtain a borate-containing anthracene-based compound;
(3) preparing a blue light material: reacting An anthracene-based compound containing borate with R-An-Br under the action of An organic solvent neutralization catalytic system to obtain the blue light material.
The structure of R-An-Br is as follows:
the reaction in the step (1) is a heating reflux reaction; the organic solvent is toluene and ethanol, the catalytic system comprises a catalyst and an alkaline solution, the catalyst is tetrakis (triphenylphosphine) palladium, and the alkaline solution is a potassium carbonate solution; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification;
in the step (1), the molar ratio of the 9-bromo-10- (3, 5-bis (4-tert-butylphenyl) phenyl) anthracene to the p-bromophenylboronic acid to the tetrakis (triphenylphosphine) palladium is 1: (1-1.2): (1% -1.2%).
In the step (2), the organic solvent is tetrahydrofuran, and the catalytic system comprises bis (triphenylphosphine) palladium dichloride and potassium acetate; the reaction is a heating reflux reaction; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification;
in the step (2), the molar ratio of the bromine-containing anthracene-based compound to the bis (pinacolato) borate to the bis (triphenylphosphine) palladium dichloride is 1: (1.2-1.5): (3% -5%).
The reaction in the step (3) is a heating reflux reaction; the organic solvent is toluene and ethanol, the catalytic system comprises a catalyst and an alkaline solution, the catalyst is tetrakis (triphenylphosphine) palladium, and the alkaline solution is a potassium carbonate solution; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification;
in the step (3), the mol ratio of the bromide to the p-bromophenylboronic acid to the tetrakis (triphenylphosphine) palladium is 1: (1-1.2): (1% -2%). The anthracene-based deep blue light material has good solubility in organic solvents, such as toluene and xylene (the solubility is more than 20mg/mL), and is easy to synthesize and purify.
The emission peaks of the anthracene-based deep blue light material film are 445nm, 440nm and 448nm respectively, and the anthracene-based deep blue light material film is used for emitting deep blue light.
The anthracene-based deep blue light material has good thermal stability and film morphology stability.
The anthracene-based deep blue light material is applied to preparing luminescent materials.
The anthracene-based deep blue light material is applied to electroluminescent devices, particularly non-doped devices.
The anthracene-based deep blue light molecular material has high luminous efficiency and low efficiency roll-off in a non-doped state.
An anthracene-based light-emitting material generally has Triplet-Triplet annihilation characteristics (TTA). However, since the light emission process involves a long-lived triplet excited state, a quenching phenomenon of light emission tends to occur in a solid state. The blue light molecular material of the invention introduces the aryl end group substituted by soluble tree branches to overcome the characteristic of easy quenching of luminescence of TTA type luminescent material in solid state, and improve the solubility of the luminescent material, thereby being beneficial to synthesis, purification and film formation; the introduction of electron-withdrawing or electron-deficient groups is beneficial to reducing the efficiency of roll-off at high current density and improving the luminous efficiency.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the anthracene-based deep blue light material prepared by the method is high in synthesis yield, simple in purification and capable of realizing large-scale preparation;
(2) the end group of the anthracene-based deep blue light material prepared by the invention is an aryl group substituted by soluble branches, and has better solubility. Due to the introduction of Dendron groups and the spatial configuration of the whole molecule, the material can be dissolved in various organic solvents such as toluene, chloroform, chlorobenzene and the like, and is beneficial to forming a uniform film through solution processing ways such as spin coating and the like;
(3) the anthracene-based deep blue light material prepared by the invention has good film forming property and film shape stability; the rigidity of the anthracene group and the benzene ring enables the material to have better thermal stability, and the aryl group substituted by the soluble branch has larger steric hindrance effect, so that the aggregation of the material is inhibited, and the performance and the service life of the device are promoted;
(4) the anthracene-based blue light materials CN-1, Py-2 and Q-3 prepared by the invention are primarily applied to non-doped devices to obtain deep blue light emitting devices with the light emitting efficiency of 1000 cd.m-2Previously, the External Quantum Efficiency (EQE) and Current Efficiency (CE) of the device increased with increasing brightness, with the maximumEQE 5.71%, 4.2%, 4.4%, color coordinates (0.15,0.08), (0.15,0.10), (0.15, 0.07); the device has lower efficiency roll-off at 3000 cd.m-2When the process is carried out, the EQE is still respectively as high as 5.57 percent, 3.5 percent and 4.4 percent; meanwhile, the current density and the brightness are in a nonlinear relation. Thus, the high-efficiency stable undoped device can be attributed to TTA effect of the anthracene-based blue light material.
