CN104059630B - A kind of novel red phosphorescence material and synthetic method thereof - Google Patents
A kind of novel red phosphorescence material and synthetic method thereof Download PDFInfo
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- CN104059630B CN104059630B CN201310111762.4A CN201310111762A CN104059630B CN 104059630 B CN104059630 B CN 104059630B CN 201310111762 A CN201310111762 A CN 201310111762A CN 104059630 B CN104059630 B CN 104059630B
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Abstract
The present invention discloses a kind of novel red phosphorescence material, and structural formula is:It is an advantage of the current invention that, described red phosphorescence material introduces metal iridium complex, increase rigidity and the stability of phosphor material, introduce the solvability that β-heptadione ligand improves iridium complex phosphorescence material simultaneously, so that this kind of phosphor material is easier to coating processing. Simultaneously material shows good thermostability, and in addition, structure introduces band bromine group, it is possible to other compound copolymerization with specific function group, therefore also can be used as polymerization single polymerization monomer and prepares polymer luminescent material. And its simple synthetic method, practical, it is possible to be applied in luminescent material as red phosphorescence material.
Description
Technical field
The invention belongs to photoelectric material technical field, particularly relate to a kind of novel red phosphorescence material and synthetic method thereof.
Background technology
Organic electroluminescence device has that driving voltage is low, fast response time, visual angle wide ranges, it is easy to realizes the advantages such as resolving power height, weight are light, large-area flat-plate display, is described as " 21st century flat panel display ". Organic electromechanical phosphorescent material can utilize singlet and Triplet exciton simultaneously, has luminous efficiency advantages of higher, becomes the focus of Recent study.
Relative to high-performance and day by day ripe green and blue phosphorescent material, the progress of red light material obviously falls behind. The Btp that early stage representative complexes of red light iridium designs from Forrest group2Ir (acac), glow peak is positioned at 616nm, and its maximum external quantum efficiency reaches about 7%. 2005, RayabrapuDK have developed 3 kinds of red phosphorescence material based on alkane alkene base quinoline, and the glow peak of its device is positioned at 620-650nm, and external quantum efficiency reaches as high as 7.23%, and luminosity is 26400cd/m2, the design being developed as phosphor material of this type of material provides thinking (AdvMater, 2005,17:349-353).
Still there is the problem that luminous quantum efficiency is low, purity of color is poor in current red phosphorescent complex of iridium. The major cause causing this kind of situation is because ruddiness comes from jumping of the narrower energy inter-stage of energy gap, and there is certain difficulty when carrying out ligand design in the heavy metal complex in narrow forbidden band, secondly red light material system also exists stronger pi-pi bond interact, very strong charge transfer characteristic is had between part, thus make that narrow band gap exists more radiationless relaxation passage, exacerbate the quencher of phosphorescent substance, reduce the quantum yield of ruddiness system. Therefore the red phosphorescence material of design and synthesis high comprehensive performance, will become the important topic of electroluminescent organic material research.
Summary of the invention
It is an object of the present invention to provide a kind of have good stability, film-forming properties and luminescent properties containing complex of iridium, for red phosphorescence material provides new alternative kind.
Novel red phosphorescence material structural formula of the present invention is:
Described red phosphorescence material reacts obtained by complex of iridium dimer and β-heptadione when protection of inert gas, and solvent for use is ethylene glycol ethyl ether or N-Methyl pyrrolidone, and alkali is Na2CO3Or K2CO3The aqueous solution, rare gas element is nitrogen, and temperature of reaction is 125-130 DEG C, and the reaction times is 16-24h.
Described complex of iridium dimer is 4-(the bromo-thiophene of 4-)-phenylpyridine iridium dimer; obtained when protection of inert gas by 4-(the bromo-thiophene of 4-)-phenylpyridine and three chloride hydrate iridium; solvent for use is ethylene glycol ethyl ether; rare gas element is nitrogen; temperature of reaction is 125-130 DEG C, reaction times 24-30h.
Described 4-(the bromo-thiophene of 4-)-phenylpyridine, is obtained when protection of inert gas by the bromo-phenylpyridine boric acid of 4-and 2,5-dibromo thiophene, and solvent for use is toluene or dimethylbenzene, and catalyzer is Pd (PPh3)4, alkali is Na2CO3Or K2CO3The aqueous solution, rare gas element is nitrogen, and temperature of reaction is 95-105 DEG C, reaction times 24-36h.
The bromo-phenylpyridine boric acid of described 4-, is obtained when protection of inert gas by the bromo-phenylpyridine of 4-and trimethyl borate, and reaction solvent is anhydrous THF; catalyzer is reagent n-butyllithium; rare gas element is nitrogen, and temperature of reaction is subzero 50-78 DEG C, reaction times 12h.
