CN101469003B - Metal organic complexes, preparation thereof, luminescent material and luminescent device - Google Patents
Metal organic complexes, preparation thereof, luminescent material and luminescent device Download PDFInfo
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- CN101469003B CN101469003B CN200710161057XA CN200710161057A CN101469003B CN 101469003 B CN101469003 B CN 101469003B CN 200710161057X A CN200710161057X A CN 200710161057XA CN 200710161057 A CN200710161057 A CN 200710161057A CN 101469003 B CN101469003 B CN 101469003B
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Abstract
The invention relates to complexes, a preparation method thereof, and a luminescent material and a luminescent device. The invention provides metal organic complexes and a preparation method thereof, and the luminescent material containing the complexes and an organic electroluminescent device. The complexes are compounds shown by general formula (1), wherein R1 can be a hydrogen atom, methyl, ethyl, propyl or butyl; R2 can be cyan, trifluoromethyl, a fluorine atom or a hydrogen atom; and R3 can be cyan, trifluoromethyl, a fluorine atom or a hydrogen atom. The provided luminescent material and the organic electroluminescent device have the luminescence peak position in the standard yellow light range, and have high luminescence and high luminescent efficiency.
Description
Technical field
The invention relates to a kind of title complex and preparation method thereof and luminescent material and luminescent device, more specifically about a kind of a metal-organic complex and preparation method thereof and luminescent material and organic electroluminescence device.
Background technology
Organic electroluminescence device (OLED) is a kind of new display spare, generally comprises substrate, anode layer, luminescent layer and cathode layer.Apply certain voltage between electrode, device just can be luminous.
One of yellow is the color that equivalent ruddiness and green glow are formed, rather than three primary colors " RGB ".In chromatics, gold-tinted is that the blue light in the white light is filtered out formation, also often becomes the auxiliary photochromic of blue light.Otherwise, can obtain white light with blue light by mixing yellow.
White light particularly has important use to be worth in a lot of fields in the organic electroluminescence device.In the full-color active oled panel development of high resolution, white light variegates spectral filter owing to do not need to use micro-image light cover, and is applicable to large substrate, therefore has good application prospects.At present the utilization sky blue that uses in the oled panel adds the commercialization requirement that white light source that yellow obtains can reach high-level efficiency and high stability.Therefore yellow electroluminescent organic material has also caused people's attention.
Contain the misfit thing that heavy metal atom is formed in the phosphor material mostly, utilize heavy atoms effect, the coupling of intensive spin orbital causes the energy level intermingling of singlet excited and triplet excited state, feasible originally forbidden triplet energies is alleviated and is given out light with the form of phosphorescence, the exciton energy of singlet excited and triplet excited state can be used in give out light formal, and quantum yield also will significantly promote thereupon.The novel yellow phosphorescence material of development research with improving the luminous efficiency of organic electroluminescence device, promotes further developing of organic electroluminescent technology.
5,6,11,12-tetraphenyl four benzos (Rubrene) are present best yellow material, have stronger hole capture ability, realize that more easily current carrier shifts, and the main glow peak of this material is positioned at 564 nanometers.In (Wang Jin etc., liquid crystal and demonstration, in December, 2006), introduced the luminescent device of doping yellow fluorescent material Rubrene in " making of the two luminous zones of doping Rubrene organic yellow optical device ".The high-high brightness of the luminescent device that obtains according to the introduction method of this article under 18 volts be 16640 may moral draw/square metre, efficient is 4.2 to bear moral and draw/pacify when 8 volts voltage, chromaticity coordinates is (0.50,0.47).Yet yellow emission peak position, luminosity and the luminous efficiency of this material are still not ideal enough.
Summary of the invention
The object of the present invention is to provide a kind of luminous peak position to be in the luminescent material that standard yellow light is launched, had high brightness and high-luminous-efficiency.
The invention provides a kind of a metal-organic complex, wherein, this title complex is the compound by general formula (1) expression:
General formula (1)
Wherein, R
1Be hydrogen atom (H), methyl (CH
3), ethyl (C
2H
5), propyl group (C
3H
7) or butyl (C
4H
9); R
2Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
3Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H).
The present invention also provides the preparation method of this a metal-organic complex, wherein, this method is included under the condition of one or more materials existence in alkali-metal oxyhydroxide, carbonate and the supercarbonate, compound that will be shown in general formula (2) and the compound reflux in organic solvent shown in general formula (3), obtain described a metal-organic complex
General formula (2)
General formula (3)
Wherein, R
1Be hydrogen atom (H), methyl (CH
3), ethyl (C
2H
5), propyl group (C
3H
7) or butyl (C
4H
9); R
2Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
3Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H).
The present invention also provides a kind of luminescent material, and this luminescent material contains a kind of a metal-organic complex, and wherein, this title complex is an a metal-organic complex provided by the invention.
