CN112442053B - Blue fluorescent doping material with good thermal stability and high efficiency and organic electroluminescent device - Google Patents

Blue fluorescent doping material with good thermal stability and high efficiency and organic electroluminescent device Download PDF

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CN112442053B
CN112442053B CN201910820663.0A CN201910820663A CN112442053B CN 112442053 B CN112442053 B CN 112442053B CN 201910820663 A CN201910820663 A CN 201910820663A CN 112442053 B CN112442053 B CN 112442053B
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钱超
许军
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Nanjing Topto Materials Co Ltd
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Abstract

The invention discloses a blue fluorescent doping material with good thermal stability and high efficiency and an organic electroluminescent device, and the structural formula is as follows:
Figure DDA0002184750370000011
the blue light doped material is applied to the organic electroluminescent device, the luminous efficiency is improved to a certain extent under the same current density, the starting voltage of the device is reduced, the power consumption of the device is relatively reduced, and the service life of the device is correspondingly prolonged.

Description

Blue fluorescent doping material with good thermal stability and high efficiency and organic electroluminescent device
Technical Field
The invention belongs to the technical field of organic electroluminescence, and particularly relates to a blue fluorescent doped material with good thermal stability and high efficiency and an organic electroluminescent device.
Background
As a next-generation flat panel display technology, Organic light-emitting diodes (OLEDs) have advantages of active light emission, low driving voltage, fast response speed, wide viewing angle, thin and light device, and flexible display, and have recently received wide attention from the academic and industrial fields. For realizing full-color display of OLEDs, red, green, and blue light-emitting materials are indispensable. Among them, a blue light material is particularly important, which can provide not only necessary blue emission light but also green and red light by energy transfer. Moreover, the blue light material is also the key to effectively reduce the energy consumption of full-color OLEDs. However, since the energy gap of the blue light material is wide, the energy level matching between the electron orbital level and the carrier injection/transmission material is poor, and the working stability of the material is reduced by the high excited state energy level, so that the development of a high-performance blue light material luminescent device is very difficult. At present, the research on red light and green light materials is relatively mature, the performance of devices of the red light and green light materials reaches the level of practical application, the performance of blue light OLEDs needs to be further improved, and factors which greatly affect the performance of the blue light OLEDs are more, wherein the doped materials are hot spots of the current research.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a blue fluorescent doping material with good thermal stability and high efficiency and an organic electroluminescent device.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a blue fluorescent doping material with good thermal stability and high efficiency has the following structural formula:
Figure BDA0002184750350000011
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted silane group or silicon derivative group, substituted or unsubstituted C1-C10 linear or branched alkyl group, substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C1-C10 heteroalkyl group, substituted or unsubstituted C2-C10 alkenyl group, substituted or unsubstituted C2-C10 alkynyl group, substituted or unsubstituted C6-C60 aromatic hydrocarbon group, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon group.
Further, each of the R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 is independently hydrogen, deuterium, a fluorine atom, a cyano group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted neopentyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted methylphenyl group, a substituted or unsubstituted ethylphenyl group, a substituted or unsubstituted isopropylphenyl group, a substituted or unsubstituted isobutylphenyl group, a substituted or unsubstituted tert-butylphenyl group, a substituted or unsubstituted neopentylphenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted isopropylphenyl group, a substituted or unsubstituted isobutylphenyl group, a substituted or unsubstituted tert-butylphenyl group, a substituted or unsubstituted neopentylphenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, Substituted or unsubstituted azaanthracenyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted dimethylamino, substituted or unsubstituted diphenylamino, substituted or unsubstituted fluorenyl, substituted or unsubstituted oxyfluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl, and substituted or unsubstituted 9, 9-spirobifluorenyl.
Further, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 is independently hydrogen, deuterium, a fluorine atom, a cyano group, a trimethylsilyl group, a triphenylsilyl group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a methoxy group, a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, an isobutylphenyl group, a tert-butylphenyl group, a neopentylphenyl group, an anthracenyl group, a naphthyl group, a phenanthryl group, an azaanthracenyl group, a naphthyridinyl group, a pyridyl group, a pyrimidinyl group, a dimethylamino group, a dianilinyl group, a fluorenyl group, an oxyfluorenyl group, a dibenzothienyl group, a carbazolyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, and 9, 9-spirobifluorenyl group;
wherein the trimethylsilyl group, the triphenylsilyl group, the methyl group, the ethyl group, the isopropyl group, the isobutyl group, the tert-butyl group, the neopentyl group, the methoxy group, the phenyl group, the methylphenyl group, the ethylphenyl group, the isopropylphenyl group, the isobutylphenyl group, the tert-butylphenyl group, the neopentylphenyl group, the anthracenyl group, the naphthyl group, the phenanthryl group, the azaanthracenyl group, the naphthyridinyl group, the pyridyl group, the pyrimidinyl group, the dimethylamino group, the diphenylamine group, the fluorenyl group, the oxyfluorenyl group, the dibenzothienyl group, the carbazolyl group, the 9, 9-dimethylfluorenyl group, the 9, 9-diphenylfluorenyl group, the 9, 9-spirobifluorenyl group are unsubstituted or are obtained by substituting at least one hydrogen by at least one of deuterium, a fluorine atom, a cyano group, a linear or branched alkyl group of C1-C4, and a phenyl group.
