CN1325474C - Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials - Google Patents
Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials Download PDFInfo
- Publication number
- CN1325474C CN1325474C CNB2004100160488A CN200410016048A CN1325474C CN 1325474 C CN1325474 C CN 1325474C CN B2004100160488 A CNB2004100160488 A CN B2004100160488A CN 200410016048 A CN200410016048 A CN 200410016048A CN 1325474 C CN1325474 C CN 1325474C
- Authority
- CN
- China
- Prior art keywords
- dipyridyl
- bromo
- synthetic
- luminescent
- electroluminescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The present invention discloses a novel bipyridine (namely 2, 2'-bipyridine, the same in the following) derivative namely a Ln-beta-diketone ternary electroluminescent coordination compound and a preparation method thereof (Ln is a rare-earth ion). The luminescent material is convenient and is easy to obtain through modular design. The electronic structure and the electron and cavity injection and transmission performance of the material are conveniently regulated by introducing electron-attracting groups, such as fluorobenzene, or electron-enriching groups, such as arylamine, etc. in the material. Red electroluminescent devices ((Ln is Eu<3+>) made from the present invention have the advantages of favorable luminescent performance, high color purity, large luminescent luminance, low starting voltage and high luminescent efficiency. Especially, the devices still emit the proper pure red light of rare-earth ions under high voltage.
Description
Technical field
The present invention relates to the novel electroluminescent organic material of a class, belong to technical field of electronic materials.Particularly, the organic electroluminescence device that the present invention relates to rare earth complex molecule material and use this quasi-molecule relates in particular to the preparation technology of the synthetic of class dipyridyl derivatives-Ln-beta-diketon ternary electroluminescent title complex (Ln=rare earth ion) and application and relevant luminescent device.
Technical background
From 1987, electroluminescent organic material and device (organic light emitting diodes, OLEDs) rise, because its huge applications prospect in technique of display of new generation, caused the extensive concern of scientific circles and international renowned company and play an active part in.The common technique of display of electroluminescent organic material and device and other is compared, has to be convenient to design, and the luminous efficiency height, the visual angle is wide, and response speed is fast, ultra-thin, light weight, glow color can cover advantages such as whole visible region.The typical structure of OLED comprises cathode layer, anode layer, and the organic luminous layer between this is two-layer, can comprise one or more functional layers in electron transfer layer, hole transmission layer and the luminescent layer in the organic luminous layer.
Adopting well behaved luminescent material is the important foundation for preparing in this type of OLED device, and it is most important therefore to develop this type of luminescent material.
The organometallic complex luminescent material has that structure is determined, easily separated purification and fluorescence efficiency advantages of higher, occupies critical role in the development of new electroluminescent organic material.Wherein, RE compound material is because its luminous unique property is subjected to broad research at present.The luminous unique distinction of rare earth compounding is: its luminous narrowband emission that presents at first, make the display device of high color purity easily.Secondly, the rare earth compounding luminescence process be by the organic ligand excited singlet state through intersystem crossing to excited triplet state, to rare earth ion the 4f electronics is excited transmission ofenergy again, emit corresponding radiation light-wave when they get back to ground state, the electroluminescent device internal quantum efficiency can reach 100% in theory.Therefore, design, synthesize and develop RE compound material and seem particularly important with novel light-emitting and charge transport properties.
Summary of the invention
The objective of the invention is to a synthetic class novel electroluminescent material, and adopt this material preparation high efficiency electroluminous device.
This type of material that the present invention proposes, the neutral ligand and the beta-diketon anion ligand complex rare-earth ion that are formed by the derivative of dipyridyl form, and structure is as follows:
In the said structure formula, Ar, R, R ', X, Y are substituting group, Ln is Nd
3+(neodymium), Er
3+(erbium), Pr
3+(praseodymium), Sm
3+(samarium), Eu
3+(europium), Tb
3+(terbium), Tm
3+(thulium).
X=H or Y;
X
1-X
5Be H or F; X
1-X
5In at least one is a fluorine; Perhaps
Y＝
R=H or cyano group benzene; R ' is phenyl, α-thienyl or Alpha-Naphthyl;
Ar=R
1Ar
1R
1=H or CF
3Or F or polyfluoro substituted benzene; Ar
1Be phenyl.
