CN102899022A - Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device - Google Patents
Iridium-containing organic electroluminescent material and preparation method thereof, and organic electroluminescent device Download PDFInfo
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Abstract
The invention relates to an iridium-containing organic electroluminescent material which has the following structural formula I, wherein R represents an alkyl of C1-C4. The iridium-containing organic electroluminescent material comprises a dipyridine ligand with the alkyl and fluoride groups thereon, can increase carrier injection and transmission capability of the luminescent material, and has relatively high internal quantum efficiency and electroluminescent efficiency. Besides, the iridium-containing organic electroluminescent material has the characteristic of relatively strong blue phosphor emission in a room temperature, can effectively broaden research scope of blue-light emitting materials, and provides further technical support for researches of blue-light emitting devices or white-light emitting devices with high colour purity and high luminous efficiency. Furthermore, the invention also relates to a preparation method for the iridium-containing organic electroluminescent material and an organic electroluminescent device.
Description
[technical field]
The present invention relates to technical field of organic electroluminescence, relate in particular to a kind of iridium electroluminescent organic material and preparation method thereof and organic electroluminescence device of containing.
[background technology]
Organic electroluminescent refers to organic materials under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.It is early stage because that the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. is former thereby so that the research of organic electroluminescent is stayed cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened the new prelude to electroluminescent organic material research.But owing to be subject to the spinning restriction of statistical theory, the theoretical internal quantum efficiency limit of fluorescent material only is 25%, how to take full advantage of all the other phosphorescence of 75% and realizes that higher luminous efficiency has become the hot research direction in this field after this.1997, Forrest etc. found the electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material is broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, such as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, because good stability, reaction conditions is gentle in building-up process, and have very high electroluminescent properties, in research process subsequently, accounting for dominant position always.And in order to make device obtain full-color demonstration, generally must obtain simultaneously ruddiness, green glow and the blue light material of excellent performance.Compare with green light material with ruddiness, the development of blue light material lags behind comparatively speaking, and the efficient that improves blue light material and purity of color have just become the breakthrough point of people's researchs.Two [2-(2,4 difluorobenzene base) pyridine-N, C
2] (pyridine carboxylic acid) to close iridium (FIrpic) be one of more iridium metals organic coordination compound blue phosphorescent electroluminescent material of report.Although people have carried out various optimizations to FIrpic class OLED structure, device performance also is greatly improved, but the weakness of FIrpic maximum is exactly the blue light of being sent out is sky blue, blue light color purity is not good enough, the CIE of each OLED device of making changes between (0.13～0.17,0.29～0.39).Therefore, the blue phosphorescent organic electroluminescent material of developing high color purity becomes a megatrend of expanding the blue light material research field.
[summary of the invention]
Based on this, be necessary to provide the higher blue phosphorescent of a kind of purity of color to contain iridium electroluminescent organic material and preparation method thereof.
A kind of iridium electroluminescent organic material that contains has following structural formula I:
This contains in the iridium electroluminescent organic material molecule and contains bipyridine ligand, and on it also with alkyl, fluorine-based, can improve carrier injection and the transmittability of luminescent material, have higher internal quantum efficiency and electroluminescent efficiency.In addition, adopting high field part 2-pyridine carboxylic acid in its molecule is assistant ligand, make the effective blue shift of its luminescent spectrum, thereby contain the iridium electroluminescent organic material and at room temperature have stronger blue phosphorescent emission characteristics, research range that can the efficient extn blue light material is for the blue-light device of high color purity, high-luminous-efficiency or the research of white light parts provide further technical support.
A kind of preparation method who contains the iridium electroluminescent organic material comprises the steps:
Step 1: prepare or provide compd A, Compound C that following structural formula represents,
And IrCl
33H
2O, wherein, R is C
1～C
4Alkyl;
Step 2: under the oxygen free condition, with compd A and IrCl
33H
2O carried out back flow reaction in 3: 1 in molar ratio～5: 1 in solvent, generate two endo compound B, and reaction formula is as follows,
Step 3: under anaerobic and the weak basic condition, two endo compound B and Compound C were carried out ligand exchange reaction generation Compound I in 1: 2.5 in molar ratio～1: 3.5 in solvent, reaction formula is as follows,
Preferably, in the step 2, described solvent is cellosolvo; In the step 3, described solvent is cellosolvo, 1,2-ethylene dichloride, glycerine or tetrahydrofuran (THF), and the temperature of described ligand exchange reaction is the back flow reaction temperature.
