CN102898475A - 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. Aiming at overcoming the disadvantage of a conventional material, the iridium-containing organic electroluminescent material introduces an alkyl function group on dipyridine, introduces a strong field ligand of 5-(2'-pyridyl)tetrazole as an auxiliary ligand, enabling the luminescence spectrum of the iridium-containing organic electroluminescent material to be blueshifted effectively and allowing the iridium-containing organic electroluminescent material to have higher colour purity of blue light than that of the conventional material. Besides, the invention also relates to a preparation method for the iridium-containing organic electroluminescent material and an organic electroluminescent device including the iridium-containing organic electroluminescent material.
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 a kind of organic electroluminescence device of containing.
[background technology]
Organic electroluminescent (EL) 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 made 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 the good stability of its compound, 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.Up to now, two [2-(4 ', 6 '-difluorophenyl) pyridine-N, C
2'] (2-pyridine carboxylic acid) to close iridium (FIrpic) be that the document patent report gets one of Ir (III) a metal-organic complex blue phosphorescent electroluminescent material at most.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 the OLED device of making changes between (0.13～0.17,0.29～0.39).
Therefore, develop the higher electroluminescent organic material of blue light color purity and become a megatrend of expanding the blue light material research field.
[summary of the invention]
Based on this, be necessary to provide a kind of blue light color purity higher contain iridium electroluminescent organic material and preparation method thereof.
In addition, also be necessary to provide a kind of above-mentioned organic electroluminescence device that contains the iridium electroluminescent organic material that comprises.
A kind of iridium electroluminescent organic material that contains has following structural formula I:
Wherein, R is C
1～C
4Alkyl.
A kind of preparation method who contains the iridium electroluminescent organic material comprises the steps:
Step 1, the compd A that provides following structural formula to represent:
Step 3, under oxygen free condition, the Compound C of described two endo compound B and 5-by name (2 '-pyridyl) tetrazolium is carried out ligand exchange reaction according to 1: 2.5～1: 3.5 mol ratio generate the described iridium electroluminescent organic material that contains with following structural formula I in solvent, reaction formula is as follows:
Preferably, in the step 2, solvent is cellosolvo;
In the step 3, solvent is 1,2-ethylene dichloride, glycerine, cellosolvo 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, two endo compound B and Compound C described in the step 3 are reacted under the co-catalyst effect of sodium methylate and silver triflate composition.
Preferably, also comprise the purification procedures to Compound I after the step 3: at first in the reacted mixed solution of step 3, add distilled water, separate out solid, solid collected by filtration, obtain containing the crude product of Compound I, then wash with deionized water, ether successively that the mixed solution take ethyl acetate and normal hexane separates as elutriant carries out silica gel column chromatography to described crude product behind the described crude product, obtain the described Compound I of purifying.
Preferably, described compd A prepares as follows:
At first, the Compound D and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent:
Wherein, R is C
1～C
4Alkyl;
Secondly, under anhydrous and oxygen-free ,-78 ℃ condition, Compound D and diisopropylamine lithium were reacted in solvent in 1: 1 in molar ratio～1: 1.5, then adding trimethyl borate at room temperature reacts and obtains compd E, wherein, the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, and reaction formula is as follows:
At last, described compd E and described compound F 17-hydroxy-corticosterone 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 solvent that uses in Compound D and the described diisopropylamine lithium reaction process is anhydrous diethyl ether, and described diisopropylamine lithium adopts the form of the tetrahydrofuran solution of diisopropylamine lithium to add;
The temperature of Suzuki linked reaction is the back flow reaction temperature, and solvent is the mixed solution of tetrahydrofuran (THF) and water, and the catalyzer that uses is K
2CO
3With Pd (PPh
3)
4Co-catalyst, K
2CO
3Molar weight is 10 times of described compound F 17-hydroxy-corticosterone, Pd (PPh
3)
4Molar weight be 0.5% of described compound F 17-hydroxy-corticosterone.