Further, the blue fluorescent doped material is any one of the following compounds of structural formula:
Figure BDA0002184750350000021
Figure BDA0002184750350000031
Figure BDA0002184750350000041
Figure BDA0002184750350000051
Figure BDA0002184750350000061
Figure BDA0002184750350000071
further, the preparation method of the blue fluorescent doping material comprises the following steps:
Figure BDA0002184750350000072
adding the compound A into tert-butyl benzene under the protection of inert gas, stirring and cooling to-78-40 ℃, slowly dropping N-pentane solution of tert-butyl lithium, recovering the room temperature after dropping, stirring for 30-50 min, then cooling to-78-40 ℃, slowly adding boron tribromide, stirring for 30-50 min, slowly adding N, N-diisopropylamine, heating to 155-165 ℃, reacting for 12-15 h, cooling to room temperature, slowly pouring the reaction liquid into an ice water mixture, quenching, separating an organic phase, drying, and purifying to obtain the blue fluorescent doped material.
Furthermore, the blue fluorescent doping material is applied to the preparation of organic electroluminescent devices.
An organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked, wherein the luminescent layer contains a host material and a doping material, and the doping material is at least one of the blue fluorescent doping materials.
Further, the doping amount of the blue fluorescent doping material is 1-7% of the mass of the main body material.
Further, the doping amount of the blue fluorescent doping material is 5% of the mass of the host material.
An electronic display device comprising the above organic electroluminescent device.
The room temperature of the invention is 25 +/-5 ℃.
The invention has the beneficial effects that:
the blue fluorescent doped material designed by the invention has a large conjugated system, so that the rigidity and the electron cloud density of material molecules are greatly improved, and the thermal stability and the luminous efficiency of the material are further remarkably improved. Meanwhile, the boron atom (B) and the nitrogen atom (N) jointly form a seven-membered ring and a six-membered ring, so that a spatial electron supply system is formed between the boron atom and the nitrogen atom, and the electron supply system greatly improves the luminous efficiency of material molecules. Thereby remarkably improving the luminous efficiency of the organic electroluminescent device. The material has good conjugation effect, rigidity and stability, so that the service life of the organic electroluminescent device is ensured.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device provided by the present invention;
the reference numbers in the figures represent respectively: 1-cathode, 2-electron injection layer, 3-electron transport layer, 4-luminescent layer, 5-hole transport layer, 6-hole injection layer, 7-anode.
FIG. 2 is a data plot of a TGA test of control example 1 (BD-1);
FIG. 3 is a data plot of a TGA test of control example 2 (BD-2);
FIG. 4 is a data plot of TGA testing of a blue fluorescent doped material (1) in the present invention;
as can be seen from the TGA spectrum, the thermal stability of the blue fluorescent dopant material (1) of the present invention is far superior to that of comparative example 1(BD-1) and comparative example 2 (BD-2).
Detailed Description
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
Figure BDA0002184750350000081
the synthesis method of the blue fluorescent doping material (1) comprises the following steps:
(1)
Figure BDA0002184750350000091
under the protection of nitrogen, adding compound 1-a (5.0g, 438.95g/mol, 11.39mmol), compound 1-b (1eq, 2.32g, 203.94g/mol, 11.39mmol), sodium tert-butoxide (1.1eq, 1.2g, 96.1g/mol, 12.53mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.52g, 915g/mol, 0.57mmol), tri-tert-butylphosphine (0.05eq, 0.12g, 202.32g/mol, 0.57mol), toluene (50ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 50ml of water, stirring for 15min, filtering to obtain a filtrate, separating the filtrate through diatomite to obtain an organic phase, drying by anhydrous magnesium sulfate, purifying by dry column chromatography to obtain compound 1-c (4.72g, 80.6%) EI yield: 514 (M)+)。
(2)
Figure BDA0002184750350000092
Under the protection of nitrogen, compound 1-c (4.5g, 514.98g/mol, 8.74mmol), compound 1-d (1eq, 1.48g, 169.09g/mol, 8.74mmol), sodium tert-butoxide (1.1eq, 0.92g, 96.1g/mol, 9.61mmol), tris (N-tert-butyl ether)(dibenzylideneacetone) dipalladium (0.05eq, 0.4g, 915g/mol, 0.44mmol), tri-tert-butylphosphine (0.05eq, 0.088g, 202.32g/mol, 0.44mol) and toluene (45ml) were added to a reaction flask, after the addition was completed, the temperature was raised to reflux reaction for 5 hours, after the reaction was completed, the temperature was lowered to room temperature, 50ml of water was added, stirring was carried out for 15 minutes, filtration was carried out to obtain a filtrate, the filtrate was filtered through celite, liquid separation was carried out to obtain an organic phase, the organic phase was dried with anhydrous magnesium sulfate and then spin-dried, and column chromatography purification was carried out to obtain compound 1-e (4.08g, yield 77.2%), ms (ei): 604 (M)+)。
(3)
Figure BDA0002184750350000093
Compound 1-e (3.8g, 604.15g/mol, 6.29mmol) was added to tert-butylbenzene (38ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 10.16ml, 13.21mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 6.3g, 250.52g/mol, 25.16mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 2.55g, 101.2g/mol, 25.16mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain a blue fluorescence-doped material (1) (1.25g, yield 36.1%), MS (EI): 552 (M)+)。