By fluorescence, its optical physics performance is characterized by ultraviolet spectrometer, by the thermostability of thermogravimetric analysis test material.
Compared with prior art, it is an advantage of the current invention that, described red phosphorescence material introduces metal iridium complex, increase rigidity and the stability of phosphor material, introduce the solvability that β-heptadione ligand improves iridium complex phosphorescence material, so that this kind of phosphor material is easier to coating processing simultaneously. Simultaneously material shows good thermostability, and in addition, structure introduces band bromine group, it is possible to other compound copolymerization with specific function group, therefore also can be used as polymerization single polymerization monomer and prepares polymer luminescent material.
Accompanying drawing explanation
Fig. 1 is the synthesis path of this red phosphorescence material;
Fig. 2 is the thermogravimetric curve of the red phosphorescence material prepared by embodiment 1.
Fig. 3 is the uv absorption spectra of the red phosphorescence material prepared by embodiment 1;
Fig. 4 is the fluorescence pattern of the red phosphorescence material prepared by embodiment 1.
Embodiment
The synthesis (synthetic route is shown in Fig. 1) of red phosphorescence material of the present invention and the mensuration of physicals is illustrated further below by embodiment.
Embodiment 1:
(1) the bromo-phenylpyridine (10g of 4-is taken; 0.041mol) add in 150mL tri-neck round-bottomed flask; add 50mL tetrahydrofuran (THF) (refluxing drying treatment with sodium) under nitrogen protection; system is placed in ice bath (acetone-dry ice), keeps anhydrous and oxygen-free. When temperature is down to about-78 DEG C, n-Butyl Lithium (24mL, 2.5M, 0.06mol) is dripped slowly into reaction system, the about 30min of whole process. Keep temperature to stir 1h after adding, then trimethyl borate (6.93mL, 0.06mol) is dripped slowly into system, after, at-78 DEG C of stable stirring 2h. Stopping temperature control, equitemperature continues reaction 6h after rising to room temperature, add water termination reaction, acid with dilute hydrochloric acid modulation, continues to stir 2h.Underpressure distillation removes tetrahydrofuran (THF), adds sodium chloride saturated solution subsequently, obtains the bromo-phenylpyridine boric acid of 4-, product rate 80%.
(2) 4-bromo-phenylpyridine boric acid (4g, 0.02mol) is taken, 2,5-dibromo thiophene (4.8g, 2.24mL0.02mol), Pd (PPh3)4(0.231g, 0.2mmol, 1%), K2CO3The aqueous solution (8g, 20mL), toluene (80mL) is placed in the three neck round-bottomed flasks of 150mL, is warming up to 95 DEG C, stirs 24h in the atmosphere of nitrogen. After reaction terminates, it is cooled to room temperature, the difficult molten material being filtered to remove in mixture, add water extraction with separating funnel, removing water layer, underpressure distillation removes the solvent in organic layer, subsequently using methylene dichloride: sherwood oil=10: 1 as leacheate, 4-(the bromo-thiophene of 4-)-phenylpyridine is obtained, product rate 80% with silica gel column chromatography separating purification.
(3) 4-(the bromo-thiophene of 4-)-phenylpyridine (1.3g, 4.12mmol) is taken, IrCl3·3H2O (0.52g, 1.64mmol) adds in the round-bottomed flask of 100mL, adds ethylene glycol ethyl ether (45mL) subsequently, H2O (15mL). Being warming up to 125 DEG C, lucifuge stirs 24h in the atmosphere of nitrogen. Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless, obtains 4-(the bromo-thiophene of 4-)-thick product of phenylpyridine iridium dimer.
(4) 4-(the bromo-thiophene of 4-)-phenylpyridine iridium dimer (1.18g, 0.69mmol) is taken, DPM dpm,dipivalomethane (0.317g, 1.72mmol0.36mL), Na2CO3(0.365g, 3.44mmol) adds in 100mL round-bottomed flask, adds ethylene glycol ethyl ether 40mL subsequently, is warming up to 125 DEG C, and lucifuge stirs 16h in the atmosphere of anhydrous and oxygen-free. Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless. Subsequently with methylene dichloride and sherwood oil recrystallization, preliminary remove insoluble impurity, taking toluene: sherwood oil=2: 1 as leacheate, obtains red phosphorescence material with alumina column separation and purification, product rate 50%.
