CN105949245A - Yellow light emitting iridium phosphorescence coordination compound and method for preparing same - Google Patents
Yellow light emitting iridium phosphorescence coordination compound and method for preparing same Download PDFInfo
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- CN105949245A CN105949245A CN201610352175.8A CN201610352175A CN105949245A CN 105949245 A CN105949245 A CN 105949245A CN 201610352175 A CN201610352175 A CN 201610352175A CN 105949245 A CN105949245 A CN 105949245A
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- iridium
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention discloses a yellow light emitting iridium phosphorescence coordination compound and a method for preparing the same. The yellow light emitting iridium phosphorescence coordination compound is structurally characterized in that 2, 4-(3, 5-dimethyl phenyl) bipyridine is used as a cyclometalated ligand, and acetylacetone, 2, 2, 6, 6-tetramethyl-3, 5-heptanedione or 2-picolinic acid are used as auxiliary ligands. The yellow light emitting iridium phosphorescence coordination compound and the method have the advantages that the emission wavelengths of three iridium phosphorescence coordination compounds are 565 nm, 575 nm and 550 nm respectively, and the iridium phosphorescence coordination compounds are yellow light emitting iridium phosphorescence coordination compounds prepared by the aid of the method.
Description
Technical field
The present invention relates to Organic Light Emitting Diode (OLED) electroluminescent phosphorescence Material Field, specifically one class Yellow light-emitting low temperature
Iridium phosphorescent complexes and preparation method thereof.
Background technology
Organic Light Emitting Diode (OLED, Organic Light Emitting Diodes) as efficient electro-optic conversion technology,
Have the thinnest lighter, active illuminating (being not required to backlight), wide viewing angle, high-resolution, response is fast, energy consumption is low and shock resistance
The advantages such as excellent, the potential low manufacturing cost of energy and easily realization are flexible, represent in flat pannel display and solid-state illumination field
Go out tempting development prospect, be an emerging strategic industries emerged.
Luminous organic material is one of key material of OLED, and it directly affects the performance of OLED.
In the development of OLED, it is worth mentioning at this point that the Thompson of University of Southern California in 1998, Princeton University
Phosphorescent complexes is incorporated into the luminescent layer of OLED by the horse what light of Forrest and Jilin University etc. as luminescent material, makes
The maximum internal quantum efficiency of device is brought up to the 100% of phosphor material by the 25% of original fluorescent material.
Up to the present, OLED based on iridium phosphorescent complexes has the highest luminous efficiency.Join by changing ring metal
Body and the structure of assistant ligand, all can regulate and control maximum emission wavelength and the luminous efficiency of iridium phosphorescent complexes, it is achieved to luminescence
The regulation and control of color.One of important use of yellow phosphorescence material is to realize white light emission, it is common that gold-tinted and RGB three face
Color or gold-tinted and blue light mix by a certain percentage and realize white light emission, are used primarily in solid-state illumination field.Usual little molecule iridium
Phosphorescent complexes is assembled due to molecule and is produced concentration quenching, causes that luminous efficiency is low, service life is short.Based on this, this
Bright by introducing the concentration quenching that methyl minimizing molecule gathering causes, design has synthesized the iridium phosphorus of three kinds of novel yellow emission
Light coordination compound.
Summary of the invention
It is an object of the invention to provide iridium phosphorescent complexes of the novel Yellow light-emitting low temperature of a class and preparation method thereof.