Example 2:
Figure BDA0002184750350000101
the synthesis method of the blue fluorescent doping material (6) comprises the following steps:
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000102
Under the protection of nitrogen, adding compound 2-a (2g, 514.98g/mol, 3.88mmol), compound 2-b (1eq, 0.87g, 225.15g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain filtrate, separating by diatomite filtration to obtain an organic phase, drying by anhydrous drying, and purifying by column chromatography to obtain compound 2-c (1.94g, 75.8 MS): 660 (M)+)。
Figure BDA0002184750350000111
Under the protection of nitrogen, compound 2-c (1.8g, 660.21g/mol, 2.73mmol) was added to tert-butylbenzene (18ml), stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 4.41ml, 5.73mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.73g, 250.52g/mol, 10.91mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.1g, 101.2g/mol, 10.91mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain a blue fluorescent doped material (6) (0.59g, yield 35.5%), ms (ei): 608 (M)+)。
Example 3:
Figure BDA0002184750350000112
the synthesis method of the blue fluorescent doping material (11) comprises the following steps:
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000113
Under the protection of nitrogen, adding compound 3-a (2g, 514.98g/mol, 3.88mmol), compound 3-b (1eq, 1.54g, 397.18g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying to obtain compound 3-c (2.3g, 71.2%) after column chromatography purification: 832 (M)+)。
(3)
Figure BDA0002184750350000121
Compound 3-c (2g, 832.24g/mol, 2.4mmol) was added to tert-butylbenzene (20ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 3.88ml, 5.05mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.41g, 250.52g/mol, 9.61mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 0.97g, 101.2g/mol, 9.61mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into ice water mixture for quenching, separating organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain blue fluorescent doped material (11) (0.6g, yield 32.3%), ms (ei): 780 (M)+)。
Example 4:
Figure BDA0002184750350000122
the synthesis method of the blue fluorescent doping material (14) comprises the following steps:
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000123
Under the protection of nitrogen, adding compound 4-a (2g, 514.98g/mol, 3.88mmol), compound 4-b (1eq, 0.72g, 186.12g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain filtrate, separating by diatomite filtration to obtain an organic phase, drying by anhydrous drying, and purifying by column chromatography to obtain compound 4-c (1.77g, 73.6 ms): 621 (M)+)。
(3)
Figure BDA0002184750350000131
Compound 4-c (1.6g, 621.18g/mol, 2.58mmol) was added to tert-butylbenzene (16ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 4.16ml, 5.41mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.58g, 250.52g/mol, 10.3mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.04g, 101.2g/mol, 10.3mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into ice water mixture for quenching, separating organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain blue fluorescent doped material (14) (0.47g, yield 32.3%), ms (ei): 569 (M)+)。
Example 5:
Figure BDA0002184750350000132
the synthesis method of the blue fluorescent doping material (28) is as follows:
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000141
Under the protection of nitrogen, adding compound 5-a (2g, 514.98g/mol, 3.88mmol), compound 5-b (1eq, 1.05g, 270.12g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying to obtain compound 5-c (1.99g, 72% by column chromatography) yield (EI): 705 (M)+)。
(3)
Figure BDA0002184750350000142
Adding a compound 5-c (1.8g, 705.17g/mol and 2.55mmol) into tert-butyl benzene (18ml) under the protection of nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution (2.1eq, 1.3M, 4.12ml and 5.36mmol) of tert-butyl lithium, recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.56g, 250.52g/mol and 10.2mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.03g, 101.2g/mol and 10.2mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring a reaction solution into an ice water mixture, and quenchingAfter the organic phase was separated, dried over anhydrous magnesium sulfate, and then spin-dried, and purified by column chromatography to obtain a blue fluorescent doped material (28) (0.55g, yield 32.8%), ms (ei): 653 (M)+)。
Example 6:
Figure BDA0002184750350000151
the synthesis method of the blue fluorescent doping material (40) comprises the following steps:
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000152
Under the protection of nitrogen, adding compound 6-a (2g, 514.98g/mol, 3.88mmol), compound 6-b (1eq, 0.86g, 220.19g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying to obtain compound 6-c (1.8g, 70.7%) after column chromatography (EI): 655 (M)+)。
(3)
Figure BDA0002184750350000153
Adding a compound 6-c (1.7g, 655.25g/mol, 2.59mmol) into tert-butyl benzene (17ml) under the protection of nitrogen, stirring and cooling to-78 ℃, slowly dropping n-pentane solution (2.1eq, 1.3M, 4.19ml, 5.45mmol) of tert-butyl lithium, recovering the room temperature after dropping, stirring for 50min, cooling to-78 ℃, and cooling boron tribromide (4eq, 2.6g, 250.52 g/mol)10.38mmol) was slowly added thereto, stirred for 30min, N-diisopropylamine (4eq, 1.05g, 101.2g/mol, 10.38mmol) was slowly added thereto, heated to 165 ℃ to react for 14h, cooled to room temperature, the reaction solution was slowly poured into an ice-water mixture to quench, the organic phase was separated, dried over anhydrous magnesium sulfate and spin-dried, and column chromatography purification was carried out to obtain a blue fluorescent doped material (40) (0.51g, yield 32.4%), ms (ei): 603 (M)+)。