The synthetic method of above-claimed cpd is as follows:
Part is synthetic: wherein contains (many) and fluoridizes 2 of benzene, 2 '-dipyridyl derivatives, with 4-bromo-2,2 '-dipyridyl or 4,4 '-two bromo-2,2 '-dipyridyl are module, K
2CO
3Be alkali, the Pd (PPh of catalytic amount
3)
4React by Suzuki, with corresponding (many) fluorobenzenes boric acid coupling, boric acid: the bromo-derivative mol ratio is 1.0～2.0 when bromo dipyridyl (bromo-derivative be single), or 2.0～3.0: 1 when bromo dipyridyl (bromo-derivative be two)], through column chromatography for separation or recrystallization, obtain high-purity target product part;
Wherein contain
With
2,2 '-dipyridyl derivatives is with 4-bromo-2,2 '-dipyridyl or 4,4 '-two bromo-2,2 '-dipyridyl are module, in the presence of Anhydrous potassium carbonate and catalytic amount copper, synthetic with corresponding secondary amine through the Ullmann reaction, obtain high-purity target product part through column chromatography for separation or recrystallization.
Title complex is synthetic: put into LnCl in flask
3(1 equivalent, wherein, Ln is Nd
3+, Er
3+, Pr
3+, Sm
3+, Eu
3+, Tb
3+, Tm
3+A kind of), beta-diketonate ligand (3 equivalent) and dehydrated alcohol, 50-70 ℃ of stirring, solution clarification back adds 1-2.5M sodium hydroxide solution (3 equivalent), backflow 25-150 minute, add part (1 equivalent), reacted 5-7 hour.Evaporate to dryness with methylene dichloride dissolving, filters, and filtrate is through washing, drying, and the product that obtains behind the evaporate to dryness is with acetonitrile or methylene dichloride/normal hexane mixed solution recrystallization.
Suzuki of the present invention reaction be a kind of with palladium salt as catalyzer, under alkalescence, anaerobic and lucifuge condition, the C-C linked reaction that takes place between aryl bromide and the aryl boric acid.
Ullmann reaction of the present invention is a kind of carbon-nitrogen bond linked reaction of carrying out in the presence of Anhydrous potassium carbonate and catalytic amount copper.
Above-mentioned title complex can be used as the luminescent layer material in the electroluminescent device.The structure of this electroluminescent device and preparation:
1, the structure of device of the present invention is ITO/TPD/Eu
3+Complex:CBP/BCP/Alq/LiF/Al.
2, evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (anode) at first, vacuum plating luminescent layer (CBP:Eu then
3+Complex (x%)); Continue vacuum evaporation one deck electric transmission/hole blocking layer material B CP; Be vacuum evaporation electron transfer layer materials A lq afterwards; Follow vacuum evaporation LiF; Negative electrode Al in the last vacuum evaporation.
Rare-earth complexes luminous material of the present invention conveniently is easy to get by modular design; By in material, introducing electron-withdrawing group, as fluorobenzene, or introduce the electron rich group, as arylamine etc., thereby regulate the electronic structure of material easily.Red electroluminescent device (the Ln=Eu that utilizes the present invention to make
3+) luminescent properties is good: the purity of color height, luminosity is big, trigger voltage is low, luminous efficiency is high.Particularly, under high voltage, device still sends the distinctive pure ruddiness of rare earth ion.
Description of drawings
Fig. 1 is the device architecture figure among the present invention.
Fig. 2 is the electroluminescent properties phenogram of the device one of compound of the present invention.Wherein (a) is current efficiency, (b) is luminous efficiency, (c) is brightness, (d) is electroluminescent intensity.
Fig. 3 is the electroluminescent properties phenogram of the device two of compound of the present invention.Wherein (a) is current efficiency, (b) is luminous efficiency, (c) is brightness, (d) is electroluminescent intensity.
Fig. 4 is the structural formula figure of TPD.
Fig. 5 is the structural formula figure of CBP.
Fig. 6 is the structural formula figure of BCP.
Embodiment
Below introduce specific embodiments of the invention.