Preferably, also comprise the purification procedures to compd B after the step 2: at first the reacted mixed solution of step 2 is carried out concentrating under reduced pressure and process, obtain concentrated solution; Then take methylene dichloride as elutriant described concentrated solution is carried out silica gel column chromatography and separate, obtain the described compd B of purifying.
Preferably, also comprise the purification procedures to Compound I after the step 3: at first remove the solvent in the rear mixed solution of step 3 reaction, add distilled water, separate out solid, solid collected by filtration obtains containing the crude product of Compound I, then use successively normal hexane, the described crude product of ether supersound washing for several times after, separate as elutriant carries out silica gel column chromatography to described crude product with the mixed solution of methylene dichloride take normal hexane, obtain the described Compound I of purifying.
Preferably, the preparation process of compd A comprises the steps:
The Compound D and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent,
Under the anhydrous and oxygen-free condition, at first Compound D was reacted in solvent with diisopropylamine lithium in 1: 1 in molar ratio～1: 1.5, obtain containing 2, the mixture of 6-difluoro pyridine base-3-lithium, then described mixture and trimethyl borate reaction are obtained compd E, wherein, the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, and reaction formula is as follows:
The compd E and the compound F 17-hydroxy-corticosterone that make were carried out the Suzuki linked reaction in 1.5: 1 in molar ratio～2: 1 in solvent, generate described compd A, reaction formula is as follows:
Preferably, the temperature in Compound D and the diisopropylamine lithium reaction process is-78 ℃, and the solvent of use is the new ether that steams, and the temperature of mixture and trimethyl borate reaction is room temperature;
The temperature of Suzuki linked reaction is the back flow reaction temperature; The catalyzer that uses is K
2CO
3With Pd (PPh
3)
4Co-catalyst, wherein K
2CO
3Molar weight is 10 times of compound F 17-hydroxy-corticosterone, Pd (PPh
3)
4Molar weight be 0.5% of compound F 17-hydroxy-corticosterone; Solvent is the mixed solution of tetrahydrofuran (THF) and water.
Preferably, also comprise purification procedures to compd E: at first be 5% NaOH aqueous solution termination reaction with massfraction; Then be that pH of mixed value behind the HCl aqueous solution conditioned reaction of 3M is to neutral, again with merging organic phase behind the ethyl acetate extraction with concentration; Concentrate at last organic phase, obtain the described compd E of purifying.
Preferably, also comprise the purification procedures to compd A: at first add distilled water in the mixed solution after the Suzuki linked reaction, with merging organic phase behind the ethyl acetate extraction; Then use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Make eluent with ethyl acetate and the mixed solution of normal hexane at last and filtrate is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
Above-mentioned preparation method's principle is simple, easy and simple to handle, low for equipment requirements, but wide popularization and application.
In addition, also be necessary the blue phosphorescent organic electroluminescent device that provides a kind of purity of color higher.
A kind of organic electroluminescence device comprises luminescent layer, and contains the Compound I that following structural formula represents in the described luminescent layer:
Wherein, R is C
1～C
4Alkyl.
Material of main part in above-claimed cpd I and the organic electroluminescence device luminescent layer has preferably consistency, can be widely used in preparation blue light or white-light phosphor photoelectricity electroluminescence device.Electroluminescent device is owing to contain the blue phosphorescent luminescent material of high color purity in the luminescent layer, can launch high purity blue light and the advantage of device performance preferably thereby it has.