Example 7:
Figure BDA0002184750350000161
the synthesis method of the blue fluorescent doping material (43) is as follows:
(1)
Figure BDA0002184750350000162
under the protection of nitrogen, adding compound 7-a (4g, 438.95g/mol, 9.11mmol), compound 7-b (1eq, 2.99g, 328.06g/mol, 9.11mmol), sodium tert-butoxide (1.1eq, 0.96g, 96.1g/mol, 10.02mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.42g, 915g/mol, 0.46mmol), tri-tert-butylphosphine (0.05eq, 0.092g, 202.32g/mol, 0.46mol), and toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is completed, cooling to room temperature after the reaction is completed, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying by column chromatography to obtain compound 7-c (3.74g, 8964.64%) EI: 639 (M)+)。
(2)
Figure BDA0002184750350000171
Under the protection of nitrogen, compound 7-c (3.5g, 639.1g/mol, 5.48mmol), compound 7-d (1eq, 0.86g, 217.17g/mol, 5.48mmol), sodium tert-butoxide (1.1eq, 0.58g, 96.1 mmol)g/mol, 6.02mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.25g, 915g/mol, 0.27mmol), tri-tert-butylphosphine (0.05eq, 0.055g, 202.32g/mol, 0.27mol), toluene (35ml) were added to a reaction flask, after the addition, the temperature was raised to reflux reaction for 5h, after the reaction was completed, the temperature was lowered to room temperature, 35ml of water was added, stirring was carried out for 15min, then filtrate was obtained, filtrate was filtered through celite, liquid separation was carried out to obtain an organic phase, the organic phase was dried with anhydrous magnesium sulfate and then spin-dried, and after column chromatography purification, compound 7-e (2.68g, yield 63.1%), ms (ei): 776 (M)+)。
(3)
Figure BDA0002184750350000172
Under the protection of nitrogen, compound 7-e (2.5g, 776.35g/mol, 3.22mmol) was added to tert-butylbenzene (25ml), stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 5.2ml, 6.76mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 3.23g, 250.52g/mol, 12.88mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.3g, 101.2g/mol, 12.88mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain a blue fluorescence doping material (43) (0.79g, yield 33.8%), MS (EI): 724 (M)+)。
Example 8:
Figure BDA0002184750350000181
the synthesis method of the blue fluorescent doping material (54) is as follows:
(1)
Figure BDA0002184750350000182
nitrogen gasUnder protection, compound 8-a (4g, 514.98g/mol, 7.77mmol), compound 8-b (1eq, 3.08g, 396.04g/mol, 7.77mmol), sodium tert-butoxide (1.1eq, 0.82g, 96.1g/mol, 8.55mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.36g, 915g/mol, 0.39mmol), tri-tert-butylphosphine (0.05eq, 0.079g, 202.32g/mol, 0.39mol), toluene (40ml) were added to a reaction flask, after the addition, the mixture was heated to reflux reaction for 5h, after the reaction was completed, 40ml of water was added to room temperature, the mixture was stirred for 15min, the filtrate was filtered through celite, the filtrate was separated to obtain an organic phase, the organic phase was dried over anhydrous magnesium sulfate, and after column chromatography purification, compound 8-c (4g, ms, 65.6%) was obtained: 783 (M)+)。
(2)
Figure BDA0002184750350000183
Under the protection of nitrogen, adding 8-c (4g, 783.11g/mol, 5.11mmol), 8-d (1eq, 0.86g, 169.09g/mol, 5.11mmol), sodium tert-butoxide (1.1eq, 0.54g, 96.1g/mol, 5.62mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.23g, 915g/mol, 0.26mmol), tri-tert-butylphosphine (0.05eq, 0.052g, 202.32g/mol, 0.26mol), and toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is completed, cooling to room temperature after the reaction is completed, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying to obtain a compound 8-e (3.2g, 8978.9%) after column chromatography, and obtaining a yield (EI): 872 (M)+)。
(3)
Figure BDA0002184750350000191
Under the protection of nitrogen, compound 8-e (3g, 872.27g/mol, 3.44mmol) is added into tert-butyl benzene (30ml), the temperature is reduced to-78 ℃ under stirring, a n-pentane solution of tert-butyl lithium (2.1eq, 1.3M, 5.55ml, 7.22mmol) is slowly dropped, and the room temperature is recovered after droppingStirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 3.45g, 250.52g/mol, 13.76mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.39g, 101.2g/mol, 13.76mmol), heating to 165 ℃ for reaction for 14h, cooling to room temperature, slowly pouring the reaction liquid into an ice water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, and purifying by column chromatography to obtain a blue fluorescence-doped material (54) (0.91g, yield 32.4%), MS (EI): 820 (M)+)。
Example 9:
Figure BDA0002184750350000192
the synthesis method of the blue fluorescent doping material (65) is as follows:
(1)
Figure BDA0002184750350000201
under the protection of nitrogen, adding compound 9-a (4g, 615.02g/mol, 6.5mmol), compound 9-b (1eq, 1.33g, 203.94g/mol, 6.5mmol), sodium tert-butoxide (1.1eq, 0.69g, 96.1g/mol, 7.15mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.3g, 915g/mol, 0.33mmol), tri-tert-butylphosphine (0.05eq, 0.066g, 202.32g/mol, 0.33mol), toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying by column chromatography to obtain compound 9-c (3.31g, 898.8%) EI: 691 (M)+)。