Drawings
FIG. 1a is the nuclear magnetic resonance hydrogen spectrum of the anthracene-based blue light material CN-1 prepared in example 1; FIG. 1b is the NMR spectrum of the blue anthracene-based material Py-2 prepared in example 2; FIG. 1c is the NMR spectrum of the blue anthracene-based material Q-3 prepared in example 3;
FIG. 2 is a thermogravimetric curve of anthracene-based blue light materials CN-1, Py-2 and Q-3;
FIG. 3a is a differential scanning calorimetry curve of the anthracene-based blue light material CN-1 prepared in example 1; FIG. 3b is a differential scanning calorimetry curve of the anthracene-based blue light material Py-2 prepared in example 2; FIG. 3c is a differential scanning calorimetry curve of the anthracenyl blue light material Q-3 prepared in example 3;
FIG. 4a shows the anthracene-based blue light emitting material CN-1 prepared in example 1 in toluene (1.0 × 10)-5mol·L-1) And normalized absorption and photoluminescence spectra of thin films on silica glass FIG. 4b shows the anthracene-based blue light emitting material Py-2 prepared in example 2 in toluene (. about.1.0 1.0 × 10)-5mol L-1) And normalized absorption and photoluminescence spectra of thin films on silica glass FIG. 4c shows the anthracene-based blue-emitting material Q-3 prepared in example 3 in toluene (. about.1.0 1.0 × 10)-5mol L-1) And normalized absorption and photoluminescence spectra of thin films on quartz glass;
FIG. 5 is an oxidation curve of the anthracene-based blue light emitting materials CN-1, Py-2 and Q-3 prepared in the example;
FIG. 6a is a current density-voltage-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 of the anthracene-based deep blue light materials prepared in examples 1, 2 and 3; FIG. 6b is the current efficiency-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 in the anthracene-based deep blue light materials prepared in examples 1, 2 and 3; FIG. 6c is the power efficiency-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 in the anthracene-based deep blue light materials prepared in examples 1, 2 and 3; FIG. 6d is the external quantum efficiency-luminance curve of the blue light device without doping anthracene-based TTA deep blue light materials CN-1, Py-2 and Q-3 prepared in examples 1, 2 and 3;
FIG. 7a is a normalized electroluminescence intensity-wavelength curve of the anthracene-based deep blue light material CN-1 prepared in example 1 in an undoped device; FIG. 7b is a normalized electroluminescence intensity-wavelength curve of the anthracene-based deep blue light material Py-2 prepared in example 2 in an undoped device; FIG. 7c is a graph of normalized electroluminescence intensity versus wavelength for the anthracene-based deep blue light material Q-3 prepared in example 3 in an undoped device;
FIG. 8 is a current density-luminance curve of the blue non-doped blue light devices of the anthracene-based blue light materials CN-1, Py-2 and Q-3 prepared in examples 1, 2 and 3.
Detailed Description
The preparation of the anthracene-based blue light emitting material is further illustrated with reference to specific examples, but the scope of the invention is not limited to the examples.