[description of drawings]
Fig. 1 is the preparation flow synoptic diagram that contains the iridium electroluminescent organic material among the embodiment 1;
Fig. 2 is the utilizing emitted light spectrogram that contains the iridium electroluminescent organic material among the embodiment 1;
Fig. 3 is the structural representation of organic electroluminescence device among the embodiment 5.
[embodiment]
The below mainly is described in further detail with organic electroluminescence device containing iridium electroluminescent organic material and preparation method thereof in conjunction with the drawings and the specific embodiments.
Iridium (Ir) a metal-organic complex is a kind of phosphorescent light-emitting materials with shorter phosphorescent lifetime (1～14 μ s).Present embodiment contain the iridium electroluminescent organic material, have molecular formula (dfpyRpy)
2Irpic, wherein, dfpy represents on the cyclic metal complexes one 2, two fluorine-based substituent pyridine rings of 6-bit strip; Rpy then represents the pyridine ring of another 4-bit strip alkyl substituent on the cyclic metal complexes; Two pyridine rings connect into dipyridyl with 2-, 3-position respectively; Pic represents assistant ligand pyridine carboxylic acid in the title complex.The concrete structure formula is as follows:
(dfpyRpy)
2Irpic:I:
Wherein, R is C
1～C
4Alkyl.
Containing in the iridium electroluminescent organic material molecule of present embodiment contains bipyridine ligand, and also with alkyl, fluorine-based, can improve carrier injection and the transmittability of luminescent material on it, have higher internal quantum efficiency and electroluminescent efficiency, in addition, (dfpyRpy)
2It is assistant ligand that Irpic adopts high field part 2-pyridine carboxylic acid, makes the effective blue shift of its luminescent spectrum.
The material of main part that contains in iridium electroluminescent organic material and the organic electroluminescence device luminescent layer has preferably consistency, and the doping object that can be used as in the luminescent layer is widely used in the organic electroluminescence device field for preparing blue or white phosphorescence.
The above-mentioned a kind of preparation method who contains the iridium electroluminescent organic material comprises the steps:
Unless below each step special stipulation, all under the anhydrous and oxygen-free condition, carry out, as at N
2Or atmosphere of inert gases is inferior, the solvent that solvent for use provided except each step, can also adopt other and reactant to have the solvent of better intermiscibility.
Step S1: in ether solvent, with Compound D (2, the 6-difluoro pyridine) with tetrahydrofuran (THF) (THF) solution of N-Lithiodiisopropylamide (LDA) after reaction under-78 ℃ of low temperature makes 2,6-difluoro pyridine base-3-lithium, at room temperature with trimethyl borate (B (OMe)
3) reaction makes compd E (2,6-, two fluoro-3-boric acid pyridines), wherein, Compound D was with the mol ratio of diisopropylamine lithium 1: 1～1: 1.5, and the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, and reaction formula is as follows:
In preferred embodiment, further comprise the purification procedures to compd E after the step S1: be that 5% the NaOH aqueous solution stops mixed solution and reacts with massfraction at first, then be that the HCl aqueous solution of 3M transfers the pH of mixed value to neutral with concentration, then repeatedly extract rear merging organic phase with ethyl acetate; Concentrated organic phase obtains compd E after the vacuum-drying at last.
Step S2: in the mixed solvent that tetrahydrofuran (THF) and water form, with compd E and compound F 17-hydroxy-corticosterone (4-alkyl-2-bromopyridine) at salt of wormwood (K
2CO
3) and tetra-triphenylphosphine palladium (Pd (PPh
3)
4) under the mixed catalyst effect that forms, carry out the Suzuki linked reaction under the reflux state, make compd A, reaction formula is as follows:
In preferred embodiment, further comprise the purification procedures to compd A after the step S2: after at first in reaction mixture, adding an amount of distilled water, repeatedly extract with ethyl acetate, merge organic phase; Then use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Use at last ethyl acetate: the normal hexane mixed solution is made eluent the filtrate residue is carried out the silica gel column chromatography separation, obtains the described compd A of purifying.