(2)
Figure BDA0002184750350000202
Under the protection of nitrogen, compound 9-c (3.2g, 691.05g/mol, 4.63mmol), compound 9-d (1eq, 0.78g, 169.09g/mol, 4.63mmol), sodium tert-butoxide (1.1eq, 0.49g, 96.1g/mol, 5.09mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.21g, 915g/mol, 0.23mmol), tri-tert-butylphosphine (0.05eq, 0.047g, 202.32g/mol, 0.23mol), toluene (32ml) were added to a reaction flask, after the addition, the temperature was raised to reflux reaction for 5 hours, after the reaction was completed, 32ml of water was added to the reaction flask, after the reaction was completed, the reaction solution was stirred for 15min, and then filtered to obtain a filtrate, after filtration of the filtrate, the organic phase was dried over anhydrous magnesium sulfate, and then subjected to column chromatography purification to obtain compound 9-e (2.54g, yield 70.3%), EI: 780 (M)+)。
(3)
Figure BDA0002184750350000203
Compound 9-e (2.4g, 780.21g/mol, 3.08mmol) was added to tert-butylbenzene (24ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 4.98ml, 6.47mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 3.09g, 250.52g/mol, 12.32mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.25g, 101.2g/mol, 12.32mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain a blue fluorescence doped material (65) (0.78g, yield 34.7%), MS (EI): 728 (M)+)。
Example 10:
Figure BDA0002184750350000211
the synthesis method of the blue fluorescent doping material (86) is as follows:
(1)
Figure BDA0002184750350000212
under the protection of nitrogen, adding compound 10-a (4g, 455.99g/mol, 8.77mmol), compound 10-b (1eq, 1.33g, 203.94g/mol, 8.77mmol), sodium tert-butoxide (1.1eq, 0.93g, 96.1g/mol, 9.65mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.4g, 915g/mol, 0.44mmol), tri-tert-butylphosphine (0.05eq, 0.089g, 202.32g/mol, 0.44mol), and toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is completed, cooling to room temperature after the reaction is completed, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying by column chromatography to obtain compound 10-c (3.41g, 890.73%) EI: 532 (M)+)。
(2)
Figure BDA0002184750350000221
Under the protection of nitrogen, adding compound 10-c (3.2g, 532.02g/mol, 6.01mmol), compound 10-d (1eq, 1.12g, 186.12g/mol, 6.01mmol), sodium tert-butoxide (1.1eq, 0.64g, 96.1g/mol, 6.62mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.28g, 915g/mol, 0.3mmol), tri-tert-butylphosphine (0.05eq, 0.061g, 202.32g/mol, 0.3mol), toluene (32ml) into a reaction bottle, heating to reflux reaction for 5h after the completion of the reaction, cooling to room temperature after the completion of the reaction, adding 32ml of water, stirring for 15min, filtering to obtain a filtrate, separating the filtrate through diatomite to obtain an organic phase, drying the organic phase by anhydrous magnesium sulfate, purifying by column chromatography to obtain compound 10-e (2.73g, MS 71.2%) yield: 638 (M)+)。
(3)
Figure BDA0002184750350000222
Under the protection of nitrogen, compound 10-e (2.6g, 638.22g/mol, 4.07mmol) is added into tert-butyl benzene (26ml), the temperature is reduced to-78 ℃ under stirring, and tert-butyl lithium is addedSlowly dropping N-pentane solution (2.1eq, 1.3M, 6.58ml, 8.56mmol), recovering room temperature after dropping, stirring for 50min, then cooling to-78 ℃, slowly adding boron tribromide (4eq, 4.08g, 250.52g/mol, 16.29mmol), stirring for 30min, then slowly adding N, N-diisopropylamine (4eq, 1.65g, 101.2g/mol, 16.29mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring the reaction liquid into an ice-water mixture, quenching, separating an organic phase, drying by anhydrous magnesium sulfate, performing rotary drying, and purifying by column chromatography to obtain a blue fluorescent doped material (86) (0.79g, yield 33.3%), and MS (EI): 586 (M)+)。
Example 11:
Figure BDA0002184750350000231
the synthesis method of the blue fluorescent doping material (104) comprises the following steps:
(1)
Figure BDA0002184750350000232
under the protection of nitrogen, adding compound 11-a (4g, 591.02g/mol, 6.77mmol), compound 11-b (1eq, 1.89g, 279.97g/mol, 6.77mmol), sodium tert-butoxide (1.1eq, 0.72g, 96.1g/mol, 7.44mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.31g, 915g/mol, 0.34mmol), tri-tert-butylphosphine (0.05eq, 0.068g, 202.32g/mol, 0.34mol), toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying by column chromatography to obtain compound 11-c (3.54g, 70.3%) EI: 743 (M)+)。
(2)
Figure BDA0002184750350000233
Under the protection of nitrogen, adding compound 11-c (3.4g, 743.08g/mol, 4.58mmol), compound 11-d (1eq, 1.47g, 321.15g/mol, 4.58mmol), sodium tert-butoxide (1.1eq, 0.48g, 96.1g/mol, 5.03mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.21g, 915g/mol, 0.23mmol), tri-tert-butylphosphine (0.05eq, 0.046g, 202.32g/mol, 0.23mol), toluene (34ml) into a reaction bottle, heating to reflux reaction for 5h after the reaction is finished, cooling to room temperature after the reaction is finished, adding 34ml of water, stirring for 15min, filtering to obtain a filtrate, separating the filtrate through diatomite to obtain an organic phase, drying the organic phase by anhydrous magnesium sulfate, purifying by column chromatography to obtain compound 11-e (2.33g, 8978.6%) and (yield): 743 (M)+)。
(3)
Figure BDA0002184750350000241