Example 1 Anthracene-based blue light Material CN-1
An anthryl TTA blue light material CN-1[4- (10- (4,4 ' -bis-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthryl-9-yl) phenyl) anthryl-9-yl) benzonitrile ], which has the following structure:
the preparation method of the anthracene-based blue light material CN-1 comprises the following steps:
step one, preparation of 4- (anthracene-9-yl) benzonitrile:
4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzonitrile (10.7g,46.7mmol), 9-bromoanthracene (12.6g,49mmol) and an aqueous potassium carbonate solution (30mL,2M) were added to tetrahydrofuran (150mL) under a nitrogen atmosphere, and after stirring for 20min, tetrakis (triphenylphosphine) palladium (180mg,0.155mmol) was added, reacted overnight at 70 ℃, and the tetrahydrofuran was distilled off under reduced pressure, followed by extraction drying, and purification by silica gel column separation to give a golden yellow solid (eluent: PE/DCM) with a yield of about 86% (11.2 g).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3,ppm):8.54(s,1H),8.06(d,J＝8.5Hz,2H),7.90-7.86(m,2H),7.58-7.54(m,2H),7.53-7.45(m,4H),7.39-7.36(m,2H)。
step two, preparation of 4- (10-bromoanthracene-9-yl) benzonitrile:
dissolving 4- (anthracene-9-yl) benzonitrile (11g,39mmol) in dichloromethane (100mL), adding N-bromosuccinimide (7g,39mmol) in batches, heating and stirring at 50 ℃ in a dark place, tracking the reaction process by TLC until all raw materials are reacted, adding water to stop the reaction, extracting for multiple times by dichloromethane, drying an organic layer by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, separating and purifying by a silica gel column to remove color, and finally recrystallizing by ethanol to obtain a golden yellow flaky solid. Yield 90% (12.5 g).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3)8.63(d,J＝8.9Hz,1H),7.93-7.85(m,1H),7.62-7.59(m,1H),7.57-7.51(m,1H),7.49-7.47(m,1H),7.42–7.39(m,1H)。
step three, preparation of 9- (4-bromophenyl) -10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracene:
9-bromo-10- (3, 5-bis (4-tert-butylphenyl) phenyl) anthracene (5g,8.3mmol), 4-bromobenzeneboronic acid (2g,10mmol), a potassium carbonate solution (10mL,2M), and ethanol (10mL) were added to toluene (50mL) under a nitrogen atmosphere, after 20min, tetrakis (triphenylphosphine) palladium (120mg,0.10mmol) was added, the mixture was heated under reflux and stirred for 10h, the toluene was removed by distillation under reduced pressure, the mixture was extracted and dried, and the mixture was purified by silica gel column separation (PE/DCM), to obtain 2.5g (yield 44%) of a white solid.
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(400MHz,CDCl3)8.03(s,1H),7.90-7.80(m,2H),7.76(d,J＝8.2Hz,2H),7.75-7.50(m,8H),7.49(d,J＝8.3Hz,4H),7.46-7.28(m,6H),1.37(s,18H)。
step four, preparation of 2- (4- (10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan:
dissolving 9- (4-bromophenyl) -10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthracene (2g,3mmol), bis (pinacolato) borate (1.2g,4.5mmol) and potassium acetate (900mg,9mmol) in 60mL tetrahydrofuran under nitrogen atmosphere, exhausting for 20min, adding bis (triphenylphosphine) palladium dichloride (105mg,0.15mmol), and heating under reflux for 5 h; after the reaction was completed, tetrahydrofuran was distilled off under reduced pressure, extracted and dried, and then separated and purified by a silica gel column to obtain an eluent (PE/DCM) with a yield of about 93% (2 g).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(400MHz,CDCl3)8.14-7.96(m,3H),7.89-7.82(m,2H),7.77-7.61(m,8H),7.58-7.44(m,6H),7.40-7.27(m,4H),1.43(s,12H),1.37(s,18H)。
step five, preparation of 4- (10- (4- (10- (4,4 "-bis-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) anthracen-9-yl) benzonitrile:
under nitrogen atmosphere, 2- (4- (10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (1g,1.4mmol), 4- (10-bromoanthracen-9-yl) benzonitrile (500mg,1.4mmol), potassium carbonate solution (2mL,2M) and ethanol (2mL) were added to toluene (60mL), after 20min tetrakis (triphenylphosphine) palladium (32mg,0.028mmol) was added, and after extraction and drying, silica gel column separation and purification was carried out, and recrystallization from petroleum ether gave 1.1g of product in 91% yield.