The iridium phosphorescent complexes of three kinds of Yellow light-emitting low temperatures that the present invention provides, they are two [2,4-bis-(3,5-3,5-dimethylphenyl) pyrroles
Pyridine] acetyl acetone iridium, two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridines] (2,2,6,6-dipivaloylmethane acid) close iridium
Closing iridium with two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] (2-pyridine carboxylic acid), they have following structural formula:
The invention provides a kind of method preparing above-mentioned iridium phosphorescent complexes, it comprises the following steps:
(1) synthesis of part
The synthesis of 2,4-bis-(3,5-3,5-dimethylphenyl) pyridine be with 2,4-dichloropyridine and 3,5-dimethylphenyl boronic acid as raw material,
Tetra-triphenylphosphine palladium be catalyst, oxolane and water be solvent, obtain part by suzuki coupling reaction.Concrete
Synthetic route and reaction condition are as follows:
(2) synthesis of iridium phosphorescent complexes
Under an argon atmosphere, with hydrated iridium trichloride as raw material, 2,4-bis-(3,5-3,5-dimethylphenyl) pyridine is ring metal
Part, ethylene glycol monoethyl ether and water (3:1) are solvent, back flow reaction 24 hours at 120 DEG C, cooling, filter,
Obtain double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } after drying and close iridochloride, the most respectively with 2.5 times of materials
The assistant ligand (acetylacetone,2,4-pentanedione, 2,2,6,6-dipivaloylmethanes or pyridine carboxylic acid) of amount, at alkalescence condition and 135 DEG C
Back flow reaction 4 hours, filters, and dichloromethane is quick crosses post, dichloromethane and methanol mixed solvent recrystallization, obtains phase
The iridium phosphorescent complexes answered.Concrete synthetic route and reaction condition are as follows:
The present invention use elementary analysis, proton nmr spectra (1H NMR and 13C NMR), mass spectrum confirm part and
The structure of complex of iridium, the optical physics being obtained iridium phosphorescent complexes by uv-vis spectra and photoluminescence spectra is joined
Number.
It is a feature of the present invention that iridium phosphorescent complexes of obtaining a class Yellow light-emitting low temperature and preparation method thereof, provide for OLED
The selection of three kinds of luminous bodys.
Accompanying drawing explanation
Fig. 1 is the photoluminescence spectra of two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] acetyl acetone iridium；
Fig. 2 is the photoluminescence spectra that two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridines] (acid of 2,2,6,6-dipivaloylmethane) close iridium；
Fig. 3 is the photoluminescence spectra that two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] (2-pyridine carboxylic acid) closes iridium.
Detailed description of the invention
Embodiment one:
The synthesis of 2,4-bis-(3,5-3,5-dimethylphenyl) pyridine:
2 are added in the three neck round bottom of 1L, 4-dichloropyridine (18.4g, 124.3mmol), 3,5-dimethylphenyl boronic acid
(37.0g, 136.73mmol), and four (triphenyl phosphorus) palladium (2.5g, 2.16mmol) and natrium carbonicum calcinatum (61.8g, 583.02
Mmol), 200mL oxolane and 200mL secondary deionized water are then added, at N2Under protection, 70 DEG C are returned
Stream reaction 24h, removes solvent after being cooled to room temperature, adds a large amount of deionized water, and dichloromethane extracts three times, extraction
Adding methanol in organic facies, four (triphenyl phosphorus) palladium solid of precipitation reclaims, and filtrate uses anhydrous MgSO4It is dried.Cross
After filtering solvent, residue is crossed post and is obtained pale yellow oil 43.2g, productivity 78%.
1. elementary analysis: theoretical value (%): C 87.76H 7.36N 4.87,
Measured value (%): C 87.74H 7.35N 4.88
2. nuclear magnetic resoance spectrum:1H-NMR(CDCl3,ppm):8.71(d,1H),7.89(m,1H),7.65(s,2H),7.42(dt,1H),
7.31(m,2H),7.10(d,2H),2.42(s,12H)；
3.ESI+-MS:m/z theoretical value: 287.40, measured value: 287
Embodiment two:
The synthesis of double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } conjunction iridochloride:
Addition hydrated iridium trichloride (15.0g, 42.0mmol) in 500ml three neck round bottom, 2,4-bis-(3,5-
3,5-dimethylphenyl) pyridine (30.0g, 14.5mmol), add 270ml ethylene glycol monoethyl ether and 90ml bis-times afterwards
Deionized water, under argon shield, 120 DEG C of back flow reaction 24hrs.Being cooled to room temperature, filter, ethanol used respectively by filter cake
Wash with water, 60 DEG C of vacuum drying 24hrs, obtain double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } and close iridochloride
28.88g, productivity 85.6%.