The present invention also provides a kind of organic electroluminescence device, and this organic electroluminescence device comprises substrate, anode layer, luminescent layer and cathode layer, and wherein, described luminescent layer is a luminescent material provided by the invention.
According to luminescent material provided by the invention and organic electroluminescence device, its luminous peak position is in the standard yellow light scope, has high brightness and high-luminous-efficiency.
Description of drawings
Fig. 1 is the structural representation of organic electroluminescence device.
Fig. 2 is the PL spectrogram (photoluminescence spectra figure) of a metal-organic complex A1.
Fig. 3 is the EL spectrogram (electroluminescent spectrum figure) of luminescent device B1.
Fig. 4 is the EL spectrogram (electroluminescent spectrum figure) of luminescent device B2.
Fig. 5 is the EL spectrogram (electroluminescent spectrum figure) of luminescent device B3.
Embodiment
According to a metal-organic complex provided by the invention, this title complex is the compound by general formula (1) expression:
General formula (1)
Wherein, R
1Be hydrogen atom (H), methyl (CH
3), ethyl (C
2H
5), propyl group (C
3H
7) or butyl (C
4H
9); R
2Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
3Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H).
Under the preferable case, according to the present invention, described a metal-organic complex is, 1-phenyl isoquinolin quinoline-2-pyridine carboxylic acid closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-5-cyanopyridine closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-5-5-flumethiazine closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-5-fluorine pyridine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-5-cyanopyridine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-5-5-flumethiazine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-5-cyanopyridine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-5-5-flumethiazine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-5-cyanopyridine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-5-5-flumethiazine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-cyanopyridine closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-5-flumethiazine closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-4-cyanopyridine closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-4-5-flumethiazine closes platinum, 1-phenyl isoquinolin quinoline-2-formic acid-4-fluorine pyridine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-4-cyanopyridine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum, 1-(4-aminomethyl phenyl) isoquinoline 99.9-2-formic acid-4-fluorine pyridine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-4-cyanopyridine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum, 1-(4-ethylphenyl) isoquinoline 99.9-2-formic acid-4-fluorine pyridine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-4-cyanopyridine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum, 1-(4-propyl group phenyl) isoquinoline 99.9-2-formic acid-4-fluorine pyridine closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-cyanopyridine closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum, or 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-fluorine pyridine closes platinum.
Under the further preferred situation, described title complex is that 1-phenyl isoquinolin quinoline-2-pyridine carboxylic acid closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, or 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum.
Preparation method according to a metal-organic complex provided by the invention, this method is included under the condition of one or more materials existence in alkali-metal oxyhydroxide, carbonate and the supercarbonate, compound that will be shown in general formula (2) and the compound reflux in organic solvent shown in general formula (3), obtain described a metal-organic complex
General formula (2)
General formula (3)
Wherein, R
1Be hydrogen atom (H), methyl (CH
3), ethyl (C
2H
5), propyl group (C
3H
7) or butyl (C
4H
9); R
2Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
3Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H).
The theoretical consumption of compound shown in general formula (2) and the compound shown in general formula (3) is mol ratio 1: 2-2.5, in order to improve the productive rate of reaction, under the preferable case, the consumption of compound (2) and the compound shown in general formula (3) is mol ratio 1: 2-4, more preferably 1: 2.5-3.
The consumption of described alkali-metal oxyhydroxide, carbonate and supercarbonate makes the pH value of reaction system be shown as weakly alkaline, under the preferable case, the consumption of one or more materials in described alkali-metal oxyhydroxide, carbonate and the supercarbonate makes the pH value of reaction system be 8-10.Described alkali-metal oxyhydroxide, carbonate and supercarbonate can be in potassium hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash, saleratus, the sodium bicarbonate one or more.
Described organic solvent is conventional organic solvent, cellosolvo, 1 for example, and 2-propylene glycol, ethanol, glycol monoethyl ether are preferably cellosolvo.The consumption of organic solvent is not particularly limited, as long as guarantee to mix with above-mentioned reactant, generally, the compound shown in general formula (2) and the weight ratio of solvent are 1: 15-50 is preferably 1: 20-30.
The condition of described reflux can be preferably 15-25 hour for backflow 10-30 under the condition of protection of inert gas hour, and the temperature of backflow is 85-100 ℃, is preferably 90-95 ℃.Described rare gas element can be any gas that does not participate in reacting, and is preferably the gas of nitrogen or neutral element.
According to the present invention, the method of a metal-organic complex that separation and purification obtains can adopt the separation purification method of the various routines of this area, as methods such as chromatographies, the concrete operation method of separation and purification and condition are conventionally known to one of skill in the art, and those skilled in the art can select suitable condition according to the actually operating needs.
Described compound shown in general formula (2) can be by following reaction scheme 1 preparation.