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3)8.06(s,1H),8.04-7.85(m,8H),7.81-7.65(m,12H),7.62(d,J＝8.7Hz,2H),7.58-7.48(m,8H),7.48-7.37(m,4H),1.38(s,18H)。MS(APCI)m/z：[M+H+]calcd.for C67H53N，872.42；Found，872.9(100％)。Anal.calcd.For C67H53N:C 92.27,H 6.13,N 1.61。Found:C 92.24,H 6.37,N 1.55。
example 2 Anthracene-based blue light Material Py-2
An anthryl blue light material Py-2[3- (10- (4- (10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthracene-9-yl) phenyl) anthracene-9-yl) pyridine ], which has the following structure:
the preparation method of the anthracene-based blue light material Py-2 comprises the following steps:
step one, preparation of 3- (anthracene-9-yl) pyridine:
pyridine-3-boric acid (2.5g,20mmol), 9-bromoanthracene (8.5g,24mmol), a potassium carbonate solution (20mL,2M) and ethanol (10mL) are added into toluene (50mL) under a nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (160mg,0.14mmol) is added after 20min, heating reflux reaction is carried out for 12h, after the reaction is finished, the toluene is removed by reduced pressure distillation, extraction and drying are carried out, and silica gel column separation and purification (PE/DCM) are carried out. 2g of a white solid was obtained (yield 51%).
Step two, preparation of 3- (10-bromoanthracene-9-yl) pyridine:
dissolving 3- (anthracene-9-yl) pyridine (2g,7.8mmol) in dichloromethane solution, adding N-bromosuccinimide (1.4g,7.8mmol) in batches, heating and stirring at 50 ℃ in a dark place, reacting for about 2h, confirming the reaction degree by climbing a plate, adding water to stop the reaction, extracting with dichloromethane for multiple times, drying an organic layer with anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, separating and purifying a silica gel column to remove color, and finally recrystallizing with ethanol to obtain 2.4g of yellow solid (yield 95%).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(400MHz,CDCl3)8.84(s,1H),8.66(t,J＝10.2Hz,3H),7.81-7.75(m,1H),7.66-7.53(m,5H),7.46-7.38(m,2H)。
step three, preparation of 3- (10- (4- (10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) anthracen-9-yl) pyridine:
2- (4- (10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (1g,1.4mmol), 3- (10-bromoanthracen-9-yl) pyridine (470mg,1.4mmol), potassium carbonate solution (2mL,2M) and ethanol (2mL) were added to toluene (40mL) under nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (32mg,0.028mmol) was added after 20min, the mixture was refluxed for 10h, and after completion of the reaction, toluene was distilled off under reduced pressure and extracted and dried, and purified by silica gel column separation, and eluted with PE/DCM.
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(400MHz,CDCl3)8.90-8.81(m,2H),8.09-7.88(m,8H),7.86-7.58(m,13H),7.59-7.36(m,12H),1.50-1.26(s,18H)。MS(APCI)m/z：[M+H+]calcd.for C65H53N，848.41；Found，848.6(100％)。Anal.calcd.For C65H53N:C 92.05,H6.30,N 1.65。Found:C 91.72,H 6.33,N1.59。
example 3 Anthracene-based blue light Material Q-3
An anthracene-based blue light emitting material Q-3[2- (4- (10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -terphenyl ] -5' -yl) anthracene-9-yl) phenyl) quinoline ], which has the following structure:
the preparation method of the anthracene-based blue light material Q-3 comprises the following steps:
step one, preparation of 2- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) quinoline:
under nitrogen atmosphere, 2- (4-bromophenyl) quinoline (3.5g,12.3mmol), bis (pinacolato) borate (4.7g,18.5mmol) and potassium acetate (3.6g,36mmol) were dissolved in 50mL tetrahydrofuran, after 20min of air discharge, bis (triphenylphosphine) palladium dichloride (100mg,0.142mmol) was added, and after the reaction was completed, the mixture was subjected to reflux overnight reaction, multiple extractions, silica gel column separation and purification, and finally ethanol recrystallization to obtain 3g of the product (yield 73%).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3)8.26-8.15(m,4H),7.97(d,J＝8.2Hz,2H),7.91(d,J＝8.6Hz,1H),7.86-7.80(m,1H),7.73(ddd,J＝8.4,6.9,1.4Hz,1H),7.57-7.50(m,1H),1.38(s,12H)。
step two, preparation of 2- (4- (anthracen-9-yl) phenyl) quinoline:
2- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) quinoline (2.2g,6.6mmol), 9-bromoanthracene (2.5g,10mmol), a potassium carbonate solution (7mL,2M), and ethanol (7mL) were added to toluene (50mL) under a nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (161mg,0.14mmol) was added after 20min, the mixture was refluxed overnight, and after removal of toluene by distillation under reduced pressure, extraction and drying were performed, and isolation and purification by a silica gel column (PE/DCM) gave 2.3g of a white solid (yield 97%).