Embodiment three:
The synthesis of two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] acetyl acetone iridium:
In 500ml three neck round bottom, add double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } close iridochloride (15.0
G, 9.4mmol), natrium carbonicum calcinatum (4.95g, 46.9mmol), acetylacetone,2,4-pentanedione (2.25g, 20.6mmol), add afterwards
Enter 300mL ethylene glycol monoethyl ether, repeatedly take out applying argon gas three times, under argon shield, 135 DEG C of back flow reaction 24h.Cold
But to room temperature, mixture is poured in a large amount of water, filters, and filter cake dissolves with dichloromethane after drying, and crosses post, goes out solvent
After, obtain target product 13.1g, productivity 87.5% after residue dichloromethane and recrystallizing methanol.
1. elementary analysis: theoretical value (%): C 65.33H 5.48N 3.24,
Measured value (%): C65.35H 5.47N 3.21
2. nuclear magnetic resoance spectrum:1H-NMR(CDCl3,ppm):8.42(d,2H),8.04(d,2H),7.48(s,2H),7.43(s,4H),
7.21(dd,2H),7.12(s,2H),6.52(s,2H),5.12(s,1H),2.44(s,13H),2.31(s,6H),1.71(s,6H),
1.43(s,6H)；
3.ESI-MS:m/z theoretical value: 864.11, measured value: 864
4. photoluminescence spectra: maximum emission wavelength is 565nm (Fig. 1), for yellow emission iridium phosphorescent complexes.
Embodiment four:
The synthesis of two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridines] (acid of 2,2,6,6-dipivaloylmethane) conjunction iridium:
In 500ml three neck round bottom, add double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } close iridochloride (10.0
G, 6.3mmol), natrium carbonicum calcinatum (3.3g, 31.3mmol), 2,2,6,6-dipivaloylmethanes (2.53g, 13.7mmol),
Add 150mL ethylene glycol monoethyl ether afterwards, repeatedly take out applying argon gas three times, under argon shield, 135 DEG C of back flow reaction
24h.Being cooled to room temperature, mixture is poured in a large amount of water, filters, and filter cake dissolves with dichloromethane after drying, and crosses post,
Go out after solvent, after residue dichloromethane and recrystallizing methanol, obtain target product 10.03g, productivity 84.7%.
1. elementary analysis: theoretical value (%): C 67.13H 6.27N 2.95,
Measured value (%): C 67.11H 6.25N 2.92
1. nuclear magnetic resoance spectrum:1H-NMR(CDCl3,ppm):8.27(d,2H),8.02(d,2H),7.46(s,2H),7.40(s,4H),
5.42(s,1H),2.46(s,12H),2.33(s,6H),1.49(s,6H),0.84(s,18H).
3.ESI-MS:m/z theoretical value: 948.26, measured value: 948
4. photoluminescence spectra: maximum emission wavelength is 575nm, for yellow emission iridium phosphorescent complexes (Fig. 2)
Embodiment five:
The synthesis of two [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] (2-pyridine carboxylic acid) conjunction iridium:
In 500ml three neck round bottom, add double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } close iridochloride (7.5
G, 4.7mmol), natrium carbonicum calcinatum (2.48g, 23.5mmol), 2-pyridine carboxylic acid (1.27g, 10.3mmol), add afterwards
Enter 150mL ethylene glycol monoethyl ether, repeatedly take out applying argon gas three times, under argon shield, 135 DEG C of back flow reaction 24h.Cold
But to room temperature, mixture is poured in a large amount of water, filters, and filter cake dissolves with dichloromethane after drying, and crosses post, goes out solvent
After, obtain target product 6.91g, productivity 83.1% after residue dichloromethane and recrystallizing methanol.