Embodiment 2:
(1) the bromo-phenylpyridine (10g of 4-is taken; 0.041mol) add in 150mL tri-neck round-bottomed flask; add 50mL tetrahydrofuran (THF) (refluxing drying treatment with sodium) under nitrogen protection; system is placed in ice bath (acetone-dry ice), keeps anhydrous and oxygen-free. When temperature is down to about-78 DEG C, n-Butyl Lithium (24mL, 2.5M, 0.06mol) is dripped slowly into reaction system, the about 30min of whole process. Keep temperature to stir 1h after adding, then trimethyl borate (6.93mL, 0.06mol) is dripped slowly into system, after, at-78 DEG C of stable stirring 2h. Stopping temperature control, equitemperature continues reaction 6h after rising to room temperature, add water termination reaction, acid with dilute hydrochloric acid modulation, continues to stir 2h. Underpressure distillation removes tetrahydrofuran (THF), adds sodium chloride saturated solution subsequently, obtains the bromo-phenylpyridine boric acid of 4-, product rate 80%.
(2) 4-bromo-phenylpyridine boric acid (4g, 0.02mol) is taken, 2,5-dibromo thiophene (4.8g, 2.24mL0.02mol), Pd (PPh3)4(0.231g, 0.2mmol, 1%), K2CO3The aqueous solution (8g, 20mL), toluene (80mL) is placed in the three neck round-bottomed flasks of 150mL, is warming up to 105 DEG C, stirs 24h in the atmosphere of nitrogen. After reaction terminates, it is cooled to room temperature, the difficult molten material being filtered to remove in mixture,, add water extraction with separating funnel, remove water layer, underpressure distillation removes the solvent in organic layer, subsequently using methylene dichloride: sherwood oil=10: 1 as leacheate, obtain 4-(the bromo-thiophene of 4-)-phenylpyridine with silica gel column chromatography separating purification, product rate 82%.
(3) 4-(the bromo-thiophene of 4-)-phenylpyridine (1.3g, 4.12mmol) is taken, IrCl3·3H2O (0.52g, 1.64mmol) adds in the round-bottomed flask of 100mL, adds ethylene glycol ethyl ether (45mL) subsequently, H2O (15mL). Being warming up to 130 DEG C, lucifuge stirs 30h in the atmosphere of nitrogen. Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless, obtains 4-(the bromo-thiophene of 4-)-thick product of phenylpyridine iridium dimer.
(4) 4-(the bromo-thiophene of 4-)-phenylpyridine iridium dimer (1.18g, 0.69mmol) is taken, DPM dpm,dipivalomethane (0.317g, 1.72mmol0.36mL), Na2CO3(0.365g, 3.44mmol) adds in 100mL round-bottomed flask, adds ethylene glycol ethyl ether 40mL subsequently, is warming up to 130 DEG C, and lucifuge stirs 24h in the atmosphere of anhydrous and oxygen-free. Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless. Subsequently with methylene dichloride and sherwood oil recrystallization, preliminary remove insoluble impurity, taking toluene: sherwood oil=2: 1 as leacheate, obtains red phosphorescence material with alumina column separation and purification, product rate 58%. Other and embodiment 1 are similar.
Embodiment 3:
(1) the bromo-phenylpyridine (10g of 4-is taken; 0.041mol) add in 150mL tri-neck round-bottomed flask; add 50mL tetrahydrofuran (THF) (refluxing drying treatment with sodium) under nitrogen protection; system is placed in ice bath (acetone-dry ice), keeps anhydrous and oxygen-free. When temperature is down to about-78 DEG C, n-Butyl Lithium (24mL, 2.5M, 0.06mol) is dripped slowly into reaction system, the about 30min of whole process. Keep temperature to stir 1h after adding, then trimethyl borate (6.93mL, 0.06mol) is dripped slowly into system, after, at-78 DEG C of stable stirring 2h. Stopping temperature control, equitemperature continues reaction 6h after rising to room temperature, add water termination reaction, acid with dilute hydrochloric acid modulation, continues to stir 2h. Underpressure distillation removes tetrahydrofuran (THF), adds sodium chloride saturated solution subsequently, obtains the bromo-phenylpyridine boric acid of 4-, product rate 80%.
(2) 4-bromo-phenylpyridine boric acid (4g, 0.02mol) is taken, 2,5-dibromo thiophene (4.8g, 2.24mL0.02mol), Pd (PPh3)4(0.231g, 0.2mmol, 1%), K2CO3The aqueous solution (8g, 20mL), toluene (80mL) is placed in the three neck round-bottomed flasks of 150mL, is warming up to 95 DEG C, stirs 36h in the atmosphere of nitrogen. After reaction terminates, it is cooled to room temperature, the difficult molten material being filtered to remove in mixture, add water extraction with separating funnel, removing water layer, underpressure distillation removes the solvent in organic layer, subsequently using methylene dichloride: sherwood oil=10: 1 as leacheate, 4-(the bromo-thiophene of 4-)-phenylpyridine is obtained, product rate 82% with silica gel column chromatography separating purification.