Example 1: europium-carbazolyl-containing dipyridyl neutral ligand-beta-diketon ternary complex synthetic
1. carbazolyl-containing dipyridyl neutral ligand is synthetic
(1) single oxygen dipyridyl is synthetic
(28.0g 179mmol), chloroform (400ml), stirs 35min under the ice-water bath condition, (40.1g 232mmol), at 35 ℃ of reaction 24h, uses 5%Na to add metachloroperbenzoic acid then to add dipyridyl in flask
2CO
3Solution (200ml) washing three times, the water layer chloroform extraction merges organic layer, uses anhydrous magnesium sulfate drying, filters evaporate to dryness.Product is refluxed in ether, and the evaporate to dryness diethyl ether solution obtains yellow solid afterwards.Cross column purification, obtain faint yellow solid product (22.0g, 70%) behind the evaporate to dryness.
1H?NMR(400MHz，CDCl
3)：δ/ppm＝7.20-7.31(3H，m)，7.79(m，1H)，8.13(dd，1H)，8.27(d，1H)，8.68(d，1H)，8.85(d，1H).
(2) 4-nitro list oxygen dipyridyl is synthetic
With single oxygen dipyridyl (10.5g, 61.0mmol) put into flask, under the ice-water bath condition, add the vitriol oil (105ml) and saltpetre (41.6g, 301mmol), be warming up to 70 ℃ of reaction 24h afterwards, reaction is poured the yellow jelly that obtains in the ice into after finishing, and water layer is green, transfers pH=7 with NaOH solution, separate out a large amount of yellow oil this moment, use chloroform extraction, the organic layer anhydrous magnesium sulfate drying that obtains filters evaporate to dryness and obtains red product, use ethyl alcohol recrystallization, obtain light yellow crystal, be product (7.0g, 55%).
1H?NMR(400MHz，CDCl
3)：δ/ppm＝7.40(m，1H)，7.84(m，1H)，8.03(dd，1H)，8.33(d，1H)，9.13(d，1H).
(3) 4-bromine dipyridyl is synthetic
With 4-nitro list oxygen dipyridyl (7.00g, 32.2mmol) and Glacial acetic acid (140ml) be added in the flask, add acetyl bromide (35.0ml) while stirring, have this moment glassy yellow precipitation to generate.Add phosphorus tribromide (35.0ml) subsequently, temperature of reaction is controlled at 40 ℃, and (precipitation disappears substantially) is warming up to 80 ℃ behind the 15min, backflow 1.5h postcooling leaves standstill precipitation is separated out, and upper solution is carefully inclined to, and precipitation is used the hot water dissolving, transfer to pH=9 with NaOH solution again, back chloroform extraction, organic layer anhydrous magnesium sulfate drying, filter, obtain yellow thick product behind the evaporate to dryness, through purifying, evaporate to dryness obtains white translucent solid, be 4-bromine dipyridyl (6.2g, 81.4%).
1H?NMR(400MHz，CDCl
3)：δ/ppm＝7.34(m，1H)，7.48(dd，1H)，7.83(m，1H)，8.38(d，1H)，8.48(d，1H)，8.62(d，1H)，8.68(d，1H).
(4) the basic ethyl ester of toluene-4-sulfonic acid 2-carbazole-9 is synthetic
(1.15g, 6mmol) (1.04g 5mmol) is dissolved in the tetrahydrofuran (THF) (20ml), adds triethylamine (5ml) again, stirs, and spends the night with 9-hydroxyethyl carbazole with 4-methyl-Phenylsulfonic acid chlorine.Filter, with filtrate revolving steam dark yellow oily liquid, in this liquid, add ether, make it dissolving, add ethanol then, the adularescent crystal is separated out immediately, suction filtration, oven dry, product (1.4g, 82%).
1H?NMR(500MHz，CDCl
3)：δ/ppm＝2.25(s，3H)，4.41(t，2H)，4.52(t，2H)，6.83(d，2H)，7.21-7.27(m，6H)，7.40(dd，2H)，7.99(d，2H).