Wherein, R
1Be hydrogen atom (H), methyl (CH
3), ethyl (C
2H
5), propyl group (C
3H
7) or butyl (C
4H
9).
Wherein, pyridine derivate can by and thionaphthene boric acid or its derivative under the condition that catalyzer exists; in the mixture of first organic solvent and water, react; separate the compound shown in general formula (4) that generates; compound that again will be shown in general formula (4) and Tetrachloroplatinum under the protection of inert gas condition in the mixture of second organic solvent and water reflux; reaction soln is filtered, obtain the compound shown in general formula (2).
The theoretical consumption of pyridine derivate and thionaphthene boric acid or its derivative is mol ratio 1: 1, in order to improve the productive rate of reaction, under the preferable case, the consumption of pyridine derivate and thionaphthene boric acid or its derivative is mol ratio 1: 1.1-1.4, more preferably 1: 1.2-1.3.Described catalyzer can be four (triphenyl phosphorus) palladium, palladium, dichloro two (thricyclohexyl phosphorus), Pd (Pt-Bu)
3, in the palladium/carbon catalyst one or more, be preferably four (triphenyl phosphorus) palladium; Weight with pyridine derivate is benchmark, and catalyst consumption is 1-6 weight %, is preferably 2-4 weight %.Described first organic solvent can for arbitrarily not with water-soluble organic solvent, as in benzene,toluene,xylene, the trichloromethane one or more, be preferably toluene; First organic solvent and water blended ratio are 1: 0.5-2 is preferably 1: 0.9-1.2; The amount of described first organic solvent is not particularly limited, as long as guarantee to mix with above-mentioned reactant, generally, the weight ratio of pyridine derivate, first organic solvent and water is 1: 20-60: 20-60 is preferably 1: 30-50: 30-50.According to the present invention, the various separation methods that the 1-phenyl isoquinolin quinoline shown in general formula (4) that generates or the isolating method of its derivative can be adopted this area routine, as methods such as washing, separatory and extractions, isolating concrete operation method and condition are conventionally known to one of skill in the art.
The theoretical consumption of Tetrachloroplatinum and the reaction of the compound shown in general formula (4) is mol ratio 1: 2, in order to improve the productive rate of reaction, under the preferable case, the consumption of Tetrachloroplatinum and the compound shown in general formula (4) reaction is 1: 2.3-5, more preferably 1: 2.5-3.Described rare gas element can be any gas that does not participate in reacting, and is preferably the gas of nitrogen or neutral element.The temperature that refluxes is 85-100 ℃, is preferably 90-95 ℃; The time of refluxing is 10-30 hour, is preferably 15-25 hour.Second solvent is a cellosolvo, 1, and one or more in 2-propylene glycol, ethanol, the glycol monoethyl ether are preferably cellosolvo; Second organic solvent and water blended ratio are 1: 0.2-0.5 is preferably 1: 0.3-0.4; The amount of second organic solvent is not particularly limited, as long as guarantee to mix with above-mentioned reactant, generally, the weight ratio of the compound shown in general formula (4), first organic solvent and water is 1: 15-50: 5-25 is preferably 1: 20-30: 7-10.
Described compound shown in general formula (3) can obtain by commercial the purchase, or according to following reaction scheme 2 preparations.
R
2Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
3Be cyano group (CN), trifluoromethyl (CF
3), fluorine atom (F) or hydrogen atom (H); R
4Be bromine atoms.
Wherein, pyridine derivate and potassium acetate under the condition that cupric iodide exists, in organic solvent, are carried out first reflux under protection of inert gas; obtain the compound shown in general formula (5); it is separated the back in the aqueous solution, under the condition that potassium permanganate exists, carry out second reflux; obtain the compound shown in general formula (6); filter, then pH value of filtrate is transferred to 3-4 after, product is separated.
The theoretical consumption of described pyridine derivate and potassium acetate reaction is mol ratio 1: 1, and in order to improve the productive rate of reaction, the consumption of pyridine derivate and potassium acetate reaction is mol ratio 1: 1.1-1.5, is preferably 1: 1.2-1.4.Pyridine derivate and cupric iodide consumption are mol ratio 1: 1.1-1.8, are preferably 1: 1.4-1.6.Described organic solvent is one or more in dimethyl formamide, dioxane, the dimethyl sulfoxide (DMSO), is preferably dimethyl formamide.Described rare gas element can be any gas that does not participate in reacting, and is preferably nitrogen and neutral element gas.The temperature of described reflux can be 120-150 ℃, is preferably 140-145 ℃, and the time of backflow can be 10-20 hour, is preferably 14-16 hour.2-picoline shown in general formula (5) or the isolating method of 2-pyridine derivatives are conventional separation method, and as extraction, separatory, washing, drying, filtration and vacuum fractionation, its method is conventionally known to one of skill in the art.
