CN1107098C - Phenolic group-pyridine or metal coordination compound of its derivative and their application as electroluminescence material - Google Patents
Phenolic group-pyridine or metal coordination compound of its derivative and their application as electroluminescence material Download PDFInfo
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Abstract
The present invention aims to provide a series of novel electroluminescent materials: the metallic coordination compounds of phenolic group-pyridine and phenolic group-pyridine derivatives. The materials are suitable for preparing organic electroluminescent devices. Each of the organic electroluminescent devices prepared by the present invention is composed of a positive pole (is composed of a glass substrate (1) and ITO (2)), a negative pole (3), a current carrier transmission layer (4) between the positive pole and the negative pole, and a luminescent layer (5), wherein the luminescent layer is mainly composed of the compound related by the present invention. The compound of the present invention has the advantages of simple preparation technology, high luminescent efficiency of the prepared luminescent devices, low starting voltage, long service life, etc.
Description
The organic electroluminescent phenomenon is found existing three times more than ten years, before 1987, because the great drawback (cut-in voltage＞200V), limited its application of organic electroluminescence device.Because the continuous breakthrough of material and device technology, organic electroluminescent has been reached or over past ten years near the practicability stage.
Nineteen sixty-five Gurnee etc. has delivered patent (U.S.Pat.No.3,172,862 about organic electroluminescence device first; 3,173,050).Dresner in 1973 have also delivered the patent (U.S.Pat.No.3,170,167) of organic electroluminescence device aspect.Many aromatic rings organic compound such as anthracene in these inventions, four acenes, five acenes etc. are used to electroluminescent organic material.Early stage device primary structure is characterized as single layer structure, and the thickness of organic luminous layer is greater than 1mm, and the cut-in voltage of device is more than 200V.
The eighties, the Tang etc. of U.S. Kodak company at first found ultra-thin multilayer device structure, the cut-in voltage of device was reduced greatly (U.S.Pat.No.4,356,429).The essential characteristic of its device is to be substrate with the conductive glass, and first evaporation last layer hole injection layer (100nm) also is a transport layer simultaneously, spin coating last layer electron transfer layer also is a luminescent layer simultaneously then, plates layer of metal at last as negative pole, this device cut-in voltage is 20V, and brightness is 5cd/m
2Employing aromatic multi-amine such as the VanSlyke of Kodak company is that hole mobile material carries out the device preparation afterwards, and device performance is improved greatly, and brightness can reach 340cd/m
2
The VansSlyke and the Tang of U.S. Kodak company find Alq first
3(oxine aluminium) has after the good electroluminescent properties, and people are in succession with oxine and derivative and Al
3+, Zn
2+, Ga
3+, Be
2+Deng having synthesized a series of electroluminescent materials, the most of jaundice of these materials green glows, some blue light-emitting (is seen U.S.Pat.No.4,720,432; U.S.Pat.No.4,539,507; C.W.Tang, S.A.VanSlyke, Appl.Phys.Lett.1987,51,913; U.S.Pat.No.5,151,629; Hamada, Jpn.J.Appl.Phys., Part2., 1992,32, L514; Matsumura, Jpn.J.Appl.Phys., 1996,35,5357; Burrows, J.Appys., 1996,79,7991).The Sano of Japan Sanyo company etc. are at U.S.Pat.5, have prepared blue-light device with western Buddhist alkali-Zn complex as luminescent layer in 432,014.Hamada of it should be noted that Japanese Sanyo company etc. synthesizes 10-hydroxy benzo quinoline compound, and its electroluminescent properties has surpassed Alq
3(Chem.Lett. such as Hamada, 1993,905).
Because the discovery of electroluminescent material and the continuing to optimize of device architecture of some excellent propertys make organic electroluminescent obtain some breakthroughs.(see U.S.Pat.Nos.5,151,629; 5,150,006; 5,141,671; 5,073,446; 5,061,569; 5,059,862; 5,059,861; 5,047,687; 4,950,950; 5,104,740; 5,227,252; 5,256,945; 5,069,975; 5,122,711; 5,554,450; 5,683,823; 5,593,788; 5,645,948; 5,451,343; 5,623,080; 5,395,862).Be that the small molecules electroluminescent device or the efficient of polymer electroluminescent device all can reach several 1m/w, at 100cd/m
2Under the brightness, the half-life can reach more than 10,000 hours.
In general, the electroluminescent material of high comprehensive performance still seldom, especially blue light and red light material still less, this panchromatic demonstration and last industrialization for organic electroluminescent is an obstacle.Therefore the electroluminescent material of developing excellent property is extremely important.
The objective of the invention is, provide some can blue light-emitting, the novel materials for electroluminescence of ruddiness, gold-tinted etc., these materials are adapted to the preparation of electroluminescent device.
Find that after deliberation the title complex that is formed with some metals by phenolic group-pyridine and derivative thereof has good electroluminescence characters.Of the present invention to liking the compound of formula (1):
Its Chinese style (O) representative is the fragrant monocycle of basic structure skeleton, many rings, heterocyclic system with the phenylol.Its Chinese style (N) representative is the monocycle of basic structure skeleton, many rings, heterocyclic system with the pyridine group.R
1And R
2Can be identical or different, be alkyl, alkoxyl group, aromatic nucleus, aromatic heterocycle, organic amine.
Bidentate or multiple tooth chelating ligand that its Chinese style (L) representative is linked to each other and forms by singly-bound by phenylol derivative (O) and pyridinyl derivatives (N), ligating atom is oxygen and nitrogen.
In the formula (1), M is divalence or trivalent metal atom, as: Zn
2+, Be
2+, B
3+, Al
3+, Ga
3+, n=1-2.
The title complex that formula of the present invention (1) is served as reasons (L) and metal ion forms.Be applicable to by the compound of formula of the present invention (1) to prepare blueness, the xanchromatic electroluminescent device, simultaneously, formula of the present invention (1) compound and other red light material such as rubrene mix (rubrene 5%), can prepare the ruddiness device.