Step S3: in the reaction system take cellosolvo as solvent, compd A and three water and iridous chloride (IrCl
33H
2O) 3: 1 in molar ratio～5: 1, in oxygen free condition, reaction generated two endo compounds (dfpyRpy) under the reflux state
2Ir (μ-Cl)-(dfpyRpy)
2, also be compd B, reaction formula is as follows:
In preferred embodiment, further comprise the purification procedures to compd B after the step S3: at first the question response mixed solution is chilled to after the room temperature naturally to its concentrating under reduced pressure; Then take methylene dichloride as elutriant debris is carried out silica gel column chromatography and separate, obtain two endo compound B of purifying.
Step S4: with 1, the 2-ethylene dichloride is in the reaction system of solvent, Compound C and two endo compound B under the co-catalyst effect that sodium methylate and silver triflate form, are carried out ligand exchange reaction under the reflux state, obtain target product I ((dfpyRpy)
2Irpic), reaction formula is as follows:
In preferred embodiment, further comprise the purification procedures to Compound I after the step S4: after at first the question response mixed solution is chilled to room temperature naturally, the concentrated steaming except an amount of solvent; Then an amount of distilled water of impouring is collected solid, normal hexane, ether supersound washing to separate out solid; Take normal hexane and methylene dichloride mixed solution as elutriant crude product being carried out silica gel column chromatography at last separates and obtains pure target product I.
Sodium methylate can also substitute with other alkaline compounds among the above-mentioned steps S4, such as salt of wormwood, sodium phosphate, potassiumphosphate, yellow soda ash, sodium ethylate, potassium methylate, potassium ethylate etc.Solvent can also be cellosolvo, trichloromethane or tetrahydrofuran (THF) etc.
Above-mentioned preparation method's principle is simple, easy and simple to handle, low for equipment requirements, but wide popularization and application.
Below be the specific embodiment part:
Embodiment 1: title complex two (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (2-pyridine carboxylic acid) close iridium [(dfpyMepy)
2Irpic] synthetic, please in conjunction with Fig. 1:
Synthesizing of (1) 2,6-two fluoro-3-boric acid pyridines
Under the nitrogen protection, the N-Lithiodiisopropylamide THF solution of 7.5mL (12mmol) 1.6M slowly drops to-78 ℃ and contains 0.91mL (10mmol) 2, in the mixed solution of 6-difluoro pyridine and 40mL ether, keeps-78 ℃ of temperature stirring reaction 1h.The question response system is warming up to room temperature after adding 1.40mL (12.5mmol) trimethyl borate naturally, continues stirring reaction 1h.It is 5% NaOH aqueous solution termination reaction that reaction mixture slowly adds the 20mL massfraction, stir 10min after, dropwise add the HCl aqueous solution adjust pH of an amount of 3M to neutral.Ethyl acetate repeatedly extracts, and merges organic phase, and rotation is steamed and desolventized, and gets white solid thing 1.43g, and yield is 90%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.45(d，1H)，6.94(d，1H)，5.33(s，2H)。
(2) 2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl [dfpyMepy] synthetic
Under the nitrogen protection, 0.45mL (4.00mmol) 2-bromo-4-picoline, 1.02g (6.40mmol) 2,6-two fluoro-3-boric acid pyridines, 0.0374g (0.032mmol) Pd (PPh
3)
4After being dissolved in 25mL THF, adding 10mL massfraction is 5% K
2The COX aqueous solution is heated to reflux state, stirring reaction 18h.Naturally after being chilled to room temperature, add an amount of distilled water, an amount of ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 3 separates as elutriant carries out silica gel column chromatography, gets colorless solid product 0.53g, and yield is 64.3%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.58(d，1H)，8.43(d，1H)，7.70(s，1H)，7.62(d，1H)，6.92(d，1H)，2.61(s，3H)。
(3) two endo compounds (dfpyMepy)
2Ir (the Ir (dfpyMepy) of μ-Cl)
2Synthetic