Compound 11-e (2.2g, 743.08g/mol, 2.96mmol) was added to tert-butylbenzene (22ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 4.78ml, 6.22mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.97g, 250.52g/mol, 11.84mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.2g, 101.2g/mol, 11.84mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain a blue fluorescence doping material (104) (0.91g, yield 31.2%), MS (EI): 984 (M)+)。
Example 12:
Figure BDA0002184750350000242
the synthesis method of the blue fluorescent doping material (113) comprises the following steps:
(1)
Figure BDA0002184750350000243
under the protection of nitrogen, adding 12-a (4g, 603.02g/mol, 6.63mmol), 12-b (1eq, 1.89g, 368.01g/mol, 6.63mmol), sodium tert-butoxide (1.1eq, 0.7g, 96.1g/mol, 7.29mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.3g, 915g/mol, 0.33mmol), tri-tert-butylphosphine (0.05eq, 0.067g, 202.32g/mol, 0.33mol), toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 40ml of water, stirring for 15min, filtering to obtain filtrate, separating by using diatomite to obtain an organic phase after filtration, drying by using anhydrous drying, and purifying by column chromatography to obtain 12-c (3.73g, 66.8 MS): 843 (M)+)。
(2)
Figure BDA0002184750350000251
Under the protection of nitrogen, adding 12-c (3.5g, 843.11g/mol, 4.15mmol), 12-d (1eq, 0.7g, 169.09g/mol, 4.15mmol), sodium tert-butoxide (1.1eq, 0.44g, 96.1g/mol, 4.57mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.19g, 915g/mol, 0.21mmol), tri-tert-butylphosphine (0.05eq, 0.04g, 202.32g/mol, 0.21mol), toluene (35ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 35ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous magnesium sulfate, purifying through dry column chromatography to obtain 12-e (2.75g, 71.1%) EI: 932 (M)+)。
(3)
Figure BDA0002184750350000252
Under the protection of nitrogen, compound 12-e (2)5g, 932.27g/mol and 2.68mmol) is added into tert-butyl benzene (25ml), the temperature is reduced to-78 ℃ by stirring, N-pentane solution of tert-butyl lithium (2.1eq, 1.3M, 4.33ml and 5.63mmol) is slowly dropped, after dropping, the room temperature is recovered, the temperature is reduced to-78 ℃ again after stirring for 50min, boron tribromide (4eq, 2.69g, 250.52g/mol and 10.73mmol) is slowly added, after stirring for 30min, N-diisopropylamine (4eq, 1.09g, 101.2g/mol and 10.73mmol) is slowly added, the temperature is increased to 165 ℃ for reaction for 14h, the reaction liquid is cooled to the room temperature, the reaction liquid is slowly poured into an ice water mixture for quenching, after separating out an organic phase, the organic phase is dried by anhydrous magnesium sulfate, and then is dried by spin-drying, and after column chromatography purification, blue fluorescent doped material (113) is obtained (0.75g, EI yield 31.6 percent): 880 (M)+)。
Example 13:
Figure BDA0002184750350000261
the synthesis method of the blue fluorescent doping material (118) comprises the following steps:
(1)
Figure BDA0002184750350000262
under the protection of nitrogen, adding compound 13-a (4g, 667.05g/mol, 6mmol), compound 13-b (1eq, 1.22g, 203.94g/mol, 6mmol), sodium tert-butoxide (1.1eq, 0.63g, 96.1g/mol, 6.6mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.27g, 915g/mol, 0.3mmol), tri-tert-butylphosphine (0.05eq, 0.06g, 202.32g/mol, 0.3mol), and toluene (40ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is completed, cooling to room temperature after the reaction is completed, adding 40ml of water, stirring for 15min, filtering to obtain a filtrate, filtering the filtrate through kieselguhr, separating to obtain an organic phase, drying through anhydrous magnesium sulfate, purifying through column chromatography to obtain compound 13-c (3.23g, MS yield 72.6%): 743 (M)+)。
(2)
Figure BDA0002184750350000271
Under the protection of nitrogen, adding compound 13-c (3g, 743.08g/mol, 4.04mmol), compound 13-d (1eq, 0.7g, 321.15g/mol, 4.04mmol), sodium tert-butoxide (1.1eq, 0.43g, 96.1g/mol, 4.44mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.18g, 915g/mol, 0.2mmol), tri-tert-butylphosphine (0.05eq, 0.041g, 202.32g/mol, 0.2mol), toluene (30ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 35ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying to obtain compound 13-e (2.6g, 65.3%) after column chromatography (EI): 984 (M)+)。
(3)
Figure BDA0002184750350000272
Compound 13-e (2.5g, 984.3g/mol, 2.54mmol) was added to tert-butylbenzene (25ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 4.1ml, 5.33mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.55g, 250.52g/mol, 10.16mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 1.03g, 101.2g/mol, 10.16mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into an ice-water mixture for quenching, separating an organic phase, drying with anhydrous magnesium sulfate, spin-drying, and purifying by column chromatography to obtain a blue fluorescence doped material (118) (0.73g, yield 30.9%), MS (EI): 932 (M)+)。
Example 14:
Figure BDA0002184750350000281
step (1) is the same as in example 1
(2)
Figure BDA0002184750350000282
Under the protection of nitrogen, adding compound 14-a (2g, 514.98g/mol, 3.88mmol), compound 14-b (1eq, 1.59g, 410.18g/mol, 3.88mmol), sodium tert-butoxide (1.1eq, 0.41g, 96.1g/mol, 4.27mmol), tris (dibenzylideneacetone) dipalladium (0.05eq, 0.178g, 915g/mol, 0.19mmol), tri-tert-butylphosphine (0.05eq, 0.039g, 202.32g/mol, 0.19mol), toluene (20ml) into a reaction bottle, heating to reflux reaction for 5h after the addition is finished, cooling to room temperature after the reaction is finished, adding 20ml of water, stirring for 15min, filtering to obtain a filtrate, separating through diatomite to obtain an organic phase, drying through anhydrous rotary magnesium sulfate, purifying by column chromatography to obtain compound 14-c (1.81g, 55.2%) EI: 845 (M)+)。