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3)8.52(s,1H),8.43-8.35(m,2H),8.33-8.20(m,2H),8.04(dd,J＝19.8,8.5Hz,3H),7.91-7.84(m,1H),7.81-7.72(m,3H),7.65-7.54(m,3H),7.52-7.43(m,2H),7.37(dd,J＝8.8,1.3Hz,2H)。
step three, preparation of 2- (4- (10- (4,4 "-di-tert-butyl- [1,1':3', 1" -terphenyl ] -5' -yl) anthracen-9-yl) phenyl) quinoline:
adding 2- (4- (10- (4,4 ' -di-tert-butyl- [1,1':3', 1' -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (1g,1.4mmol), 2- (4- (anthracen-9-yl) phenyl) quinoline (644mg,1.4mmol), potassium carbonate solution (2mL,2M) and ethanol (2mL) to toluene (50mL) under nitrogen atmosphere, adding tetrakis (triphenylphosphine) palladium (32mg,0.028mmol) after 20min, heating and refluxing for 10h, removing toluene by distillation under reduced pressure, extracting and drying, separating and purifying with silica gel column, eluting with PE/DCM, and then recrystallizing with petroleum ether to obtain 1g of product, the yield thereof was found to be 80%.
Hydrogen nuclear magnetic resonance spectroscopy analysis results:1H NMR(500MHz,CDCl3)8.45(d,J＝8.0Hz,2H),8.40-8.20(m,2H),8.97-8.11(m,6H),7.97-7.85(m,5H),7.85-7.63(m,13H),7.59(t,J＝7.5Hz,1H),7.56-7.32(m,12H),1.38(s,18H)。MS(APCI)m/z：[M+H+]calcd.for C75H59N，974.46；Found，974.9(100％)。Anal.calcd.For C75H59N:C 92.46,H 6.10,N 1.44。Found:C 92.37,H 6.08,N 1.40。
material and device performance tests were performed on the anthracene-based blue light materials CN-1, Py-2, Q-3 prepared in example 1, example 2 and example 3.
(1) Hydrogen spectrum of nuclear magnetic resonance
FIG. 1a is the nuclear magnetic resonance hydrogen spectrum of the anthracene-based blue light material CN-1 prepared in example 1;
FIG. 1b is the NMR spectrum of the blue anthracene-based material Py-2 prepared in example 2;
FIG. 1c shows the NMR spectrum of the blue-light anthracene-based material Q-3 prepared in example 3.
(2) Thermodynamic properties
FIG. 2 shows the thermogravimetric curves of the anthracene-based blue-light materials CN-1, Py-2 and Q-3 prepared in the examples.
FIG. 3a is a differential scanning calorimetry curve of the anthracene-based blue light material CN-1 prepared in example 1.
FIG. 3b is a differential scanning calorimetry curve of the anthracene-based blue light material Py-2 prepared in example 2;
FIG. 3c is a differential scanning calorimetry curve of the anthracenyl blue light material Q-3 prepared in example 3.