By title complex of the present invention advantage wherein is that film forming character is good, the luminous efficiency height.
The part of title complex of the present invention (L) can synthesize by method like the known class on the document (sees L Daczmark, R.Balicki, J.Lipkowski, P.Boronicz, A.Grabowska, J.Chem.Soc.Perkin Trans.Z, 1994,1603; R.A.Abromovitch, S.Kato, G.M.Singer, J.Am.Chem.Soc.1971,93,3074).For preparation 2-(2-hydroxy phenyl)-pyridine or derivatives thereof is undertaken by following reaction pattern 1:
Reaction pattern 1: 
Reaction pattern 1 is suitable for all replacement situations of formula (L), for R
1For strong electrophilic group, as NO
2, CN, CF
3Deng using reaction pattern 2 Synthetic 2s-(2-hydroxy phenyl)-pyridine derivate.
Reaction pattern 2:
The title complex of 2-(2-hydroxy phenyl)-pyridine or derivatives thereof can be undertaken by reaction pattern 3.
Reaction pattern 3:
N=1-8, m=1-4
Above-mentioned reaction pattern 1,2,3 is example with phenolic group (O) and pyridyl (N) for monocyclic situation only, and the synthetic method and the reaction conditions of other fragrant many rings, condensed ring, heterocyclic system are similar.This compounds all has good electroluminescence characters, can be widely used in the electroluminescent device.
(L) for skeleton structure is bidentate or the multiple tooth chelating ligand that is linked to each other by singly-bound by pyridine or pyridine derivate and phenylol or phenylol derivative, formula of the present invention (1) is the title complex that is generated by formula (L) compound and metal reaction.
By reaction pattern 1, the raw material that synthesis type (L) compound adopts is 2-bromo-methyl-phenoxide or derivatives thereof and 2-bromo-pyridine or derivatives thereof.Because reaction intermediate is relatively more responsive to oxygen and water, so in the entire reaction course, reaction system will be used nitrogen protection, otherwise reaction does not take place or productive rate is extremely low.Preparation formula (L) compound is at first made Grignard reagent with 2-bromo-methyl-phenoxide or derivatives thereof and metal M g reaction, this Grignard reagent continues to generate with 2-bromo-pyridine or derivatives thereof generation linked reaction the coupled product of pyridine or derivatives thereof and methyl-phenoxide or derivatives thereof, this product demethylation under strong acid condition generates target product formula (L) compound, and crude product can get the product (L) of purity very high (98%) through column chromatography purification.This reaction process is suitable for preparing formula (L) compound that all replace situation.
If the phenylol or derivatives thereof in the formula (L) has strong electron-withdrawing substituent (as: NO
2, NC, CF
3) time, can be by reaction pattern 2 preparation target compounds.At first with the p-Nitroaniline or derivatives thereof (to itrile group aniline or derivatives thereof, p-trifluoromethylaniline or derivatives thereof all can) with Sodium Nitrite prepared in reaction oil of mirbane diazonium salt under acidic conditions, the coupling in acetonitrile of this diazonium salt and pyridine nitric oxide, coupled product isomerization under alkaline condition generates formula (L) compound that phenylol has strong electron-withdrawing substituent.The advantage of reaction pattern 2 is that reaction process need not blanketing with inert gas, because reaction intermediate is insensitive to oxygen or water, its limitation is to prepare formula (L) compound that the phenylol or derivatives thereof has strong electron-withdrawing substituent.
The synthetic general method of invention formula (1) compound is in methyl alcohol, methylene dichloride or the aqueous solution, to make BeSO by reaction pattern 3
4 ', GaCl
3 ', ZnCl
2, BF
3, MgSO
4, A1
2(SO
4)
3Deng with formula (L) part room temperature reaction under alkaline condition, get final product production (1) compound.Concrete experiment condition is seen example.
Compound of the present invention can be used as electroluminescent material and prepares electroluminescent device, especially can be used for the active coating of electroluminescent device.So-called active coating is exactly to be placed on to have the organic thin film layer that visible light sends in the electric field.
Therefore object of the present invention also is formula of the present invention (1) compound as the application of electroluminescent material and contains the application of the mixture of formula (1) compound as electroluminescent material.
By electroluminescent spectrum, brightness, the test of current/voltage characteristic analytical procedure, its characteristic of electroluminescent device of using formula of the present invention (1) compound is as follows: cut-in voltage＜5V, brightness can reach 100cd/m
2-3000cd/m
2, luminous efficiency can reach 0.2-31m/w, and can reach more than 500 hours device lifetime.This shows that the synthetic method of the compound of formula of the present invention (1) is simple, purification is convenient, be applied to electroluminescent material has characteristics such as cut-in voltage is low, brightness is high, luminous efficiency is high, the life-span is long.
The application of formula of the present invention (1) compound in electroluminescent device now is described in conjunction with the accompanying drawings.Object of the present invention can be used for preparing the electroluminescent device that has one or more active coatings, and in these active coatings at least one deck contain one or more compounds of the present invention.Active coating can be a light-emitting layer and/or a migrating layer and/or a charge injection layer.The basic structure of this type of luminescent device as shown in Figure 1, this figure is the electroluminescent device of pair of lamina structure, it is by attached to the ITO on the transparent glass 1 (tin indium oxide) conductive layer (positive pole) 2 and metal (Al, Mg: Ag alloy, Ca, Na, K) layer (consequent pole) 3 and two active coatings being clipped between the two poles of the earth constitute, and these two active coatings also are simultaneously that electron transport material 5 constitutes by hole mobile material (as TPD) 4 and luminescent material respectively.Hole and electronics inject from chief and vice the two poles of the earth respectively, transmission in hole transmission layer and electron transfer layer (also being luminescent layer) respectively in two-layer near interface zone electronics and hole-recombination, and produces exciton, exciton is got back to ground state by radiative transition, just has light to send.This radiative color can be by changing the compound change of using as luminescent layer.Between electroluminescence layer and negative electrode, can add pack into one deck electronics injecting layer and/or electron transfer layer, can pack between electroluminescence layer and the anode one deck hole injecting layer and/or hole migrating layer.