(5) 9-[2-(4-bromo-phenoxy group)-ethyl]-the 9H-carbazole
With the basic ethyl ester of toluene-4-sulfonic acid 2-carbazole-9 (2g, 5.5mmol), 4-bromophenol (1.1g, 6.4mmol), Anhydrous potassium carbonate (3g) is put into flask, adds N, dinethylformamide (20ml) feeds nitrogen, back flow reaction 18h, reaction finishes after-filtration, and solid is washed 2-3 time with ether, adds 10ml water in the filtrate, use the separating funnel separatory after the layering, wash with water ether layer several times after, combined ether layer, use anhydrous magnesium sulfate drying, it is white solid (1.7g, 90%) that evaporate to dryness gets product.
1H?NMR(400MHz，CDCl
3)：δ/ppm＝4.30(t，2H)，4.70(t，2H)，6.66(s，2H)，7.25(s，2H)，7.29(s，2H)，7.47(s，4H)，8.10(s，2H).
(6) 9-[2-(4-dihydroxyl boric acid-phenoxy group)-ethyl]-9H-carbazole synthetic
With 9-[2-(4-bromo-phenoxy group)-ethyl]-9H-carbazole (1.8g, 5mmol) put into dry in advance good flask, the tetrahydrofuran (THF) 20ml that adds the new anhydrous and oxygen-free that steams, be cooled to-78 ℃, add the about 4ml of n-Butyl Lithium then, question response carries out adding the about 3ml of methyl-borate again after half an hour, and reaction is spent the night, hydrolysis, add methylene dichloride then up to obvious layering occurring, the water layer washed with dichloromethane, the organic layer anhydrous magnesium sulfate drying filters, revolve steaming, oven dry obtains white solid (1.2g, 75%).
1H?NMR(500MHz，DMSO)：δ/ppm＝4.39(t，2H)，4.81(d，2H)，6.78(dd，2H)，7.21(t，2H)，7.46(t，2H)，7.52(d，4H)，7.67(dd，2H)，8.14(d，2H).
(7) 9-[2-(4-bromo-phenoxy group)-ethyl]-9H-carbazole dipyridyl synthetic
With 9-[2-(4-dihydroxyl boric acid-phenoxy group)-ethyl]-the 9H-carbazole (1.0g, 2.2mmol), tetramethyl ethylene ketone (0.50g, 4.2mmol), (0.470g, 2.0mmol), toluene (60ml) puts into flask, logical nitrogen adds Pd (PPh to 4-bromine dipyridyl
3)
4(0.16g is 0.14mmol) with 2M K
2CO
3Solution (4.0ml) is at 80 ℃ of reaction 16h.Reaction finishes postcooling, separatory, and water layer merges organic layer with dichloromethane extraction twice, and drying is filtered, and evaporate to dryness is crossed column purification, obtains white solid (0.70g, 81%) behind the evaporate to dryness.
1H?NMR(400MHz，)：δ/ppm＝
1H?NMR(400MHz，CDCl
3)：δ/ppm＝4.42(m，2H)，4.77(m，2H)，6.92(d，2H)，7.26(m，4H)，7.51(m，4H)，7.66(d，2H)，7.82(m，1H)，8.11(d，2H)，8.42(d，1H)，8.60(d，1H)，8.68(m，2H).
2. europium ternary complex is synthetic
1. europium ternary complex 1 is synthetic, and structural formula is as scheming:
In flask, put into phenyl phenacyl ketone (DBM) (343mg, 1.50mmol), EuCl
36H
2(183mg 0.500mmol), adds dehydrated alcohol 25ml to O then, 60 ℃ of stirrings, solution clarification back adds 2M NaOH solution (0.75ml), adds neutral ligand 9-[2-(4-bromo-phenoxy group)-ethyl after the half an hour of refluxing]-9H-carbazole-dipyridyl (221mg, 0.5mmol), reaction 6h, evaporate to dryness, with the methylene dichloride dissolving, to filter, filtrate is through washing, drying, must get yellow powder behind the evaporate to dryness, use the acetonitrile recrystallization again, obtain orange-yellow crystal, productive rate 86%.
2. europium ternary complex 2 is synthetic, and structural formula is as scheming:
The preparation method is same 1., and (343mg, (333mg 1.50mmol) gets final product, and obtains orange-yellow crystal, productive rate 81% with methylene dichloride/normal hexane mixed solution recrystallization 1.50mmol) to change trifluoroacetyl thiophene acetone (TTA) into DBM.