Under the preferable case, described potassium permanganate adds in the solution in batches, and reaction is preferably carried out under stirring condition.Reaction times is 0.3-2 hour, is preferably 0.5-1 hour.The method of regulator solution pH value is conventionally known to one of skill in the art, as add an amount of concentrated hydrochloric acid solution in solution.Described isolating method is an ordinary method, and as filtering, underpressure distillation, backflow, lyophilize and drying, its method are conventionally known to one of skill in the art.
According to luminescent material provided by the invention, this luminescent material contains a kind of a metal-organic complex, and wherein, described title complex is an a metal-organic complex provided by the invention.
According to the present invention, described luminescent material also contains material of main part, is benchmark with the weight of described material of main part, and the content of described a metal-organic complex is 0.1-10 weight %, is preferably 2-5 weight %.
Described material of main part can be for well known to a person skilled in the art the material of main part of various routines, as, can be selected from Polyvinyl carbazole (PVK), poly-fluorenes (PFO), polyparaphenylene's derivative (as CN-PPP), tertiary butyl xenyl phenyl diazole (PBD) and a phenyl-4 (1-naphthyl)-5-phenyl-1,2,4-tripyrrole (TAZ) (Jiang C Y, Yang W, Peng J B, Xiao S, Cao Y.Adv Mater, 2004,16,573) one or more in; Under the preferable case, the material of main part in the used luminescent material of the present invention is Polyvinyl carbazole (PVK), shown in the following general formula of its structure (7).Because described Polyvinyl carbazole (PVK) is a kind of unconjugated polymkeric substance, its hole migration better performances, hole mobility is about 10
-5Cm
2V
-1S
-1High glass transition (176 ℃), film-forming properties are preferably arranged, and it dissolves in the multiple organic solvent, as benzene, chloroform, methylene dichloride, tetrahydrofuran (THF), toluene and chlorobenzene etc., so the present invention preferably adopts Polyvinyl carbazole (PVK) as the material of main part in the organic electroluminescence device luminescent material.
General formula (7)
The material of main part in the described luminescent material and the weight ratio of doping agent can be the mixing and doping ratio of routine.According to the present invention, be benchmark with the weight of described material of main part, the content of described a metal-organic complex is 0.1-10 weight %, is preferably 2-5 weight %.
According to organic electroluminescence device provided by the invention, this organic electroluminescence device comprises substrate, anode layer, luminescent layer and cathode layer successively, and wherein, described luminescent layer is a luminescent material provided by the invention.
As shown in Figure 1, the structure of described organic electroluminescence device is conventionally known to one of skill in the art, generally speaking, described organic electroluminescence device comprises substrate 1, anode layer 2, luminescent layer 3 and cathode layer 4, and described substrate 1, anode layer 2, luminescent layer 3 and cathode layer 4 are connected successively.When applying voltage between two electrodes, luminescent layer will be luminous.
Described luminescent layer 3 comprises luminescent material, and described luminescent material generally comprises material of main part and doping agent, and described doping agent can be a metal-organic complex, as phosphor material.According to the present invention, described luminescent layer is a luminescent material provided by the invention.
The thickness of described luminescent layer can be its conventional thickness, for example, can be the 10-120 nanometer, is preferably the 30-100 nanometer.
Organic electroluminescence device provided by the invention can be by known prepared in various methods with luminescent layer, for example, and method of spin coating, ink jet printing method or vacuum vapour deposition.When using method of spin coating and ink jet printing method, described material of main part and a metal-organic complex can be mixed and add an amount of solvent and make solution or slurry, on bottom, drying can obtain luminescent layer with this solution or slurry rotary coating or ink jet printing.Can determine the blending ratio of the two according to the required content of material of main part in the luminescent layer and a metal-organic complex.Vacuum vapour deposition is included under the vacuum condition, material of main part and a metal-organic complex are placed respectively independently on the heating source, with material of main part and a metal-organic complex simultaneously evaporation to bottom, form luminescent layer.It is 10 that described vacuum condition generally comprises absolute pressure
-7To 10
-6Handkerchief.Can determine the evaporation rate (weight of evaporation in the unit time) of the two according to material of main part in the luminescent layer and the required content of a metal-organic complex.Generally speaking, the ratio of the evaporation rate of material of main part and a metal-organic complex is identical with the ratio of each components contents in the luminescent layer.
Because the method for normal temperature spin coating does not need hot conditions, therefore to not influence of organic materials, simultaneously, the equipment of this method is simple, helps reducing cost, and therefore, the present invention preferably adopts the method for normal temperature spin coating to prepare organic luminous layer.
Serve as reasons except luminescent layer 3 and to adopt the luminescent material preparation of the present invention, other structure of organic electroluminescence device of the present invention can be identical with the organic electroluminescence device of routine.