These el light emitting devices can as on self luminous indicator elment such as signal lamp, aplhanumeric visual display, direction board, the photoelectronic coupler, the application in the flat-panel monitor.
Further illustrate the preparation and the application of The compounds of this invention below by example, rather than will limit the present invention with these examples.Example 1:PPH's is synthetic
(PPH)
Under nitrogen protection; make solvent with 30mlTHF (tetrahydrofuran (THF)); 6.74g (36mmol) 2-bromoanisole and excessive (＞36mmol) magnesium rod reaction; get final product the Grignard reagent of 2-bromoanisole; Grignard reagent is added drop-wise in 5.7g (36mmol) the 2-bromopyridine tetrahydrofuran (THF), and reaction mixture at room temperature stirs spend the night (12 hours).Add 10ml, the NH of 3M
4Behind the Cl aqueous solution, with the acidifying of 12ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(20ml) extraction is three times, and organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(2-methyl-phenoxide) pyridine.2-(2-methyl-phenoxide) pyridine is placed in the 50ml concentrated hydrochloric acid, and encloses in the withstand voltage Glass tubing, 190 ℃ were heated 3 hours under nitrogen protection, added 50ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation are removed to desolvate and are obtained the red-purple viscous solution, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid 4.1 grams, productive rate 66% with the frozen water cooling.The mass spectrum experiment shows molecular ion peak: 171.Ultimate analysis experimental result: by molecular formula C
11H
9NO calculated value: C:77.2%, H:5.3%, N:8.2%; Experimental value: C:77.8%, H:5.0%, N:7.9%.Example 2:DPPH's is synthetic
(DPPH)
Under nitrogen protection; make solvent with 30ml THF; 8.5g (45mmol) 2-bromoanisole and excessive (＞45mmol) magnesium rod reaction; get final product the Grignard reagent of 2-bromoanisole; Grignard reagent is added drop-wise to 11.3g (45mmol) 2; in the 6-dibromo pyridine tetrahydrofuran solution, reaction mixture at room temperature stirs spend the night (12 hours).The NH that adds 10ml 3M
4Behind the Cl aqueous solution, with the acidifying of 13ml concentrated hydrochloric acid, rotary evaporation removes the THF in desolvating then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(3 * 20ml) extractions three times, organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtain tawny oily matter.Above-mentioned product is placed the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage Glass tubing, the following 190 ℃ of heating of nitrogen protection 3 hours add 40ml water then in mixture, be neutralized to neutrality with the KOH solvent again, use CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation are removed to desolvate and are obtained the red-purple viscous solution, and viscous solution is purified with silica gel chromatographic column, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid 7.3 grams, productive rate 62% with the cold water cooling.Mass spectrum shows molecular ion peak: 263.Ultimate analysis is by molecular formula C
17H
13NO
2Calculated value: C:77.6%, H:4.9%, N:5.3%; Experimental value: C:76.9%, H:5.7%, N:4.6%.Example 3:NO
2PPH's is synthetic:
(NO
2PPH)
The 40g pyridine is mixed with the glacial acetic acid of 300ml, stir the hydrogen peroxide that splashes into 50ml 35% down, be heated to 70-80 ℃, add the 35ml hydrogen peroxide after three hours, kept nine hours, reaction back rotary evaporation is concentrated into 100ml, adds 100ml water, rotary evaporation is concentrated into 50ml again, and residue is with anhydrous Na
2CO
4Transfer to alkalescence (PH=13), with the 250ml chloroform extraction, organic phase is through anhydrous Na
2SO
4Dry back gets milk yellow pyridine nitric oxide solid 25g with the rotatory evaporator evaporate to dryness.The 4-N-methyl-p-nitroaniline of 35g is dissolved in the middle of the 50ml fluoroboric acid, place frozen water, temperature control is below 5 ℃, the 16g Sodium Nitrite is dissolved in the 10ml water, add in the fluoroboric acid system, this process need stir, keep gained precipitation being leached in two hours, with washing with alcohol for several times 4-oil of mirbane diazonium salt yellow crystals.
3.5g (37mmol) pyridine nitric oxide and 8.73g (37mmol) 4-nitro diazonium salt are dissolved in respectively in the middle of the 25ml acetonitrile, mix down at 50 ℃, stirring reaction 2 hours, there is dark solid to generate, be the coupled product of pyridine nitric oxide and nitro diazonium salt, filter to isolate solid, and it is inferior to give a baby a bath on the third day after its birth with acetonitrile, air drying.This coupled thing of 2.0g is dissolved in (60 ℃) in the hot acetonitrile of 25ml, dropwise adds the 2ml triethylamine under stirring, post precipitation to be occurred leaches precipitation, gets 4.8g NO
2The faint yellow needle-like crystal of PPH, productive rate 60%.Mass spectrum shows molecular ion peak: 216.Ultimate analysis is by molecular formula C
11H
8N
2O
3Calculated value: C:61.1%H:3.7%, N:13.0%; Experimental value: C:60.9%, H:4.1%, N:13.7%.Example 4:NCPPH's is synthetic
(NCPPH)
The 4-itrile group aniline of 35g is dissolved in the middle of the 50ml fluoroboric acid, place frozen water, temperature control is below 5 ℃, the 16g Sodium Nitrite is dissolved in the 10ml water, join in the fluoroboric acid system, this process need stir, keep gained precipitation being leached in two hours, with washing with alcohol for several times 4-itrile group phenyl diazonium salt yellow crystals.