Example 2: synthetic 1.4-(the 2,4 difluorobenzene)-bipyridine ligand of europium-contain 2,4 difluorobenzene base dipyridyl neutral ligand-beta-diketon ternary complex synthetic
Take by weighing 4-bromine dipyridyl (2g, 8.5mmol synthesize with example 1) and 2, (1.6g 10.2mmol) is dissolved in toluene to 4-difluoro boric acid benzene, and logical nitrogen adds Pd (PPh
3)
4(0.35g 0.3mmol), adds 2M K at last
2CO
3Solution (18ml), lucifuge, refluxing keeps 90～100 ℃ of temperature, reaction 12h.After reaction finishes, separatory.The toluene layer anhydrous magnesium sulfate drying filters, and revolves steaming, obtains faint yellow crude product, crosses column purification, obtains straight product (2g, 85%).
1H?NMR(500?MHz，CDCl
3)：δ/ppm＝6.99(m，2H)，7.32(m，1H)，7.48(m，1H)，7.59(dd，1H)，7.84(m，1H)，8.44(d，1H)，8.55(s，1H)，8.69(m，1H)，8.74(dd，1H).
2. europium ternary complex is synthetic
1. europium ternary complex 3 is synthetic, and structural formula is as scheming:
In flask, put into DBM (343mg, 1.50mmol), EuCl
36H
2(183mg 0.500mmol), adds dehydrated alcohol 25ml to O, 70 ℃ of stirrings, solution clarification back adds 2M NaOH solution (0.75ml), and refluxing adds neutral ligand 4-(2 after 35 minutes, 4-two fluorobenzene)-(134mg 0.5mmol), reacted 7 hours dipyridyl, evaporate to dryness with the methylene dichloride dissolving, filters, filtrate must get yellow powder through washing, drying behind the evaporate to dryness, uses the acetonitrile recrystallization again, obtain orange-yellow crystal, productive rate 84%.
2. europium ternary complex 4 is synthetic, and structural formula is as scheming:
The preparation method is same 3., and (343mg, (333mg 1.50mmol) gets final product, with obtaining orange-yellow crystal, productive rate 83% behind methylene dichloride/normal hexane mixed solution recrystallization 1.50mmol) to change TTA into DBM.
Example 3: the preparation of electroluminescent device
The structure of device of the present invention is ITO/TPD/Eu
3+Complex:CBP/BCP/Alq/LiF/Al.
Evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (anode) at first, thickness is 35-50nm; Vacuum evaporation luminescent layer then is entrained among the material of main part CBP by red light material europium ternary complex of the present invention and constitutes, and thickness is 25-40nm; Continue vacuum evaporation one deck electric transmission/hole blocking layer material B CP, thickness is 15-30nm; Be electron transfer layer Alq afterwards, thickness is 20-40nm; Then be that thickness is the LiF of 1-5nm; Metallic cathode Al in the last vacuum evaporation, thickness is 80-200nm.
Device one: ITO/TPD (40nm)/title complex 1:CBP (3%, 30nm)/BCP (20nm)/Alq (30nm)/LiF (1nm)/Al (100nm)
This device luminescent layer material is an europium complex 1, and doping content is 3%.Under forward bias, ruddiness (612nm) sent out pure by this device, and peak width at half height is 4nm, trigger voltage 5.5V, and brightness reaches as high as 480cd/m
2, maximum current efficient is 6cd/A, maximum lumen efficient is 31m/W.Brightness is at 100cd/m
2The time, current efficiency, luminous efficiency, current density, external quantum efficiency are respectively 2.53cd/A, 0.81m/W, 3.54mA/cm
-2And 2.2%.Its current efficiency curve and luminous efficiency curve be referring to Fig. 2 (a), Fig. 2 (b); Electric current-voltage curve, brightness-voltage curve is referring to Fig. 2 (c); Under different operating voltage, electroluminescent spectrum Fig. 2 (d).