The kind of described substrate 1 can generally be made by transparent material for the substrate in the organic electroluminescence device of various routines, as, can be glass, quartz or polyethylene terephthalate (PET).
Under the preferable case, between anode layer 2 and luminescent layer 3, can also there be hole injection layer and hole transmission layer with this.Hole injection layer and hole transmission layer have been conventionally known to one of skill in the art.Hole injection layer is formed on the anode layer, the general poly-dioxoethyl thiophene/poly-p styrene sulfonic acid (PEDOT:PSS) that adopts, and the thickness of hole injection layer 3 is preferably the 3-30 nanometer.Wherein, the structural formula of described PEDOT:PSS is as shown in the formula shown in (8).
General formula (8)
Hole transmission layer and cathode layer 4 can adopt known method to form, for example vacuum vapour deposition.Described vacuum vapour deposition has been conventionally known to one of skill in the art, does not repeat them here.
To specifically describe the present invention by embodiment below.
Present embodiment is used to illustrate a metal-organic complex provided by the invention.
As a specific embodiments of the present invention, embodiment 1 prepares a metal-organic complex Al according to reaction scheme 3, and 1-phenyl isoquinolin quinoline-2-pyridine carboxylic acid closes platinum [PPtpic].
Concrete grammar is, (1) get 1-chlorine isoquinoline 99.9 10 millis and rub, phenylo boric acid 14 millis rub, and four (triphenyl phosphorus) palladium, 0.1 milli rubs, yellow soda ash 30 millis rub, 30 milliliters of toluene, 30 ml waters place 250 ml flasks, stir, 90 degree left and right sides water-baths, reacted 4 hours, and told organic phase, water extracts 1 time with 20 milliliters of toluene.Merge organic phase, be washed to neutrality, the decompression desolventizing gets brown solid.It is dissolved in 30 milliliters of sherwood oils, and silica gel column chromatography, desolventizing get white solid 1.85 gram 1-phenyl isoquinolin quinolines.
(2) add in round-bottomed flask that Tetrachloroplatinum 20 millis rub and step (1) in the 1-phenyl isoquinolin quinoline 10 that obtains rub in the least, at N
2Protection adds 20 milliliters of 60 milliliters of cellosolvos and distilled water, reflux 24 hours down.Reaction solution is cooled to room temperature, filters, and precipitation is used cold dehydrated alcohol respectively, and washing with acetone obtains yellow powder 1.06 grams through vacuum-drying, is 1-phenyl isoquinolin quinoline dipolymer.
(3) in the 50ml round-bottomed flask, add the 0.5 milli 1-phenyl isoquinolin quinoline dipolymer, 1.5 millis that obtain in the step (2) pyridine carboxylic acid and the 6 millis anhydrous Na of rubbing of rubbing of rubbing
2CO
3(6mmol), at N
2Protection is injected cellosolvo (25ml) down, reflux 13h, and reaction is cooled to room temperature, filters, and with cold distilled water, dehydrated alcohol, anhydrous diethyl ether washing, thick product is eluent with the ethyl acetate to precipitation, uses neutral Al respectively
2O
3Cross post and separate, obtain yellow powder 0.50g, productive rate 51%.
1H?NMR(DMSO)：7.1(s，1H)，7.3(t，J＝7.1Hz，1H)，7.3(t，J＝7.0Hz，1H)，7.3(t，J＝7.0Hz，1H)，7.5(s，1H)，7.53(t，J＝7.6Hz，1H)，7.7(d，J＝5.0Hz，1H)，7.86(s，1H)，7.9(d，J＝7.5Hz，1H)，8.0(d，J＝9.6Hz?1H)，8.18(s，1H)，8.35(d，J＝12.5Hz，1H)，8.4(s，1H)，9.01(t，J＝6.85Hz，1H)。
Use Hitachi F-4500 fluorescence spectrophotometer records the photoluminescence spectra figure of this a metal-organic complex Al under 25 ℃, as shown in Figure 2.As can be seen from Figure 2 glow peak is positioned at about 591 nanometers, and its glow peak is in the wavelength region of gold-tinted.
This preparation embodiment illustrates the preparation of a metal-organic complex provided by the invention.
Prepare a metal-organic complex A2 according to the method identical with embodiment 1, difference is, uses 4-butylbenzene boric acid to replace the phenylo boric acid that uses among the embodiment 1, and 4-butylbenzene boric acid is bought the company in Aldrich.Final synthetic organic material 1-(4-butyl phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum (TPPtpic).