The thermal weight loss curve shows that the three blue light materials have better thermal stability and can be applied to thermal evaporation OLEDs (organic light emitting diodes) devicesd＞400℃)。
The results of DSC characterization show that all three blue-light materials have high glass transition temperature (T)g> 200 ℃); the blue light materials CN-1 and Py-2 show amorphous characteristics, and are favorable for forming good film shape stability.
(3) Physical Properties of light
FIG. 4a shows the anthracene-based blue light emitting material CN-1 prepared in example 1 in toluene (1.0 × 10)-5mol L-1) And normalized absorption and photoluminescence spectra of thin films on quartz glass;
FIG. 4b shows the anthracene-based blue light emitting material Py-2 prepared in example 2 in toluene (. about.1.0 1.0 × 10)-5mol L-1) And normalized absorption and photoluminescence spectra of thin films on quartz glass;
FIG. 4c shows the preparation of the blue-emitting anthracene-based phosphor Q-3 of example 3 in toluene (. about.1.0 1.0 × 10)-5mol L-1) And normalized absorption and photoluminescence spectra of thin films on quartz glass.
The thin film emission peaks of the compounds CN-1, Py-2 and Q-3 are 445nm, 440nm and 448nm respectively, and the emission peaks are deep blue light emission; the half-peak width is narrow, which is beneficial to obtaining a deep blue light device; the optical band gaps are respectively 2.91eV, 2.91eV and 2.85eV according to the absorption edge of the film.
(4) Electrochemical performance
FIG. 5 shows the oxidation curves of the anthracene-based blue light emitting materials CN-1, Py-2 and Q-3 prepared in the examples. The HOMO levels of the compounds CN-1, Py-2 and Q-3 were found to be-5.53 eV, -5.54eV and-5.56 eV, respectively, and the LUMO levels of the compounds CN-1, Py-2 and Q-3 were found to be-5.53 eV, -5.54eV and-5.56 eV, respectively, from the band gaps thereof.
(5) Performance of organic electroluminescent device
Device performance tests were performed on the anthracene-based deep blue light materials CN-1, Py-2, Q-3 prepared in examples 1, 2 and 3. The non-doped organic electroluminescent device is used as a luminescent material, and is prepared by a vacuum evaporation method, and the specific device structure is as follows: ITO/HATCN (15nm)/TAPC (60nm)/TCTA (10nm)/CN-1, Py-2or Q-3(20nm)/TPBi (40nmor 45nm)/LiF (1 nm)/Al.
The specific molecular structure of each material is as follows:
FIG. 6a is a current density-voltage-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 of the anthracene-based deep blue light materials prepared in examples 1, 2 and 3;
FIG. 6b is the current efficiency-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 in the anthracene-based deep blue light materials prepared in examples 1, 2 and 3;
FIG. 6c is the power efficiency-luminance curve of the un-doped devices CN-1, Py-2 and Q-3 in the anthracene-based deep blue light materials prepared in examples 1, 2 and 3;
FIG. 6d is the external quantum efficiency-luminance curve of the blue light device without doping anthracene-based TTA deep blue light materials CN-1, Py-2 and Q-3 prepared in examples 1, 2 and 3;
FIG. 7a is a normalized electroluminescence intensity-wavelength curve of the anthracene-based deep blue light material CN-1 prepared in example 1 in an undoped device; the EL spectrum remained unchanged with increasing voltage, indicating that the device exciton recombination zone is substantially in the emissive layer.
FIG. 7b is a normalized electroluminescence intensity-wavelength curve of the anthracene-based deep blue light material Py-2 prepared in example 2 in an undoped device; the EL spectrum remained unchanged with increasing voltage, indicating that the device exciton recombination zone is substantially in the emissive layer.
FIG. 7c is a graph of normalized electroluminescence intensity versus wavelength for the anthracene-based deep blue light material Q-3 prepared in example 3 in an undoped device; the EL spectrum remained unchanged with increasing voltage, indicating that the device exciton recombination zone is substantially in the emissive layer.