1. elementary analysis: theoretical value (%): C 64.99H 5.00N 4.74,
Measured value (%): C 64.97H 5.01N 4.73
2. nuclear magnetic resoance spectrum:1H-NMR(CDCl3,ppm):8.72(d,1H),8.23(m,1H),8.05(d,1H),7.95(d,1H),
7.80(m,2H),7.72(m,2H),7.31(m,6H),6.96(dd,3H),6.65(s,1H),6.55(d,2H),2.41(s,12H),
2.30(d,6H),1.49(s,3H),1.34(s,3H)；
3.ESI-MS:m/z theoretical value: 887.10, measured value: 887
4. photoluminescence spectra: maximum emission wavelength is 550nm (Fig. 3), for yellow emission iridium phosphorescent complexes.
Claims (2)
1. the iridium phosphorescent complexes of a class Yellow light-emitting low temperature, the iridium phosphorescence relating to three kinds of different assistant ligands coordinates
Thing, their structural formula is:
2. the method preparing the iridium phosphorescent complexes of a class Yellow light-emitting low temperature, comprises the following steps:
(1) synthesis of part:
The synthesis of 2,4-bis-(3,5-3,5-dimethylphenyl) pyridine is with 2,4-dichloropyridine and 3,5-dimethyl
Phenylboric acid be raw material, tetra-triphenylphosphine palladium be catalyst, oxolane and water be solvent, pass through suzuki
Coupling reaction obtains part, and concrete synthetic route and reaction condition are as follows:
(2) synthesis of iridium phosphorescent complexes:
Under an argon atmosphere, with hydrated iridium trichloride as raw material, 2,4-bis-(3,5-3,5-dimethylphenyl) pyrrole
Pyridine is cyclic metal complexes, and ethylene glycol monoethyl ether and water (3:1) are solvent, back flow reaction at 120 DEG C
24 hours, cooling, filter, obtain double-{ [2,4-bis-(3,5-3,5-dimethylphenyl) pyridine] } after drying and close
Iridochloride, assistant ligand (acetylacetone,2,4-pentanedione, 2,2,6, the 6-tetramethyls of the amount of the most respectively with 2.5 times of materials
Base heptadione or pyridine carboxylic acid), back flow reaction 4 hours at alkalescence condition and 135 DEG C, filters, two
Chloromethanes is quick crosses post, dichloromethane and methanol mixed solvent recrystallization, obtains corresponding iridium phosphorescence and joins
Compound.Concrete synthetic route and reaction condition are as follows:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368094A (en) * | 2008-09-25 | 2009-02-18 | 中国科学院长春光学精密机械与物理研究所 | Yellow electrophosphorescent iridium complex, preparation method and uses thereof |
| US20110049496A1 (en) * | 2009-08-31 | 2011-03-03 | Fujifilm Corporation | Organic electroluminescence device |
| WO2012166608A1 (en) * | 2011-05-27 | 2012-12-06 | Universal Display Corporation | High efficiency yellow light emitters for oled devices |
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- 2016-05-25 CN CN201610352175.8A patent/CN105949245A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368094A (en) * | 2008-09-25 | 2009-02-18 | 中国科学院长春光学精密机械与物理研究所 | Yellow electrophosphorescent iridium complex, preparation method and uses thereof |
| US20110049496A1 (en) * | 2009-08-31 | 2011-03-03 | Fujifilm Corporation | Organic electroluminescence device |
| WO2012166608A1 (en) * | 2011-05-27 | 2012-12-06 | Universal Display Corporation | High efficiency yellow light emitters for oled devices |
Non-Patent Citations (1)
| Title |
|---|
| XIAO-QING ZHANG等，: "Highly phosphorescent platinum(II) complexes based on rigid unsymmetric tetradentate ligands", 《ORGANIC ELECTRONICS》 * |
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Application publication date: 20160921 |