1H?NM?R(DMSO)：0.96(s，3H)，1.33(s，2H)，1.62(s，2H)，2.55(s，2H)，7.1(s，1H)，7.2(d，J＝8.21Hz，1H)，7.2(d，J＝8.22Hz，1H)，7.5(d，J＝8.1Hz，1H)，7.53(t，J＝15.62Hz，1H)，7.7(d，J＝6.67Hz，1H)，7.86(d，J＝6.93Hz，1H)，7.9(t，J＝15.82Hz，1H)，7.9(t，J＝15.65Hz，1H)，8.18(d，J＝7.83Hz，1H)，8.35(d，J＝7.63Hz，1H)，8.4(d，J＝7.68Hz，1H)，9.01(d，J＝7.88Hz，1H)。
The glow peak that records this a metal-organic complex A2 according to the mode identical with embodiment 1 is positioned at about 593 nanometers, and its glow peak is in the wavelength region of gold-tinted.
This preparation embodiment illustrates the preparation of a metal-organic complex provided by the invention.
Add the 2-bromo-5-fluorine pyridines that 20 millis rub in 50 milliliters of there-necked flasks, potassium acetates that 25 millis rub and 20 milliliters DMF add the 30 millis CuI that rubs, and inflated with nitrogen refluxed 15 hours at 140～145 ℃, with ether extraction 3 times, with the washing of 50mL KI saturated solution, Na
2SO
4Drying, distillation concentrating under reduced pressure gained residuum is collected 140～155 ℃ distillate, gets solid 1.15g, uses 95% ethyl alcohol recrystallization, gets 1.01g 2-methyl-5-fluorine pyridine crystal.
In 50 milliliters of there-necked flasks, add 5-fluoro-2-picoline and 20 ml waters that 7 millis rub, add the 17 millis potassium permanganate that rubs then in batches, stir 80 ℃ of backflows of controlled temperature.After treating that potassium permanganate color that last batch of adds takes off to the greatest extent, reacted 1 hour, filtered while hot washes filter cake with water again.Filtrate concentrates the back, and to regulate pH value with concentrated hydrochloric acid be 3.0-4.0, and then with the neutralizer underpressure distillation, refrigerator is cold to be put the residual solid thing with putting into after twice of the dehydrated alcohol refluxing extraction, crosses filter solid and drying, obtains the 0.55 5-fluorine pyridine carboxylic acid that restrains.
Employed 2-bromo-5-fluorine pyridine is bought in Aldrich in the present embodiment, and potassium acetate (CH3COOK), cupric iodide (CuI), dimethyl formamide (DMF), potassium permanganate (KMnO4), hydrochloric acid (HCl) etc. are all bought in Beijing chemical reagent.
Prepare a metal-organic complex A3 according to the method identical with embodiment 2, difference is, uses 5-fluorine pyridine carboxylic acid to replace pyridine carboxylic acid, makes 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine and closes platinum.
1H?NMR(DMSO)：0.96(s，3H)，1.33(s，2H)，1.62(s，2H)，2.55(s，2H)，7.1(s，1H)，7.2(d，J＝8.21Hz，1H)，7.2(d，J＝8.22Hz，1H)，7.5(d，J＝8.1Hz，1H)，7.53(t，J＝15.62Hz，1H)，7.7(d，J＝6.88Hz，1H)，7.9(t，J＝14.73Hz，1H)，7.9(t，J＝13.54Hz，1H)，7.89(d，J＝8.84Hz，1H)，8.33(d，J＝7.36Hz，1H)，8.4(d，J＝7.48Hz，1H)，8.72(d，J＝6.78Hz，1H)。
The glow peak that records this a metal-organic complex A3 according to the mode identical with embodiment 1 is positioned at about 586 nanometers, is the standard yellow light emission.
This preparation embodiment illustrates the preparation of a metal-organic complex provided by the invention.
Prepare a metal-organic complex A4 according to the method identical with embodiment 3, difference is, uses 2-bromo-4-5-flumethiazine, replaces 2-bromo-5-fluorine pyridine, makes 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine and closes platinum.
1H?NMR(DMSO)：0.96(s，3H)，1.33(s，2H)，1.62(s，2H)，2.55(s，2H)，7.1(s，1H)，7.2(d，J＝8.33Hz，1H)，7.2(d，J＝8.36Hz，1H)，7.5(d，J＝8.25Hz，1H)，7.53(t，J＝16.42Hz，1H)，7.7(d，J＝6.97Hz，1H)，7.86(t，J＝14.86Hz，1H)，7.9(t，J＝15.87Hz，1H)，7.91(d，J＝8.93Hz，1H)，8.41(d，J＝7.65Hz，1H)，8.5(d，J＝7.82Hz，1H)，9.02(d，J＝6.96Hz，1H)。
The glow peak that records this a metal-organic complex A4 according to the mode identical with embodiment 1 is positioned at about 585 nanometers, is the standard yellow light emission.
Embodiment 5
Present embodiment illustrates the preparation of luminescent material provided by the invention and organic electroluminescence device.