Be dissolved in respectively in the middle of the 25ml acetonitrile with 3.5g (37mmol) pyridine nitric oxide and to 8.0g (37mmol) 4-itrile group diazonium salt, mix down at 50 ℃, stirring reaction 2 hours, the coupled product of dark solid pyridine nitric oxide and nitro diazonium salt.This coupled thing of 2.0g is dissolved in the hot acetonitrile of 20ml (60 ℃), dropwise adds the 2ml triethylamine under stirring, post precipitation to be occurred leaches precipitation, gets the faint yellow needle-like crystal of 3.6g NCPPH, productive rate 50%, and mass spectrum shows molecular ion peak: 196.Ultimate analysis is by molecular formula C
12H
8N
2O calculated value: C:73.5%, H:4.1%, N:14.3%; Experimental value: C:72.9%, H:4.2%, N:14.6%.Example 5:PNPPH's is synthetic
(PNPPH)
40g 4-phenylpyridine is mixed with the glacial acetic acid of 300ml, stir the hydrogen peroxide that splashes into 50ml 35% down, be heated to 70-80 ℃ °, add the 35ml hydrogen peroxide after three hours, kept nine hours, reaction back rotary evaporation is concentrated into about 100ml, adds 100ml water, rotary evaporation is concentrated into 50ml again, and residue is with anhydrous Na
2CO
4Transfer to alkalescence, PH=13, with the 250ml chloroform extraction, organic phase is through anhydrous Na
2SO
4Dry back gets milk yellow 4-phenylpyridine oxynitride solid 21g with the rotatory evaporator evaporate to dryness.6.3g (37mmol) 4-phenylpyridine oxynitride and 8.0g (37mmol) 4-itrile group phenyl diazonium salt are dissolved in respectively in the middle of the 25ml acetonitrile, mix down at 50 ℃, stirring reaction 2 hours, get the coupled product of dark solid pyridine nitric oxide and nitro diazonium salt, this coupled thing of 2.0g is dissolved in (50 ℃) in the hot acetonitrile of 30ml, dropwise add the 2.5ml triethylamine under stirring, post precipitation to be occurred, precipitation is leached, get the yellow needle-like crystal 1.2g of NCPPH, productive rate 60%.Mass spectrum shows molecular ion peak: 272.Ultimate analysis is by molecular formula C
18H
12N
2O calculated value: C:79.4%, H:4.4%, N:10.3%; Experimental value: C:79.9%, H:4.1%, N:10.9%.Example 6:BePP
2Synthetic
(BePP
2)
2.6g (14mmol) BeSO
44H
2O joins in the 20ml ethanol, and 5g (28mmol) PPH part is dissolved in 20ml in the alcohol, and above-mentioned two kinds of solution are mixed, add small amount of N aOH, the pH value that makes reaction mixture is 15, and stirring at room 2 hours has faint yellow precipitation to generate, leach precipitation, with ethanol give a baby a bath on the third day after its birth time (3 * 30ml), again with ether give a baby a bath on the third day after its birth time (3 * 20ml), air drying, after purifying, distillation gets product 4.2g, productive rate 85%.Mass spectrum shows molecular ion peak: 349.Ultimate analysis is by molecular formula C
22H
16N
2O
2Be calculated value: C:75.6%, H:4.6%, N:8.0%; Experimental value: C:76.1%, H:4.8%, N:7.7%.Example 7:PPGaCl
2Synthetic
(PPGaCl
2)
2.5g (14.2mmol) GaCl
3Join in the 20ml tetrahydrofuran (THF), 2.4g (14.2mmol) the PPH part is dissolved in the 10ml tetrahydrofuran (THF), above-mentioned two kinds of solution are mixed, stirring at room 5 hours, rotary evaporation goes out to desolvate, and obtains faint yellow solid, (3 * 30ml) give a baby a bath on the third day after its birth time with ether, air drying gets product 3.4g, productive rate 78% after distillation is purified.Mass spectrum shows molecular ion peak: 311.Ultimate analysis is by molecular formula C
11H
8NOCl
2Ga calculated value: C:42.4%, H:2.6%, N:4.5%; Experimental value: C:41.6%, H:2.2%, N:5.1%.Example 8:PPBF
2Synthetic
(PPBF
2)
2.1g (14.0mmol) BF
3O (C
2H
5)
2And 2.4g (14.2mmol) PPH part is dissolved in the 30ml tetrahydrofuran (THF), refluxes and stirs 5 hours, and rotary evaporation removes and desolvates, obtain faint yellow solid, with ether give a baby a bath on the third day after its birth time (3 * 30ml), air drying, after purifying, distillation gets product 4.4g, productive rate 82%.Mass spectrum shows molecular ion peak: 219.Ultimate analysis is by molecular formula C
11H
8NOF
2B calculated value: C:60.3%, H:3.6%, N:6.4%; Experimental value: C:59.6%, H:3.2%, N:6.7%.Example 9:DPPBF's is synthetic
(DPPBF)
4.3g (30.0mmol) BF
3O (C
2H
5)
2And 7.9g (30.0mmol) DPPH part is dissolved in into to 30mlCHCl
3In, reflux to stir 2 hours, rotary evaporation removes and desolvates, and obtains white solid, with ether give a baby a bath on the third day after its birth time (3 * 30ml), rotary evaporation drain dry after, after distillation is purified product 7.5g, productive rate 86%.Mass spectrum shows molecular ion peak: 291.Ultimate analysis is by molecular formula C
17H
11NO
2FB calculated value: C:70.1%, H:3.8%, N:4.8%; Experimental value: C:70.5%, H:3.8%, N:5.2%.Example 10:DPPBOME's is synthetic
(DPPBOMe)
4.3g (30.0mmol) BF
3O (C
2H
5)
2And 7.9g (30.0mmol) DPPH part is dissolved in into to 30mlCHCl
3In, reflux to stir 2 hours, rotary evaporation removes and desolvates, and obtains white solid, with ether give a baby a bath on the third day after its birth time (3 * 30ml), after rotary evaporation removes and desolvates, after distillation is purified product 6.4g, productive rate 70%.Mass spectrum shows molecular ion peak: 303.Ultimate analysis is by molecular formula C
18H
14NO
3B calculated value: C:71.3%, H:4.6%, N:4.6%; Experimental value: C:70.7%, H:4.5%, N:4.2%.Example 11:DPPBOET's is synthetic
DPPBOET)
4.3g (30.0mmol) BF
3O (C
2H
5)
2And 7.9g (30.0mmol) DPPH part is dissolved in into to 30mlCHCl