FIG. 8 is a current density-luminance curve of the blue light device without doping anthracene-based blue light materials CN-1, Py-2 and Q-3 prepared in example 1, example 2 and example 3; the current density and the brightness are in a nonlinear relation according to the graph; and in 1000cd m-2Previously, both External Quantum Efficiency (EQE) and Current Efficiency (CE) increased with increasing brightness; in the undoped blue light device, the maximum external quantum efficiency is 5.71%, 4.2% and 4.4%, respectively. In conclusion, the synthesized anthracene-based blue light materials CN-1, Py-2 and Q-3 prepared by the invention have TTA effect.
The performance test data for a specific device is shown in table 1.
Table 1 specific device performance test data
a)1～4cd m-2；b)TPBi＝40nm；c)TPBi＝45nm
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 (8)
1. A soluble branch substituted anthracene-based deep blue light material is characterized in that: is one or more of the following chemical structures:
2. a method of preparing a soluble dendron substituted anthracenyl deep blue light emitting material as claimed in claim 1, wherein: the method comprises the following steps:
(1) preparation of 9- (4-bromophenyl) -10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracene: reacting 9-bromo-10- (3, 5-bis (4-tert-butylphenyl) phenyl) anthracene with 4-bromobenzeneboronic acid in an organic solvent under the action of a catalytic system, and performing subsequent treatment to obtain a bromo-containing anthryl compound;
(2) preparation of 2- (4- (10- (4,4 "-di-tert-butyl- [1,1':3', 1" -triphenyl ] -5' -yl) anthracen-9-yl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan: reacting the bromine-containing anthracene-based compound in the step (1) with bis-pinacol borate in an organic solvent under the action of a catalytic system, and performing subsequent treatment to obtain a borate-containing anthracene-based compound;
(3) preparing a blue light material: reacting An anthracene-based compound containing boric acid ester with R-An-Br under the action of An organic solvent neutralization catalytic system to obtain a blue light material, namely a soluble branch-substituted anthracene-based deep blue light material;
the structure of R-An-Br is as follows:
3. The method for preparing the soluble dendron substituted anthracene-based deep blue light emitting material as claimed in claim 2, wherein the soluble dendron substituted anthracene-based deep blue light emitting material comprises: the reaction in the step (1) is a heating reflux reaction; the organic solvent is toluene and ethanol, the catalytic system comprises a catalyst and an alkaline solution, the catalyst is tetrakis (triphenylphosphine) palladium, and the alkaline solution is a potassium carbonate solution; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification;
in the step (1), the molar ratio of the 9-bromo-10- (3, 5-bis (4-tert-butylphenyl) phenyl) anthracene to the p-bromophenylboronic acid to the tetrakis (triphenylphosphine) palladium is 1: (1-1.2): (1% -1.2%).
4. The method for preparing the soluble dendron substituted anthracene-based deep blue light emitting material as claimed in claim 2, wherein the soluble dendron substituted anthracene-based deep blue light emitting material comprises: in the step (2), the organic solvent is tetrahydrofuran, and the catalytic system comprises bis (triphenylphosphine) palladium dichloride and potassium acetate; the reaction is a heating reflux reaction; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification;
in the step (2), the molar ratio of the bromine-containing anthracene-based compound to the bis (pinacolato) borate to the bis (triphenylphosphine) palladium dichloride is 1: (1.2-1.5): (3% -5%).
5. The method for preparing the soluble dendron substituted anthracene-based deep blue light emitting material as claimed in claim 2, wherein the soluble dendron substituted anthracene-based deep blue light emitting material comprises: the reaction in the step (3) is a heating reflux reaction; the organic solvent is toluene and ethanol, the catalytic system comprises a catalyst and an alkaline solution, the catalyst is tetrakis (triphenylphosphine) palladium, and the alkaline solution is a potassium carbonate solution; the subsequent treatment refers to that reactants are subjected to reduced pressure concentration, extraction, drying, separation and purification.
6. Use of the soluble dendron substituted anthracene-based deep blue light material of claim 1 in the preparation of a light emitting material.
7. Use of the soluble dendron substituted anthracene based deep blue light emitting material of claim 1 in an electroluminescent device.
8. Use according to claim 7, characterized in that: the electroluminescent device is a non-doped device.
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