Be to adopt etching solution (pure water: HCl: HNO on the ito glass substrate of 0.5 nanometer at thickness
3=10: 20: 1 (volume ratio); Etching solution equivalent concentration: 6.8-7.5N) etched thickness is the ito anode and the dot matrix pattern of 200 nanometers.Use deionized water, chloroform, acetone and methyl alcohol ultrasonic cleaning then successively, cleaned 15 minutes at every turn, oven dry is placed in the Virahol preserves.
Use ozone-plasma microwave processing system (time CGWB02) to handle the above-mentioned ito glass substrate that obtains 10 minutes then.
After the taking-up, adopt the desk-top sol evenning machine of KW-4A type, with 3500 rev/mins rotating speed spin coating PEDOT/PSS (the buying company) aqueous solution in aldrich, under 90 ℃, vacuum-drying 20 minutes.Forming thickness is the hole transmission layer of 40 nanometers.
A metal-organic complex Al and PVK that preparation embodiment 1 is obtained are dissolved in the chloroformic solution, the weight ratio of Al and PVK is 5: 100, it is 2 weight % that total consumption of Al and PVK makes the total concn of solute in the above-mentioned solution (Al and PVK), with its rotating speed with 2000 rev/mins, spin-coating film on above-mentioned hole transmission layer obtains the luminescent layer that thickness is 100 nanometers.
Then, 4 * 10
-4Under the vacuum tightness of holder, adopt vacuum vapour deposition evaporation cathode material Mg: Ag (9: 1) on luminescent layer, thickness is 150 nanometers.Obtain organic electroluminescence device B1.The light-emitting zone area of gained organic electroluminescence device is 3 millimeters
2
Use Hitachi F-4500 fluorescence spectrophotometer to record the EL spectrogram (electroluminescent spectrum figure) of this luminescent device B1, the result as shown in Figure 3.As can be seen from Figure 3, the luminous main peak of this device is 592 nanometers.
The anode layer of described ruddiness organic electroluminescence device is linked to each other with the two ends of power supply with cathode layer, regulate the magnitude of voltage between anode layer and the cathode layer, use PR-705 chroma luminance tester and keithily 238 current/voltage testers to measure the maximum brightness value that this organic electroluminescence device emits beam and the colourity of this organic electroluminescence device, and calculate the luminous efficiency of this organic electroluminescence device when reaching high-high brightness according to following formula:
Luminous efficiency (bearing moral draws/pacify)=brightness (bear moral to draw/square metre)/current density (milliampere/square centimeter) * 0.1.
For one-sided luminous flat light source, 1 lumen=π * (1 bears moral draws).And calculate the maximum work efficient that this organic electroluminescence device reaches under certain driving voltage according to following formula:
Effect rate (lumens/watt)=luminous power (lumen)/[current density (milliampere/square centimeter) * driving voltage (volt)] * 0.1=π * luminous efficiency (bearing moral draws/pacify)/driving voltage (volt)
Using on the technique of display, luminous efficiency is relevant with the characteristic of luminescent material, and the luminous efficacy rate then not only has relation also relevant with the energy system design with the device panel power consumption with the characteristic of luminescent material.
This device cut-in voltage is 5 volts, and maximum work efficient is 19.6 lumens/watt, and maximum current efficient is 28.9 may moral to draw/pacify, high-high brightness can reach 37500 bear moral and draw/square metre, tristimulus coordinates is (0.57 0.36), is the safran light emission.
Embodiment 6
Present embodiment illustrates the preparation of luminescent material provided by the invention and organic electroluminescence device.
Prepare organic electroluminescence device B2 according to the method identical with embodiment 5, different is, the thickness of the hole transmission layer that spin coating obtains is 30 nanometers, on hole transmission layer, form in the luminescent layer, phosphor material is prepared A4 and the PVK that embodiment 4 obtains to be dissolved in the chloroformic solution, the weight ratio of A4 and PVK is 5: 100, it is 2 weight % that total consumption of A4 and PVK makes the total concn of solute in the above-mentioned solution (PVK of A4), with its rotating speed with 2000 rev/mins, spin-coating film on above-mentioned hole transmission layer obtains the luminescent layer that thickness is 110 nanometers.Obtain organic electroluminescence device B2.
Record the EL spectrogram of this device according to the method identical, as shown in Figure 4 with embodiment 5.As can be seen from Figure 4, main glow peak is about 585 nanometers.
Adopt the method identical to measure the luminescent properties of this luminescent device with embodiment 5, measurement result is, this device cut-in voltage is 4.3 volts, maximum work efficient is 20.5 lumens/watt, maximum current efficient is 28.9 may moral to draw/pacify, high-high brightness can reach 37600 bear moral and draw/square metre, tristimulus coordinates is (0.5,0.46), be yellow emission light.
Embodiment 7
Present embodiment illustrates the preparation of luminescent material provided by the invention and organic electroluminescence device.