3In, reflux to stir 2 hours, rotary evaporation removes and desolvates, and obtains white solid, with ether give a baby a bath on the third day after its birth time (3 * 30ml), after rotary evaporation removes and desolvates, after distillation is purified product 7.6g, productive rate 80%.Mass spectrum shows molecular ion peak: 317.Ultimate analysis is by molecular formula C
19H
16NO
3B calculated value: C:71.9%, H:5.0%, N:4.4%; Experimental value: C:71.3%, H:5.1%, N:4.1%.Example 12:DMPPH's is synthetic
(DMPPH)
Under nitrogen protection; make solvent with THF (30ml); 4.0g (20mmol) 4-methyl-2-bromoanisole and excessive magnesium rod (＞20mmol) reaction; get final product the Grignard reagent of 4-methyl-2-bromoanisole; Grignard reagent is added drop-wise in 3.5g (20 mmol) 4-methyl-2-bromopyridine tetrahydrofuran (THF) (50ml) solution, and reaction mixture at room temperature stirs spend the night (12 hours).Add 15ml, the NH of 3M
4Behind the Cl aqueous solution, with the acidifying of 15ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(20ml) extraction is three times, and organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(4-methyl-2-methyl-phenoxide)-4-methyl-pyridine.Place it in the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage glass parent tube, 190 ℃ were heated 3 hours under nitrogen protection, added 50ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying is taken out to desolvate and is obtained the red-purple viscous solution under the decompression, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 2.8 grams, productive rate 72% with the cold water cooling.Mass spectrum shows molecular ion peak: 199.Ultimate analysis is by molecular formula C
13H
13NO calculated value: C:78.4%, H:6.5%, N:7.0%; Experimental value: C:78.9%, H:6.0%, N:7.5%.Example 13:Be (DMPP)
2Synthetic
Be (DMPP)
22.6g (14mmol) BeSO
44H
2O joins in the 20ml ethanol, and 5.6g (28mmol) DMPPH part is dissolved in 25ml in the alcohol, and above-mentioned two kinds of solution are mixed, add small amount of N aOH, the pH value that makes reaction mixture is 15, and stirring at room 2 hours has faint yellow precipitation to generate, leach precipitation, with ethanol give a baby a bath on the third day after its birth time (3 * 30ml), again with ether give a baby a bath on the third day after its birth time (3 * 20ml), air drying, after purifying, distillation gets product 3.7g, productive rate 65%.Mass spectrum shows molecular ion peak: 405.Ultimate analysis is by molecular formula C
26H
24N
2O
2Be calculated value: C:77.0%, H:5.9%, N:6.9%; Experimental value: C:76.4%, H:5.8%, N:7.2%.Example 14:MOPPH's is synthetic
MOPPH
Under nitrogen protection; make solvent with THF (30ml); 4.4g (20mmol) 4-methoxyl group-2-bromoanisole and excessive magnesium rod (＞20mmol) reaction; get final product the Grignard reagent of 4-methoxyl group-2-bromoanisole; Grignard reagent is added drop-wise in 3.8g (20mmol) 4-methoxyl group-2-bromopyridine tetrahydrofuran (THF) (50ml) solution, and reaction mixture at room temperature stirs spend the night (12 hours).Add 15ml, the NH of 3M
4Behind the Cl aqueous solution, with the acidifying of 15ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(20ml) extraction is three times, and organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(4-methoxyl group-2-methyl-phenoxide)-4-methoxyl group-pyridine.Place it in the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage glass parent tube, 190 ℃ were heated 3 hours under nitrogen protection, added 50ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying is taken out to desolvate and is obtained the red-purple viscous solution under the decompression, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 3.3 grams, productive rate 75% with the cold water cooling.Mass spectrum shows molecular ion peak: 231.Ultimate analysis is by molecular formula C
13H
13NO
3Calculated value: C:67.5%, H:5.6%, N:6.1%; Experimental value: C:68.1%, H:5.3%, N:5.8%.Example 15:Be (MOPP)
2Synthetic
Be(MOPP)
2
2.6g (14mmol) BeSO
44H
2O joins in the 20ml ethanol, and 7.0g (30mmol) MOPPH part is dissolved in 25ml in the alcohol, and above-mentioned two kinds of solution are mixed, add small amount of N aOH, the pH value that makes reaction mixture is 15, and stirring at room 2 hours has faint yellow precipitation to generate, leach precipitation, with ethanol give a baby a bath on the third day after its birth time (3 * 30ml), again with ether give a baby a bath on the third day after its birth time (3 * 20ml), air drying, after purifying, distillation gets product 4.6g, productive rate 70%.Mass spectrum shows molecular ion peak: 469.Ultimate analysis is by molecular formula C
26H
24N
2O
6Be calculated value: C:66.5%, H:5.1%, N:6.0%; Experimental value: C:65.9%, H:5.5%, N:5.6%.Example 16:NPPH's is synthetic
(NPPH)
Under nitrogen protection; make solvent with THF (30ml); 5.8g (25mmol) 4-dimethylin-2-bromoanisole and excessive magnesium rod (＞25mmol) reaction; get final product the Grignard reagent of 4-dimethylin-2-bromoanisole; Grignard reagent is added drop-wise in 4.0g (25mmol) 2-bromopyridine tetrahydrofuran (THF) (25ml) solution, and reaction mixture at room temperature stirs spend the night (12 hours).Add 15ml, the NH of 3M
4Behind the Cl solution, with the acidifying of 15ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(3 * 20ml) extractions three times, organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(4-dimethylin-2-methyl-phenoxide)-pyridine.Place it in the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage Glass tubing, 190 ℃ were heated 3 hours under nitrogen protection, added 30ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation are removed to desolvate and are obtained the red-purple viscous solution, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 4.0 grams, productive rate 75% with the cold water cooling.Mass spectrum shows molecular ion peak: 214.Ultimate analysis is by molecular formula C