Device two: ITO/TPD (40nm)/title complex 3:CBP (6%, 30nm)/BCP (20nm)/Alq (30nm)/LiF (1nm)/Al (100nm)
This device luminescent layer material is an europium complex 3, doping content 6%.Under forward bias, ruddiness (613nm) sent out pure by this device, and peak width at half height is 4nm, trigger voltage 4.9V, and brightness reaches as high as 626cd/m
2Brightness is at 100cd/m
2The time, current efficiency, luminous efficiency, current density are respectively 2.03cd/A, 0.73lm/W, 4.60mA/cm
-2Its current efficiency curve and luminous efficiency curve be referring to Fig. 3 (a), Fig. 3 (b); Electric current-voltage curve, brightness-voltage curve is referring to Fig. 3 (c); Under different operating voltage, electroluminescent spectrum Fig. 3 (d).
Claims (3)
1. an electroluminescent organic material is characterized in that, this luminescent material is formed by neutral ligand and the beta-diketon anion ligand complex rare-earth ion that the derivative of dipyridyl forms, and structure is as follows:
Wherein, Ar, R, R ', X, Y are substituting group, Ln is Nd
3+, Er
3+, Pr
3+, Sm
3+, Eu
3+, Tb
3+, Tm
3+A kind of;
X=H or Y;
X
1--X
5Be H or F; X
1--X
5In at least one is a fluorine; Perhaps
Y＝
R=H or cyano group benzene; R ' is phenyl, α-thienyl or Alpha-Naphthyl;
Ar=R
1Ar
1R
1=H or CF
3Or F or polyfluoro substituted benzene; Ar
1Be phenyl.
2. the synthetic method of a RE compound material as claimed in claim 1 is characterized in that:
Part is synthetic: wherein contain 2 of fluorobenzene or phenyl polyfluoride, 2 '-dipyridyl derivatives, with 4-bromo-2,2 '-dipyridyl or 4,4 '-two bromo-2,2 '-dipyridyl are module, K
2CO
3Be alkali, the Pd (PPh of catalytic amount
3)
4, by the Suzuki reaction, with corresponding fluorobenzene or the coupling of phenyl polyfluoride boric acid, boric acid: single bromo dipyridyl mol ratio is 1.0～2.0, perhaps boric acid: two bromo dipyridyls are 2.0～3.0: 1, through column chromatography for separation or recrystallization, obtain high-purity target product part;
Wherein contain
With
2,2 '-dipyridyl derivatives is with 4-bromo-2,2 '-dipyridyl or 4,4 '-two bromo-2,2 '-dipyridyl are module, in the presence of Anhydrous potassium carbonate and catalytic amount copper, synthetic with corresponding secondary amine through the Ullmann reaction, obtain high-purity target product part through column chromatography for separation or recrystallization;
Title complex is synthetic: put into 1 normal LnCl in flask
3, 3 normal beta-diketonate ligand and dehydrated alcohols, 50-70 ℃ of stirring, solution clarification back adds 3 normal sodium hydroxide solution 1-2.5M, and backflow 25-150 minute, add 1 equivalent part, reacted 5-7 hour; Evaporate to dryness with methylene dichloride dissolving, filters, and filtrate is through washing, drying, and the product that obtains behind the evaporate to dryness is with acetonitrile or methylene dichloride/normal hexane mixed solution recrystallization; Here Ln is Nd
3+, Er
3+, Pr
3+, Sm
3+, Eu
3+, Tb
3+, Tm
3+A kind of.