Prepare organic electroluminescence device according to the method identical with embodiment 6, different is to treat that vacuum tightness reaches 4 * 10
-4Evaporation blue-fluorescence organic material layer during the Torr left and right sides.With 2～3
The speed evaporation thickness of/s is 4,4 '-two (N-carbazole) biphenyl (CBP buys in Aldrich) of 50 nanometers) and BCzVBi (the synthesized reference C.Hosokawa of BCzVBi, H.et al.Appl.Phys.Lett., 1995,67,3853), wherein BCzVBi doping quality accounts for 5% of gross weight; With 2～3
The speed evaporation thickness of/s is the CBP of 4 nanometers, at last with 5～10
The speed evaporation thickness of/s is 80 nanometer Mg: Ag (10: 9).Made device light-emitting zone area is 3 millimeters
2
Obtain organic electroluminescence device B3.
Record the electroluminescent spectrum of this device according to the method identical with embodiment 5, the result as shown in Figure 5.
Adopt the method identical to measure the luminescent properties of this luminescent device with embodiment 5, measurement result is, this device cut-in voltage is 5V, maximum work efficient is 19.3 lumens/watt, maximum current efficient is 29.8 may moral to draw/pacify, high-high brightness can reach 48700 may moral draw/square metre, tristimulus coordinates is (0.356 0.376), is comparatively ideal white light.
Claims (12)
1. an a metal-organic complex is characterized in that, described title complex is the compound by general formula (1) expression:
General formula (1)
Wherein, R
1Be hydrogen atom, methyl, ethyl, propyl group or butyl; R
2Be cyano group, trifluoromethyl, fluorine atom or hydrogen atom; R
3Be cyano group, trifluoromethyl, fluorine atom or hydrogen atom.
2. title complex according to claim 1, wherein, described title complex is that 1-phenyl isoquinolin quinoline-2-pyridine carboxylic acid closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-pyridine carboxylic acid closes platinum, 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-5-fluorine pyridine closes platinum, or 1-(4-butyl phenyl) isoquinoline 99.9-2-formic acid-4-5-flumethiazine closes platinum.
3. the preparation method of the described a metal-organic complex of claim 1, it is characterized in that, this method is included under the condition of one or more materials existence in alkali-metal oxyhydroxide, carbonate and the supercarbonate, compound that will be shown in general formula (2) and shown in general formula (3) compound reflux in organic solvent
General formula (2)
General formula (3)
Wherein, R
1Be hydrogen atom, methyl, ethyl, propyl group or butyl; R
2Be cyano group, trifluoromethyl, fluorine atom or hydrogen atom; R
3Be cyano group, trifluoromethyl, fluorine atom or hydrogen atom.
4. method according to claim 3, wherein, the mol ratio of compound shown in general formula (2) and the compound shown in general formula (3) is 1: 2-4.
5. method according to claim 3, wherein, the consumption of described alkali-metal oxyhydroxide, carbonate and supercarbonate makes the pH value of reaction system be 8-10; Described alkali-metal oxyhydroxide, carbonate and supercarbonate are one or more in potassium hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash, saleratus and the sodium bicarbonate.
6. method according to claim 3, wherein, described organic solvent is a cellosolvo, 1, one or more in 2-propylene glycol, ethanol and the glycol monoethyl ether; The 1-phenyl isoquinolin quinoline dipolymer shown in general formula (2) and the weight ratio of solvent are 1: 15-50.
7. method according to claim 3, wherein, the condition of described reflux is under the condition of protection of inert gas backflow 10-30 hour, the temperature of backflow is 85-100 ℃.
8. luminescent material, this luminescent material contains a kind of a metal-organic complex, it is characterized in that, and described title complex is claim 1 or 2 described a metal-organic complexes.
9. luminescent material according to claim 8, wherein, described luminescent material also contains material of main part.
10. luminescent material according to claim 9 wherein, is a benchmark with the weight of described material of main part, and the content of described a metal-organic complex is 0.1-10 weight %.
11., wherein, be in Polyvinyl carbazole, poly-fluorenes, polyparaphenylene's derivative and the tertiary butyl xenyl phenyl diazole one or more with described material of main part according to claim 9 or 10 described luminescent materials.
12. an organic electroluminescence device, this organic electroluminescence device comprises substrate, anode layer, luminescent layer and cathode layer, it is characterized in that, described luminescent layer is any described luminescent material among the claim 8-11.
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| CN1717411A (en) * | 2002-11-26 | 2006-01-04 | 株式会社半导体能源研究所 | Phosphorescence compound and electro field light emitting device having the same |
| CN1966510A (en) * | 2006-10-30 | 2007-05-23 | 湘潭大学 | Isoquinoline triarylamine cyclic metal complex and its uses |
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| CN1717411A (en) * | 2002-11-26 | 2006-01-04 | 株式会社半导体能源研究所 | Phosphorescence compound and electro field light emitting device having the same |
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