Under the nitrogen protection, 1.65g (8mmol) 2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to reflux state, stirring reaction 25h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.91g, yield is 71.3%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.66(d，4H)，7.57(s，4H)，6.74(s，4H)，2.70(s，12H)。
(4) title complex (dfpyMepy)
2Irpic's is synthetic
Under the nitrogen protection, 0.37g (3mmol) 2-pyridine carboxylic acid and 1.28g (1mmol) two endo compounds (dfpyMepy)
2Ir (the Ir (dfpyMepy) of μ-Cl)
2Be dissolved in the 60mL cellosolvo, under the katalysis of 0.54g (10mmol) sodium methylate and 0.5lg (2mmol) silver triflate, stirring heating is warming up to reflux state, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, an amount of distilled water of impouring has solid to separate out.Filter, collect crude product, solid is successively with after the washing under normal hexane, the ether ultrasonication, and take normal hexane: methylene dichloride=1: 3 (volume ratio) gets 1.28g pure products (dfpyMepy) for elutriant carries out the silica gel column chromatography separation to it
2Irpic, yield are 88.1%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ9.13(d，1H)，8.57(d，1H)，8.51(d，1H)，8.32(d，1H)，8.01(m，1H)，7.89(m，1H)，7.60(d，1H)，7.58(d，1H)，7.42(s，1H)，7.38(s，1H)，6.71(d，1H)，6.68(d，1H)，2.72(s，6H)。
As shown in Figure 2, concentration is about 10
-5(dfpyMepy) of M
2The CH of Irpic
2Cl
2The emmission spectrum maximum emission peak of solution under the 298K temperature has an acromion at the 469nm place simultaneously at the 448nm place, can be used as the preparation field that the blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, under the 298K temperature, with the H of 0.1M quinoline sulfate
2SO
4Solution is standard Φ PL=0.54, records concentration and is about 10
-5(dfpyMepy) of M
2Irpic CH
2Cl
2The Φ PL=0.61 of solution, (dfpyMepy) of visible present embodiment
2Irpic has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: title complex two (2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl-N, C2 ') (2-pyridine carboxylic acid) close the synthetic of iridium
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to embodiment 1;
(2) 2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl synthetic
Under the nitrogen protection, 0.48mL (4.00mmol) 2-bromo-4-ethylpyridine, 1.02g (6.40mmol) 2,6-two fluoro-3-boric acid pyridines, 0.0374g (0.032mmol) Pd (PPh
3)
4After being dissolved in 25mL THF, adding 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to reflux state, stirring reaction 18h.Naturally after being chilled to room temperature, add an amount of distilled water, an amount of ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4 separates as elutriant carries out silica gel column chromatography, gets colorless solid product 0.57g, and yield is 60.8%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.60(d，1H)，8.45(d，1H)，7.71(s，1H)，7.64(d，1H)，6.94(d，1H)，3.46(m，2H)，1.78(m，3H)。
Synthesizing of (3) two endo compounds
Under the nitrogen protection, 1.78g (8mmol) 2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to reflux state, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.90g, yield is 67.6%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.81(d，4H)，7.67(d，4H)，7.56(s，4H)，6.75(s，4H)，3.50(m，8H)，1.82(m，12H)。
(4) Complex synthesis
Under the nitrogen protection; 0.37g (3mmol) 2-pyridine carboxylic acid and 1.33g (1mmol) two endo compounds are dissolved in the 60mL cellosolvo; under the katalysis of 0.54g (10mmol) sodium methylate and 0.51g (2mmol) silver triflate; stirring heating is warming up to reflux state, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, an amount of distilled water of impouring has solid to separate out.Filter, collect crude product, solid is successively with after the washing under normal hexane, the ether ultrasonication, and take normal hexane: methylene dichloride=1: 3 (volume ratio) gets the 1.125g pure products for elutriant carries out the silica gel column chromatography separation to it, and yield is 82.8%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ9.11(d，1H)，8.56(d，1H)，8.52(d，1H)，8.32(d，1H)，8.02(m，1H)，7.88(m，1H)，7.62(d，1H)，7.58(d，1H)，7.44(s，1H)，7.40(s，1H)，6.72(d，1H)，6.69(d，1H)，3.52(m，4H)，1.77(m，6H)。