13H
14N
2O calculated value: C:72.9%, H:6.5%, N:13.1%; Experimental value: C:72.0%, H:6.3%, N:12.7%.Example 17:Zn (NPP)
2Synthetic
Zn(NPP)
2
1.2g (9.0mmol) ZnCl
2Join in the 15ml tetrahydrofuran (THF), 3.9g (18mmol) the NPPH part is dissolved in the 10ml tetrahydrofuran (THF), above-mentioned two kinds of solution are mixed, stirring at room 5 hours, rotary evaporation removes and desolvates, and obtains faint yellow solid, give a baby a bath on the third day after its birth inferior (3 * 20ml) with ether, air drying gets product 2.7g, productive rate 63% after distillation is purified.Mass spectrum shows molecular ion peak: 491.Ultimate analysis is by molecular formula C
26H
26N
4O
2Zn calculated value: C:63.5%, H:5.3%, N:11.4%; Experimental value: C:62.9%, H:5.2%, N:12.1%.Example 18:PPPH's is synthetic
(PPPH)
Under nitrogen protection; make solvent with 30ml THF; 5.6g (30mmol) 2-bromoanisole and excessive magnesium rod (＞30mmol) reaction; get final product the Grignard reagent of 2-bromoanisole; Grignard reagent is added drop-wise in 7.0g (30mmol) 4-phenyl-2-bromopyridine tetrahydrofuran (THF) (30ml) solution, and reaction mixture at room temperature stirs spend the night (12 hours).Add 30ml, the NH of 3M
4Behind the Cl aqueous solution, with the acidifying of 20ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(3 * 20ml) extractions three times, organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(2-methyl-phenoxide)-4-phenyl--pyridine.Place it in the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage Glass tubing, 190 ℃ were heated 3 hours under nitrogen protection, added 30ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation are removed to desolvate and are obtained the red-purple viscous solution, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 6.1 grams, productive rate 83% with the cold water cooling.Mass spectrum shows molecular ion peak: 247.Ultimate analysis is by molecular formula C
17H
13NO calculated value: C:82.6%, H:5.3%, N:5.7%; Experimental value: C:82.0%, H:5.0%, N:6.2%.Example 19:Be (PPP)
2Synthetic
Be(PPP)
2
2.6g (14mmol) BeSO
44H
2O joins in the 20ml ethanol, and 7.0g (28mmol) PPH part is dissolved in 30ml in the alcohol, and above-mentioned two kinds of solution are mixed, add small amount of N aOH, the pH value that makes reaction mixture is 15, and stirring at room 2 hours has faint yellow precipitation to generate, leach precipitation, with ethanol give a baby a bath on the third day after its birth time (3 * 20ml), again with ether give a baby a bath on the third day after its birth time (3 * 25ml), air drying, after purifying, distillation gets product 5.2g, productive rate 75%.Mass spectrum shows molecular ion peak: 501.Ultimate analysis is by molecular formula C
34H
24N
2O
2Be calculated value: C:81.4%, H:4.8%, N:5.6%; Experimental value: C:80.2%, H:5.2%, N:6.1%.Example 20:PYPPH's is synthetic
(PYPPH)
Under nitrogen protection; make solvent with THF (30ml); 8.0g (30mmol) 4-is than pyridine base-2-bromoanisole and the (＞30mmol) reaction of excessive magnesium rod; get final product 4-than the Grignard reagent of pyridine base-2-bromoanisole; Grignard reagent is added drop-wise in 4.7g (30mmol) 2-bromopyridine tetrahydrofuran (THF) (30ml) solution, and reaction mixture at room temperature stirs spend the night (12 hours).Add 20ml, the NH of 3M
4Behind the Cl solution, with the acidifying of 40ml concentrated hydrochloric acid, rotary evaporation is removed THF then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(3 * 20ml) extractions three times, organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtaining tawny oily matter is 2-(4-is than pyridine base-2-methyl-phenoxide)-pyridine.Place it in the 50ml concentrated hydrochloric acid, and enclose in the withstand voltage Glass tubing, 190 ℃ were heated 3 hours under nitrogen protection, added 40ml water then in mixture, were neutralized to neutrality with the KOH solvent again, used CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation removes and desolvates, and obtains the red-purple viscous solution, and viscous solution is purified with silica gel column chromatography, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 5.0 grams, productive rate 71% with the cold water cooling.Mass spectrum shows molecular ion peak: 248.Ultimate analysis is by molecular formula C
16H
12N
2O calculated value: C:77.4%, H:4.8%, 11.3%; Experimental value: C:78.0%, H:5.2%, N:10.7%.Example 21:Zn (PYPP)
2Synthetic
Zn(PYPP)
2
2g (9.0mmol) ZnCl
2Join in the 15ml tetrahydrofuran (THF), 4.5g (18mmol) the PYPPH part is dissolved in the 10ml tetrahydrofuran (THF), above-mentioned two kinds of solution are mixed, stirring at room 5 hours, the decompressing and extracting solvent obtains faint yellow solid, give a baby a bath on the third day after its birth inferior (3 * 30ml) with ether, air drying gets product 3.2g, productive rate 63% after distillation is purified.Mass spectrum shows molecular ion peak: 559.Ultimate analysis is by molecular formula C
32H
22N
4O
2Zn calculated value: C:68.7%, H:3.9%, N:10.0%: experimental value: C:68.0%, H:4.2%, N:9.5%.Example 22:DPMPH's is synthetic
(DPMPH)
Under nitrogen protection; make solvent with THF (30ml); 8.5g (45mmol) 2-bromoanisole and excessive magnesium rod (＞45mmol) reaction; get final product the Grignard reagent of 2-bromoanisole; Grignard reagent is added drop-wise to 11.3g (45mmol) 4-methyl-2; in 6-dibromo pyridine tetrahydrofuran (THF) (30ml) solution, reaction mixture at room temperature stirs spend the night (12 hours).Add 20ml, the NH of 3M