(3) 4-(the bromo-thiophene of 4-)-phenylpyridine (1.3g, 4.12mmol) is taken, IrCl3·3H2O (0.52g, 1.64mmol) adds in the round-bottomed flask of 100mL, adds ethylene glycol ethyl ether (45mL) subsequently, H2O (15mL). Being warming up to 125 DEG C, lucifuge stirs 24h in the atmosphere of nitrogen. Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless, obtains 4-(the bromo-thiophene of 4-)-thick product of phenylpyridine iridium dimer.
(4) 4-(the bromo-thiophene of 4-)-phenylpyridine iridium dimer (1.18g, 0.69mmol) is taken, DPM dpm,dipivalomethane (0.317g, 1.72mmol0.36mL), Na2CO3(0.365g, 3.44mmol) adds in 100mL round-bottomed flask, adds N-Methyl pyrrolidone 40mL subsequently, is warming up to 125 DEG C, and lucifuge stirs 16h in the atmosphere of anhydrous and oxygen-free.Reaction is cooled to room temperature after terminating, and underpressure distillation is except desolventizing, and underpressure distillation is except desolventizing, and add water sedimentation, filters, and filter cake methanol wash column to filtrate is colourless. Subsequently with methylene dichloride and sherwood oil recrystallization, preliminary remove insoluble impurity, taking toluene: sherwood oil=2: 1 as leacheate, obtains product with alumina column separation and purification, product rate 45%. Other and embodiment 1 are similar.
Embodiment 4:
Other are with embodiment 1, and synthesis 4-(the bromo-thiophene of 4-)-phenylpyridine, solvent for use is dimethylbenzene, and alkali is Na2CO3, other and embodiment 1 are similar, and product rate is 76%.
Embodiment 5:
Other synthesize described red phosphorescence material with embodiment 1, and solvent for use is N-Methyl pyrrolidone, and alkali is K2CO3, other and embodiment 1 are similar, and product rate is 52%.
Embodiment 6: by fluorescence, its optical physics performance is characterized by ultraviolet spectrometer, by the thermostability of thermogravimetric analysis test material. Figure of description is shown in by collection of illustrative plates.
Claims (5)
1. a red phosphorescent luminescent material, its structural formula is:
2. the synthetic method of a red phosphorescence material according to claim 1; it is characterized in that: described red phosphorescence material reacts obtained by complex of iridium dimer and β-heptadione when protection of inert gas; solvent for use is ethylene glycol ethyl ether or N-Methyl pyrrolidone, and alkali is Na2CO3Or K2CO3The aqueous solution, rare gas element is nitrogen, and temperature of reaction is 125-130 DEG C, and the reaction times is 16-20h.
3. synthetic method according to claim 2; it is characterized in that: complex of iridium dimer is 4-(the bromo-thiophene of 4-)-phenylpyridine iridium dimer; obtained when protection of inert gas by 4-(the bromo-thiophene of 4-)-phenylpyridine and three chloride hydrate iridium; solvent for use is ethylene glycol ethyl ether; rare gas element is nitrogen; temperature of reaction is 125-130 DEG C, reaction times 24-30h.
4. synthetic method according to claim 3; it is characterized in that: 4-(the bromo-thiophene of 4-)-phenylpyridine is by the bromo-phenylpyridine boric acid of 4-and 2; 5-dibromo thiophene is obtained when protection of inert gas, and solvent for use is toluene or dimethylbenzene, and catalyzer is Pd (PPh3)4, alkali is Na2CO3Or K2CO3The aqueous solution, rare gas element is nitrogen, and temperature of reaction is 95-105 DEG C, reaction times 24-36h.
5. synthetic method according to claim 4; it is characterized in that: 4-bromo-phenylpyridine boric acid is obtained when protection of inert gas by 4-(the bromo-thiophene of 4-)-phenylpyridine and trimethyl borate; reaction solvent is anhydrous THF; catalyzer is reagent n-butyllithium; rare gas element is nitrogen; temperature of reaction is subzero 50-78 DEG C, reaction times 12h.
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| CN113801170A (en) * | 2021-10-14 | 2021-12-17 | 东莞理工学院 | Bromine atom modified blue light absorption enhanced iridium (III) complex and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186624A (en) * | 2007-08-16 | 2008-05-28 | 清华大学 | Iridium metal complex and application thereof |
| CN102516310A (en) * | 2011-10-26 | 2012-06-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Cyclometalated iridium complex organic electrophosphorescent material, its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186624A (en) * | 2007-08-16 | 2008-05-28 | 清华大学 | Iridium metal complex and application thereof |
| CN102516310A (en) * | 2011-10-26 | 2012-06-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Cyclometalated iridium complex organic electrophosphorescent material, its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Novel light-emitting electrophosphorescent copolymers based on carbazole with an Ir complex on the backbone;Hongyu Zhen 等;《J. Mater. Chem.》;20070330;第17卷;2824–2831 * |
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