(3)
Figure BDA0002184750350000283
Compound 14-c (1.7g, 845.24g/mol, 2.01mmol) was added to tert-butylbenzene (17ml) under nitrogen, stirring and cooling to-78 ℃, slowly dropping N-pentane solution of tert-butyllithium (2.1eq, 1.3M, 3.25ml, 4.22mmol), recovering room temperature after dropping, stirring for 50min, cooling to-78 ℃, slowly adding boron tribromide (4eq, 2.02g, 250.52g/mol, 8.05mmol), stirring for 30min, slowly adding N, N-diisopropylamine (4eq, 0.81g, 101.2g/mol, 8.05mmol), heating to 165 ℃, reacting for 14h, cooling to room temperature, slowly pouring reaction liquid into ice water mixture for quenching, separating organic phase, drying with anhydrous magnesium sulfate, spin-drying, purifying by column chromatography to obtain blue fluorescent doped material (124) (0.57g, yield 35.6%), MS (EI): 793 (M)+)。
Testing the material properties:
thermal stability tests were performed on the blue fluorescent doped material of the present invention and the comparative material using a thermogravimetric analyzer (TGA-N-1000), respectively, and the test results are shown in Table 1 below,
table 1:
blue fluorescent doping material T95/℃
Comparative example 1 BD-1 368.37
Comparative example 2 BD-2 375.62
Example 1 1 496.99
Example 2 6 488.04
Example 3 11 513.62
Example 4 14 498.31
Example 5 28 507.64
Example 6 40 486.25
Example 7 43 497.26
Example 8 54 527.24
Example 9 65 513.67
Example 10 86 527.85
Example 11 104 506.52
Example 12 113 517.93
Example 13 118 524.97
Example 14 124 519.61
As can be seen from table 1, the blue fluorescent doped material of the present invention has better thermal stability than comparative examples 1 and 2, and the better thermal stability can effectively improve the efficiency and lifetime of the organic electroluminescent device.
Testing the performance of the device:
application example 1:
adopting ITO as the anode substrate material of the reflecting layer, and sequentially using water, acetone and N2Carrying out surface treatment on the glass substrate by plasma;
depositing HAT-CN with the thickness of 10nm to form a Hole Injection Layer (HIL) above the ITO anode substrate;
evaporating NPD above the Hole Injection Layer (HIL) to form a Hole Transport Layer (HTL) with the thickness of 120 nm;
ADN as a blue host material and the blue fluorescent dopant material (1) prepared in example 1 as a blue dopant material (the amount of the blue fluorescent dopant material (1) was 5% by weight of ADN) were evaporated at different rates on the Hole Transport Layer (HTL) to form a light emitting layer having a thickness of 30 nm;
evaporating PBD on the light-emitting layer to obtain an Electron Transport Layer (ETL) with the thickness of 35nm, and evaporating LiQ with the thickness of 2nm above the Electron Transport Layer (ETL) to form an Electron Injection Layer (EIL);
then magnesium (Mg) and silver (Ag) are mixed and evaporated in a ratio of 9:1 to obtain a cathode with the thickness of 15nm, DNTPD with the thickness of 50nm is deposited on the sealing layer of the cathode, and in addition, the surface of the cathode is sealed by UV hardening adhesive and sealing film (seal cap) containing a moisture remover so as to protect the organic electroluminescent device from being influenced by oxygen or moisture in the atmosphere, thus preparing the organic electroluminescent device.
Figure BDA0002184750350000301
Application examples 2 to 14
The organic electroluminescent devices of application examples 2 to 14 were fabricated by using the blue fluorescent dopant materials 6, 11, 14, 28, 40, 43, 54, 65, 86, 104, 113, 118, and 124 of examples 2 to 14 of the present invention as blue light dopant materials, respectively, and the rest of the materials were the same as those of application example 1.
Comparative example 1
The difference from application example 1 is that BD-1 and BD-2 were used as blue light doping materials, and the rest is the same as application example 1.
The characteristics of the organic electroluminescent element manufactured in the above application example and the organic electroluminescent element manufactured in the comparative example were that the current density was 10mA/cm2The results of measurements under the conditions of (1) are shown in Table 2.
Table 2:
Figure BDA0002184750350000311
as can be seen from table 2 above, when the blue-light doped material of the present invention is applied to an organic electroluminescent device, the light emitting efficiency is improved to a certain extent under the same current density, the start voltage of the device is reduced, the power consumption of the device is relatively reduced, and the lifetime of the device is correspondingly improved.

Claims (10)

1. A blue fluorescent doping material with good thermal stability and high efficiency is characterized in that the structural formula is as follows:
Figure FDA0003638941950000011
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are respectively and independently hydrogen, deuterium, halogen, cyano, unsubstituted trimethylsilyl, unsubstituted triphenylsilyl, unsubstituted C1-C10 straight-chain or branched-chain alkyl, unsubstituted C3-C10 cycloalkyl, unsubstituted C1-C10 heteroalkyl, unsubstituted C2-C10 alkenyl, unsubstituted C2-C10 alkynyl, unsubstituted C6-C60 aromatic hydrocarbon group and unsubstituted C5-C60 heteroaromatic hydrocarbon group.