4Behind the Cl solution, with the acidifying of 20ml concentrated hydrochloric acid, rotary evaporation removes the THF in desolvating then.The water layer that stays is neutralized to neutrality with KOH, uses CH
2Cl
2(3 * 20ml) extractions three times, organic layer is a tawny, uses anhydrous Na
2SO
4Dried overnight, rotary evaporation is removed CH
2Cl
2, obtain tawny oily matter.Above-mentioned product is placed the 50ml concentrated hydrochloric acid, and the following 190 ℃ of heating of nitrogen protection 3 hours add 30ml water then in mixture, be neutralized to neutrality with the KOH solvent again, use CH
2Cl
2(3 * 20ml) extraction crude products, anhydrous MgSO
4Drying, rotary evaporation are removed to desolvate and are obtained the red-purple viscous solution, and viscous solution is purified with silica gel chromatographic column, pure CHCl
3Be elutriant, obtain yellow viscous solution, obtain faint yellow solid, 8.1 grams, productive rate 65% with the cold water cooling.Mass spectrum shows molecular ion peak: 277.Ultimate analysis is by molecular formula C
18H
15NO
2Calculated value: C:78.0%, H:5.4%, N:5.1%; Experimental value: C:78.5%, H:5.3%, N:5.2%.Example 23:DPMPBF's is synthetic
(DPMPBF)
4.3g (30.0mmol) BF
3O (C
2H
5)
2And 8.3g (30.0mmol) DPMPH part is dissolved in into to 30mlCHCl
3In, reflux to stir 2 hours, the decompressing and extracting solvent obtains white solid, with ether give a baby a bath on the third day after its birth time (3 * 20ml), behind the drying under reduced pressure, after distillation is purified product 7.0g, productive rate 76%.Mass spectrum shows molecular ion peak: 305.Ultimate analysis is by molecular formula C
18H
13NO
2FB calculated value: C:70.8%, H:4.3%, N:4.6%; Experimental value: C:71.3%, H:4.1%, N:5.0%.Example 24: luminescent device [ITO/TPD/BePP
2/ Mg: Ag]
TPD
First evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 500 , then evaporation one deck BePP
2Luminescent layer, thickness are 400 , the Mg/Ag alloy (consequent pole) of 2000 on the last evaporation, Mg: Ag=10: 1 (volume ratio).In evaporate process, keep 5 * 10
-6Torr.Under forward bias, this device blue light-emitting (450nm), cut-in voltage is 4 volts, brightness can reach 1000cd/m
2, luminous efficiency is 0.31m/w.Example 25: luminescent device [ITO/TPD/BePP
2/ FLi/Al]
First evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 500 , then evaporation one deck BePP
2Luminescent layer, thickness are 400 , again the FLi of evaporation one deck 10 , the metal A l (consequent pole) of 2000 on the evaporation at last.In evaporate process, keep 6 * 10
-6Torr.Under forward bias, this device blue light-emitting (450nm), cut-in voltage is 4 volts, brightness can reach 800cd/m
2, luminous efficiency is 0.331m/w.Example 26: luminescent device [ITO/TPD/DPPBF
2/ Al]
First evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 500 , then evaporation one deck DPPBF
2Luminescent layer, thickness are 400 , the metal A l (consequent pole) of 2000 on the last evaporation.In evaporate process, keep 6 * 10
-6Torr.Under forward bias, this device jaundice light (550nm), cut-in voltage is 3.5 volts, brightness can reach 100cd/m
2, luminous efficiency is 0.051m/w.Example 27: luminescent device [ITO/PVK/DPPBF
2/ Al]
PVK
First spin coating one deck PVK hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 1000 , then evaporation one deck DPPBF
2Luminescent layer, thickness are 400 , the metal A l (consequent pole) of 2000 on the last evaporation.In evaporate process, keep 6 * 10
-6Torr.Under forward bias, this device blue light-emitting (445nm), cut-in voltage is 4.0 volts, brightness can reach 200cd/m
2, luminous efficiency is 0.1lm/w.Example 28: luminescent device [ITO/TPD/BePP
2: (mbpy) Re (CO)
3Cl/Al]
(mbpy)Re(CO)
3Cl
First evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 500 , is total to evaporation last layer BePP then
2(96wt%): (mbpy) Re (CO)
3Cl (4wt%) luminescent layer, thickness is 400 , the metal A l (consequent pole) of 2000 on the last evaporation.In evaporate process, keep 4 * 10
-6Torr, under forward bias, this device jaundice light (545nm), cut-in voltage is 3.5 volts, brightness can reach 3000cd/m
2, luminous efficiency is 1.51m/w.Example 29: luminescent device [ITO/TPD/BePP
2: PPGaCl
2/ Al]
First evaporation one deck TPD hole transmission layer on the glass substrate that is coated with ITO (tin indium oxide) (positive pole), thickness is 500 , is total to evaporation last layer BePP then
2(30wt%):: PPGaCl
2(70wt%) luminescent layer, thickness are 400 , the metal A l (consequent pole) of 2000 on the last evaporation.In evaporate process, keep 4 * 10
-6Torr, under forward bias, this device jaundice light (545nm), cut-in voltage is 4.5 volts, brightness can reach 100cd/m
2Example 30: luminescent device [ITO/PVK:PPBF
2/ Al]
First spin coating last layer PVK (contains 5%PPBF on the glass substrate that is coated with ITO (tin indium oxide) (positive pole)
2), its thickness is this 150nm, at evaporation last layer metal A l, thickness is 200nm then.In evaporate process, keep 4 * 10
-6Torr, 3 volts of the cut-in voltages of this single layer device, brightness can reach 500cd/m
2
Claims (5)
1. the organic ligand shown in the general formula (1) is the metal complexes of phenolic group-pyridine and derivative thereof,
Its Chinese style (O) representative with the phenylol be the basic structure skeleton fragrant monocycle, encircle and heterocyclic system more;
Formula (N) representative with the pyridine group be the basic structure skeleton monocycle, encircle and heterocyclic system more;
R
1And R
2Can be identical or different, be alkyl, alkoxyl group, aromatic nucleus, aromatic heterocycle, organic amine.