Embodiment 3: title complex two (2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl-N, C
2') (2-pyridine carboxylic acid) close the synthetic of iridium
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to embodiment 1;
(2) 2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl synthetic
Under the nitrogen protection, 0.50mL (4.00mmol) 2-bromo-4-propyl group pyridine, 1.02g (6.40mmol) 2,6-two fluoro-3-boric acid pyridines, 0.0374g (0.032mmol) Pd (PPh
3)
4After being dissolved in 25mL THF, adding 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to reflux state, stirring reaction 18h.Naturally after being chilled to room temperature, add an amount of distilled water, an amount of ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4 separates as elutriant carries out silica gel column chromatography, gets colorless solid product 0.57g, and yield is 60.8%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.57(d，1H)，8.48(d，1H)，7.73(s，1H)，7.66(d，1H)，6.97(d，1H)，2.97(m，2H)，1.89(m，2H)，0.98(m，3H)。
Synthesizing of (3) two endo compounds
Under the nitrogen protection, 1.87g (8mmol) 2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to reflux state, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.87g, yield is 62.6%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.68(d，4H)，7.57(s，4H)，6.76(s，4H)，3.44(m，8H)，1.78(m，8H)，0.99(m，12H)。
(4) Complex synthesis
Under the nitrogen protection; 0.37g (3mmol) 2-pyridine carboxylic acid and 1.39g (1mmol) two endo compounds are dissolved in the 60mL cellosolvo; under the katalysis of 0.54g (10mmol) sodium methylate and 0.51g (2mmol) silver triflate; stirring heating is warming up to reflux state, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, an amount of distilled water of impouring has solid to separate out.Filter, collect crude product, solid is successively with after the washing under normal hexane, the ether ultrasonication, and take normal hexane: methylene dichloride=1: 3 (volume ratio) gets the 1.24g pure products for elutriant carries out the silica gel column chromatography separation to it, and yield is 79.2%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ9.12(d，1H)，8.51(d，1H)，8.46(d，1H)，8.34(d，1H)，8.05(m，1H)，7.91(m，1H)，7.56(d，1H)，7.53(d，1H)，7.40(s，1H)，7.35(s，1H)，6.68(d，1H)，6.65(d，1H)，3.41(m，4H)，1.77(m，4H)，0.98(m，6H)。
Embodiment 4: title complex two (2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl-N, C2 ') (2-pyridine carboxylic acid) close the synthetic of iridium
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to embodiment 1;
(2) 2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl synthetic
Under the nitrogen protection, 0.47mL (4.00mmol) 2-bromo-4-butyl-pyridinium, 1.02g (6.40mmol) 2,6-two fluoro-3-boric acid pyridines, 0.0374g (0.032mmol) Pd (PPh
3)
4After being dissolved in 25mL THF, adding 10mL massfraction is 5% K
2CO
3The aqueous solution is heated to reflux state, stirring reaction 18h.Naturally after being chilled to room temperature, add an amount of distilled water, an amount of ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4 separates as elutriant carries out silica gel column chromatography, gets colorless solid product 0.61g, and yield is 61.4%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.59(d，1H)，8.50(d，1H)，7.74(s，1H)，7.68(d，1H)，6.99(d，1H)，2.92(m，2H)，1.81(m，2H)，1.13(m，2H)，0.89(m，3H)。
Synthesizing of (3) two endo compounds
Under the nitrogen protection, 1.99g (8mmol) 2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to reflux state, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Separate take methylene dichloride as the elutriant silica gel column chromatography, get product 0.85g, yield is 58.8%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ8.77(d，4H)，7.67(d，4H)，7.55(s，4H)，6.76(s，4H)，3.41(m，8H)，1.76(m，8H)，1.33(m，8H)，0.98(m，12H)。
(4) Complex synthesis