2. The blue fluorescent dopant of claim 1, where R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are each independently hydrogen, deuterium, a fluorine atom, a cyano group, an unsubstituted trimethylsilyl group, an unsubstituted triphenylsilyl group, an unsubstituted methyl group, an unsubstituted ethyl group, an unsubstituted isopropyl group, an unsubstituted isobutyl group, an unsubstituted tert-butyl group, an unsubstituted neopentyl group, an unsubstituted methoxy group, an unsubstituted phenyl group, an unsubstituted methylphenyl group, an unsubstituted ethylphenyl group, an unsubstituted isopropylphenyl group, an unsubstituted isobutylphenyl group, an unsubstituted tert-butylphenyl group, an unsubstituted neopentylphenyl group, an unsubstituted anthracenyl group, an unsubstituted naphthyl group, an unsubstituted phenanthryl group, an unsubstituted azaanthracenyl group, an unsubstituted naphthyridinyl group, an unsubstituted pyridyl group, an unsubstituted pyrimidyl group, or a, Unsubstituted dimethylamino group, unsubstituted diphenylamine group, unsubstituted fluorenyl group, unsubstituted oxyfluorenyl group, unsubstituted dibenzothienyl group, unsubstituted carbazolyl group, unsubstituted 9, 9-dimethylfluorenyl group, unsubstituted 9, 9-diphenylfluorenyl group, and unsubstituted 9, 9-spirobifluorenyl group.
3. A blue fluorescent doping material with good thermal stability and high efficiency is characterized in that the structural formula is as follows:
Figure FDA0003638941950000012
r1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are respectively and independently hydrogen, deuterium, a fluorine atom, a cyano group, a trimethylsilyl group, a triphenylsilyl group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a methoxy group, a phenyl group, a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, an isobutylphenyl group, a tert-butylphenyl group, a neopentylphenyl group, an anthracenyl group, a naphthyl group, a phenanthryl group, an azaanthracenyl group, a naphthyridinyl group, a pyridyl group, a pyrimidyl group, a dimethylamino group, a diphenylamine group, a fluorenyl group, an oxyfluorenyl group, a dibenzothienyl group, a carbazolyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-spirobifluorenyl group;
wherein the trimethylsilyl group, the triphenylsilyl group, the methyl group, the ethyl group, the isopropyl group, the isobutyl group, the tert-butyl group, the neopentyl group, the methoxy group, the phenyl group, the methylphenyl group, the ethylphenyl group, the isopropylphenyl group, the isobutylphenyl group, the tert-butylphenyl group, the neopentylphenyl group, the anthracenyl group, the naphthyl group, the phenanthryl group, the azaanthracenyl group, the naphthyridinyl group, the pyridyl group, the pyrimidinyl group, the dimethylamino group, the diphenylamine group, the fluorenyl group, the oxyfluorenyl group, the dibenzothienyl group, the carbazolyl group, the 9, 9-dimethylfluorenyl group, the 9, 9-diphenylfluorenyl group, the 9, 9-spirobifluorenyl group are unsubstituted or are obtained by substituting at least one hydrogen by at least one of deuterium, a fluorine atom, a cyano group, a linear or branched alkyl group of C1-C4, and a phenyl group.
4. A blue fluorescent doping material with good thermal stability and high efficiency is characterized in that the blue fluorescent doping material is any one of the following structural formula compounds:
Figure FDA0003638941950000021
Figure FDA0003638941950000031
Figure FDA0003638941950000041
Figure FDA0003638941950000051
Figure FDA0003638941950000061
5. the method for preparing the blue fluorescent dopant material of any one of claims 1 to 3, wherein the method comprises the following steps:
Figure FDA0003638941950000071
adding the compound A into tert-butyl benzene under the protection of inert gas, stirring and cooling to-78-40 ℃, slowly dropping N-pentane solution of tert-butyl lithium, recovering the room temperature after dropping, stirring for 30-50 min, then cooling to-78-40 ℃, slowly adding boron tribromide, stirring for 30-50 min, slowly adding N, N-diisopropylamine, heating to 155-165 ℃, reacting for 12-15 h, cooling to room temperature, slowly pouring the reaction liquid into an ice water mixture, quenching, separating an organic phase, drying, and purifying to obtain the blue fluorescent doped material.
6. Use of a blue fluorescent dopant material as claimed in any one of claims 1 to 4 in the preparation of an organic electroluminescent device.
7. An organic electroluminescent device comprising a structure in which an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked, wherein the light-emitting layer contains a host material and a dopant material, and the dopant material is at least one of the blue fluorescent dopant materials according to any one of claims 1 to 4.
8. The organic electroluminescent device according to claim 7, wherein the blue fluorescent dopant is doped in an amount of 1 to 7% by mass of the host material.
9. The organic electroluminescent device according to claim 8, wherein the blue fluorescent dopant is doped in an amount of 5% by mass of the host material.
10. An electronic display device, characterized in that it contains an organic electroluminescent device as claimed in claim 7.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109155368A (en) * 2016-04-26 2019-01-04 学校法人关西学院 Organic electric-field light-emitting element
CN109192874A (en) * 2018-08-31 2019-01-11 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
CN109411634A (en) * 2018-08-31 2019-03-01 昆山国显光电有限公司 A kind of organic electroluminescence device and display device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109155368A (en) * 2016-04-26 2019-01-04 学校法人关西学院 Organic electric-field light-emitting element
CN109192874A (en) * 2018-08-31 2019-01-11 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
CN109411634A (en) * 2018-08-31 2019-03-01 昆山国显光电有限公司 A kind of organic electroluminescence device and display device

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