3. electroluminescent organic material as claimed in claim 1 in the organic electroluminescent device as the application of luminescent layer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100160488A CN1325474C (en) | 2004-02-03 | 2004-02-03 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100160488A CN1325474C (en) | 2004-02-03 | 2004-02-03 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1557907A CN1557907A (en) | 2004-12-29 |
| CN1325474C true CN1325474C (en) | 2007-07-11 |
Family
ID=34351670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100160488A Expired - Fee Related CN1325474C (en) | 2004-02-03 | 2004-02-03 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1325474C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503965B (en) * | 2010-12-31 | 2014-07-09 | 南京大学 | Rare earth complex with light conversion function and preparation method thereof |
| CN103739926A (en) * | 2013-12-31 | 2014-04-23 | 杭州索康博能源科技有限公司 | Fluorescent EVA (ethylene-vinyl acetate) glue film |
| CN104045954B (en) * | 2014-07-04 | 2016-03-09 | 重庆理工大学 | A kind of PMMA is as the preparation method of the rare earth ruddiness film of matrix |
| CN106967101B (en) * | 2017-04-07 | 2019-04-09 | 盐城工学院 | A kind of rare earth organic light conversion agents and anti-aging light conversion film |
| CN117285926B (en) * | 2023-11-24 | 2024-01-26 | 山东济钢鲁纳新材料科技有限公司 | Alpha, alpha-terpyridyl rare earth organic red light conversion agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329127A (en) * | 2000-06-20 | 2002-01-02 | 中国科学院长春光学精密机械与物理研究所 | Rare-earth organic electroluminescence narrow-band blue light emitting material |
| CN1329128A (en) * | 2000-06-20 | 2002-01-02 | 中国科学院长春光学精密机械与物理研究所 | Rare-earth organic electroluminescence white light emitting material |
| CN1350049A (en) * | 2000-10-19 | 2002-05-22 | 中国科学院长春光学精密机械与物理研究所 | Organic RE light emitting material with narrow emission band in infrared band |
-
2004
- 2004-02-03 CN CNB2004100160488A patent/CN1325474C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329127A (en) * | 2000-06-20 | 2002-01-02 | 中国科学院长春光学精密机械与物理研究所 | Rare-earth organic electroluminescence narrow-band blue light emitting material |
| CN1329128A (en) * | 2000-06-20 | 2002-01-02 | 中国科学院长春光学精密机械与物理研究所 | Rare-earth organic electroluminescence white light emitting material |
| CN1350049A (en) * | 2000-10-19 | 2002-05-22 | 中国科学院长春光学精密机械与物理研究所 | Organic RE light emitting material with narrow emission band in infrared band |
Non-Patent Citations (1)
| Title |
|---|
| 稀土有机电致发光材料 李建宇 李海涛，精细化工，第18卷第7期 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1557907A (en) | 2004-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705166B (en) | Metal complex, organic electroluminescent material, organic electroluminescent element, and electronic device | |
| CN107722062B (en) | Metal iridium or platinum complex and organic electroluminescent device containing metal iridium or platinum complex | |
| WO2019143153A1 (en) | Novel compound and organic light emitting device using same | |
| CN108164564A (en) | A kind of metal iridium complex and the organic electroluminescence device comprising the metal iridium complex | |
| JP7458483B2 (en) | Metal complexes and their uses | |
| EP2236485A1 (en) | Organic material containing oligophenylene skeleton and light-emitting device using the same | |
| CN103833790B (en) | A series of Phosphorescent OLED material | |
| CN109942637B (en) | Metal complex and organic electroluminescent device | |
| CN108250246B (en) | Four-coordination manganese compound with bipolar structure and preparation method and application thereof | |
| CN101220034B (en) | Inverse V type ultra-gees alkali derivant electroluminescent organic material | |
| CN102911145A (en) | Dibenzo-heterocyclic spirobifluorene compound, preparation method thereof and organic electrophosphorescent device | |
| KR101252603B1 (en) | Deep-Blue Phosphorescent Iridium(III) Complexes Utilizing N-Methylimidazolyltriazoles | |
| CN103936791A (en) | Series organic electrophosphorescent material | |
| CN102101852A (en) | Coumarin derivative, preparation method thereof and application thereof in white light organic electroluminescent device | |
| CN105481901B (en) | The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex | |
| CN102796133A (en) | Rare-earth europium complex and application thereof as luminescence material | |
| CN110407838A (en) | Electroluminescent organic material and device | |
| CN112175017B (en) | Organic electrophosphorescent material and application thereof | |
| CN1325474C (en) | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials | |
| CN112321647B (en) | Iridium complex containing benzimidazole structure and application thereof | |
| CN105294781A (en) | Iridium-europium heterogeneous polynuclear metal complex and its preparation method and use | |
| CN105418679A (en) | Triphenylphosphine oxide unit bridged bipolar host material and application thereof | |
| CN112175016B (en) | Organic electrophosphorescent luminescent material and application thereof | |
| CN101440088B (en) | Metal organic complexes, preparation thereof, luminescent material and luminescent device | |
| CN104650154A (en) | Deep-red-light phosphor material iridium complex, preparation method of complex and organic light-emitting device using complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070711 Termination date: 20100203 |