Under the nitrogen protection; 0.37g (3mmol) 2-pyridine carboxylic acid and 1.44g (1mmol) two endo compounds are dissolved in the 60mL cellosolvo; under the katalysis of 0.54g (10mmol) sodium methylate and 0.51g (2mmol) silver triflate; stirring heating is warming up to reflux state, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, an amount of distilled water of impouring has solid to separate out.Filter, collect crude product, solid is successively with after the washing under normal hexane, the ether ultrasonication, and take normal hexane: methylene dichloride=1: 3 (volume ratio) gets the 1.26g pure products for elutriant carries out the silica gel column chromatography separation to it, and yield is 77.7%.Product detection data and reaction equation are as follows:
1H?NMR(400MHz，CDCl
3，ppm)：δ9.15(d，1H)，8.47(d，1H)，8.41(d，1H)，8.35(d，1H)，8.08(m，1H)，7.95(m，1H)，7.58(d，1H)，7.53(d，1H)，7.38(s，1H)，7.34(s，1H)，6.67(d，1H)，6.61(d，1H)，3.40(m，4H)，1.73(m，4H)，1.29(m，4H)，0.98(m，6H)。
Embodiment 5:
The title complex two that makes with embodiment 1 (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl) (pyridine carboxylic acid) close iridium (hereinafter to be referred as (dfpyMepy)
2Irpic) as the organic electroluminescence device of the doping object of luminescent layer, structure as shown in Figure 3:
This device is followed successively by ITO/PEDOT:PSS/PVK:7wt% (dfpyMepy)
2Irpic/BCP/Alq
3/ LiF/Al, namely glass substrate deposition one deck square resistance be the tin indium oxide (ITO) of 10～20 Ω as transparent anode, be doped with (dfpyMepy) that 7wt% present embodiment 1 prepares at ITO preparation one deck PEDOT:PSS hole injections/transport material and one deck successively by spin coating technique
2The PVK luminescent layer of Irpic, successively vacuum evaporation a layer thickness is that the BCP layer of 10nm is the Alq of 30nm as hole blocking layer, thickness on this luminescent layer again
3As electron transfer layer, thickness be the LiF of 1nm as the electronic injection buffer layer, adopting the vacuum coating technology deposit thickness at buffer layer at last is the metal A l of 120nm, as the negative electrode of device.
The organic electroluminescence device experimental data of present embodiment: under the operating voltage of 9V, the blue light of emission 450nm, purity of color is higher, and brightness is 2900cd/m
2, luminous intensity is better.
This electroluminescent device since contain in the luminescent layer purity of color and fluorescence quantum efficiency higher contain iridium blue phosphorescent organic electroluminescent material, it has higher effciency of energy transfer and luminous efficiency, can be widely used in the luminous fields such as blueness or white.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains the iridium electroluminescent organic material, it is characterized in that, has following structural formula I:
Wherein, R is C
1～C
4Alkyl.
2. a preparation method who contains the iridium electroluminescent organic material is characterized in that, comprises the steps:
Step 1: prepare or provide compd A, Compound C that following structural formula represents,
And IrCl
33H
2O, wherein, R is C
1～C
4Alkyl;
Step 2: under the oxygen free condition, with compd A and IrCl
33H
2O carried out back flow reaction in 3: 1 in molar ratio～5: 1 in solvent, generate two endo compound B, and reaction formula is as follows,
Step 3: under anaerobic and the weak basic condition, two endo compound B and Compound C were carried out ligand exchange reaction generation Compound I in 1: 2.5 in molar ratio～1: 3.5 in solvent, reaction formula is as follows,
3. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2 is characterized in that, in the step 2, described solvent is cellosolvo; In the step 3, described solvent is cellosolvo, 1,2-ethylene dichloride, glycerine or tetrahydrofuran (THF), and the temperature of described ligand exchange reaction is the back flow reaction temperature.
4. the preparation method who contains as claimed in claim 2 or claim 3 the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to compd B after the step 2: at first the reacted mixed solution of step 2 is carried out concentrating under reduced pressure and process, obtain concentrated solution; Then take methylene dichloride as elutriant described concentrated solution is carried out silica gel column chromatography and separate, obtain the described compd B of purifying.