Bidentate or multiple tooth chelating ligand that formula (L) representative is linked to each other and forms by singly-bound by phenylol derivative and pyridinyl derivatives, ligating atom is oxygen and nitrogen;
In the formula (1), M is selected from Zn
2+, Be
2+, B
3+, Al
3+Or Ga
3+In a kind of, n=1 or 2.
2. compound according to claim 1 (1) is characterized in that: the phenolic group (O) and the pyridyl (N) that form part (L) are fragrant single ring architecture.
3. compound according to claim 1 and 2 (1) is characterized in that phenolic group pyridine and derivative ligand thereof and a central metallic ions coordination form mononuclear coordination compound.
4. compound according to claim 1 and 2 (1) can be used for preparing the electroluminescent device of blue light-emitting, ruddiness, gold-tinted.
5. compound according to claim 3 (1) can be used for preparing the electroluminescent device of blue light-emitting, ruddiness, gold-tinted.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99118700A CN1107098C (en) | 1999-09-05 | 1999-09-05 | Phenolic group-pyridine or metal coordination compound of its derivative and their application as electroluminescence material |
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| CN1107098C true CN1107098C (en) | 2003-04-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341879C (en) * | 2004-12-10 | 2007-10-10 | 吉林大学 | Complexes of phenolic group-pyridine boron and application as electroluminescence material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100492243B1 (en) * | 2000-03-31 | 2005-05-31 | 캐논 가부시끼가이샤 | Organic luminescence device using novel organic boron compound, and process for producing the device |
| US6461749B2 (en) * | 2000-03-31 | 2002-10-08 | Canon Kabushiki Kaisha | Organic boron compound, process for producing the compound and organic luminescence device using the compound |
| US20020121638A1 (en) * | 2000-06-30 | 2002-09-05 | Vladimir Grushin | Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds |
| US7033681B2 (en) | 2004-03-18 | 2006-04-25 | Eastman Kodak Company | Organic element for electroluminescent devices |
| KR100846596B1 (en) * | 2007-01-18 | 2008-07-16 | 삼성에스디아이 주식회사 | Heterocycle containing organometallic complex and an organic light emitting device comprising the same |
| JP2008195623A (en) * | 2007-02-08 | 2008-08-28 | Chemiprokasei Kaisha Ltd | Novel hydroxyphenyl metal derivative comprising heterocycle, and electron injection material, electron transporting material and organic electroluminescent device each employing the same |
| US8900722B2 (en) | 2007-11-29 | 2014-12-02 | Global Oled Technology Llc | OLED device employing alkali metal cluster compounds |
| BE1020676A3 (en) * | 2012-05-08 | 2014-03-04 | Agc Glass Europe | ORGANIC PHOTONIC DEVICE |
| JP2013028600A (en) * | 2012-07-20 | 2013-02-07 | Chemiprokasei Kaisha Ltd | Novel heterocycle-containing hydroxyphenyl metal derivative, and electron injecting material, electron transporting material, and organic electroluminescence element using the same |
| JP6607597B2 (en) * | 2015-07-31 | 2019-11-20 | 国立大学法人山形大学 | Novel organic lithium complex compound, electron injection material comprising the same, and organic EL device using the same |
| CN113105491B (en) * | 2021-04-13 | 2023-06-23 | 浙江虹舞科技有限公司 | Pyridine diphenoxy boron fluoride compound, application thereof and organic electroluminescent device containing compound |
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| US4539507A (en) * | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
| US4720432A (en) * | 1987-02-11 | 1988-01-19 | Eastman Kodak Company | Electroluminescent device with organic luminescent medium |
| US5150006A (en) * | 1991-08-01 | 1992-09-22 | Eastman Kodak Company | Blue emitting internal junction organic electroluminescent device (II) |
| CN1216556A (en) * | 1996-04-17 | 1999-05-12 | 德国赫彻斯特研究技术两合公司 | Polymers with spiro atoms and their use as electroluminescent materials |
-
1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539507A (en) * | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
| US4720432A (en) * | 1987-02-11 | 1988-01-19 | Eastman Kodak Company | Electroluminescent device with organic luminescent medium |
| US5150006A (en) * | 1991-08-01 | 1992-09-22 | Eastman Kodak Company | Blue emitting internal junction organic electroluminescent device (II) |
| CN1216556A (en) * | 1996-04-17 | 1999-05-12 | 德国赫彻斯特研究技术两合公司 | Polymers with spiro atoms and their use as electroluminescent materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341879C (en) * | 2004-12-10 | 2007-10-10 | 吉林大学 | Complexes of phenolic group-pyridine boron and application as electroluminescence material |
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