5. the preparation method who contains as claimed in claim 2 or claim 3 the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to Compound I after the step 3: at first remove the solvent in the rear mixed solution of step 3 reaction, add distilled water, separate out solid, solid collected by filtration, obtain containing the crude product of Compound I, then after using successively normal hexane, the described crude product of ether supersound washing for several times, separate as elutriant carries out silica gel column chromatography to described crude product with the mixed solution of methylene dichloride take normal hexane, obtain the described Compound I of purifying.
6. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2 is characterized in that, the preparation process of compd A comprises the steps:
The Compound D and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent,
Under the anhydrous and oxygen-free condition, at first Compound D was reacted in solvent with diisopropylamine lithium in 1: 1 in molar ratio～1: 1.5, obtain containing 2, the mixture of 6-difluoro pyridine base-3-lithium, then described mixture and trimethyl borate reaction are obtained compd E, wherein, the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, reaction formula is as follows
The compd E and the compound F 17-hydroxy-corticosterone that make were carried out the Suzuki linked reaction in 1.5: 1 in molar ratio～2: 1 in solvent, generate described compd A, reaction formula is as follows,
7. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 6, it is characterized in that, temperature in Compound D and the diisopropylamine lithium reaction process is-78 ℃, and the solvent of use is the new ether that steams, and the temperature of mixture and trimethyl borate reaction is room temperature;
The temperature of Suzuki linked reaction is the back flow reaction temperature; The catalyzer that uses is K
2CO
3With Pd (PPh
3)
4Co-catalyst, wherein K
2CO
3Molar weight is 10 times of compound F 17-hydroxy-corticosterone, Pd (PPh
3)
4Molar weight be 0.5% of compound F 17-hydroxy-corticosterone; Solvent is the mixed solution of tetrahydrofuran (THF) and water.
8. such as claim 6 or the 7 described preparation methods that contain the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to compd E: at first be 5% NaOH aqueous solution termination reaction with massfraction; Then be that pH of mixed value behind the HCl aqueous solution conditioned reaction of 3M is to neutral, again with merging organic phase behind the ethyl acetate extraction with concentration; Concentrate at last organic phase, obtain the described compd E of purifying.
9. such as claim 6 or the 7 described preparation methods that contain the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to compd A: at first add distilled water in the mixed solution after the Suzuki linked reaction, with merging organic phase behind the ethyl acetate extraction; Then use anhydrous MgSO
4Dry organic phase is filtered concentrated filtrate; Make eluent with ethyl acetate and the mixed solution of normal hexane at last and filtrate is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
10. an organic electroluminescence device comprises luminescent layer, it is characterized in that, contains the Compound I that following structural formula represents in the described luminescent layer:
Wherein, R is C
1～C
4Alkyl.
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| CN104178103A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic electroluminescence material and preparation method and application |
| CN104178107A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
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| CN1664054A (en) * | 2004-02-02 | 2005-09-07 | 三星Sdi株式会社 | IR compound and organic electroluminescent device using the same |
| CN1951947A (en) * | 2005-10-18 | 2007-04-25 | 株式会社半导体能源研究所 | Organometallic complex, and light-emitting element and light-emitting device using the same |
| CN101182412A (en) * | 2007-12-18 | 2008-05-21 | 江南大学 | Amides Ir organometallic complex electroluminescent material and uses thereof |
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| CN1664054A (en) * | 2004-02-02 | 2005-09-07 | 三星Sdi株式会社 | IR compound and organic electroluminescent device using the same |
| CN1951947A (en) * | 2005-10-18 | 2007-04-25 | 株式会社半导体能源研究所 | Organometallic complex, and light-emitting element and light-emitting device using the same |
| CN101182412A (en) * | 2007-12-18 | 2008-05-21 | 江南大学 | Amides Ir organometallic complex electroluminescent material and uses thereof |
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| CN104178103A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic electroluminescence material and preparation method and application |
| CN104178107A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Blue phosphorescence iridium metal complex, preparation method and organic electroluminescent device |
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