Preferably, also comprise purification procedures to described compd E: at first be 5% NaOH aqueous solution termination reaction with massfraction; Then with concentration be pH of mixed value behind the HCl aqueous solution conditioned reaction of 3M to neutral, then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying;
Also comprise the purification procedures to compd A: at first add distilled water in the mixed solution after the Suzuki linked reaction, repeatedly extract rear merging organic phase with ethyl acetate; Then use anhydrous MgSO
4Dry organic phase is filtered and concentrated filtrate; Make eluent with ethyl acetate and the mixed solution of normal hexane at last and described filtrate is carried out silica gel column chromatography separate, obtain the described compd A of purifying.
A kind of organic electroluminescence device comprises luminescent layer, contains the Compound I that following structural formula represents in the described luminescent layer:
Wherein, R is C
1～C
4Alkyl.
This iridium electroluminescent organic material that contains is for the shortcoming of traditional material, introduce alkyl functional group at dipyridyl, introducing high field part 5-(2 '-pyridyl) tetrazolium is assistant ligand, makes the effective blue shift of its luminescent spectrum, higher with respect to traditional material blue light color purity.
[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]
Iridium (Ir) a metal-organic complex is a kind of phosphorescent light-emitting materials with shorter phosphorescent lifetime (1～14 μ s).
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.
Present embodiment contain the iridium electroluminescent organic material, have molecular formula (dfpyRpy)
2IrN
4Wherein, 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; N4 represents assistant ligand 5-in the title complex (2 '-pyridyl) tetrazolium.
The above-mentioned concrete structure formula that contains the iridium electroluminescent organic material is as follows:
Wherein, R is C
1～C
4Alkyl.
This iridium electroluminescent organic material that contains is for the shortcoming of traditional material, introduce alkyl functional group at dipyridyl, introducing high field part 5-(2 '-pyridyl) tetrazolium is assistant ligand, makes the effective blue shift of its luminescent spectrum, higher with respect to traditional material blue light color purity.
In addition, this iridium electroluminescent organic material that contains 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.
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.
A kind of above-mentioned preparation method who contains the iridium electroluminescent organic material is provided, comprises the steps:
Unless below operation special stipulation are all carried out under the anhydrous and oxygen-free condition, 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.
S1, the compd A that provides following structural formula to represent:
Compd A can prepare as follows:
At first, the Compound D and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent:
Wherein, R is C
1～C
4Alkyl.
Secondly, in ether solvent, under the condition of anhydrous and oxygen-free, the THF solution of Compound D and N-Lithiodiisopropylamide (LDA) reacted under-78 ℃ of low temperature make 2, behind 6-difluoro pyridine base-3-lithium, make at normal temperatures the compd E of 2,6-, two fluoro-3-boric acid pyridines by name with the trimethyl borate reaction; Wherein, the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, and reaction formula is as follows:
Wherein, diisopropylamine lithium adopts the form of the tetrahydrofuran solution of diisopropylamine lithium to add.
In a preferred embodiment, can also be to the separation and purification of carrying out of compd E, concrete operations are: be first 5% NaOH aqueous solution termination reaction with massfraction; Then with concentration be pH of mixed value behind the HCl aqueous solution conditioned reaction of 3M to neutral, then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying.
At last, compd E and described compound F 17-hydroxy-corticosterone 1.5: 1 in molar ratio～2: 1, in the mixed solvent of tetrahydrofuran (THF) and water composition, 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:
The temperature of Suzuki linked reaction is the back flow reaction temperature, and solvent is the mixed solution of tetrahydrofuran (THF) and water, K in the co-catalyst
2CO
3Molar weight be 10 times of described compound F 17-hydroxy-corticosterone, Pd (PPh
3)
4Molar weight be 0.5% of described compound F 17-hydroxy-corticosterone.
In a preferred embodiment, can also carry out separation and purification to compd A, concrete operations are: add distilled water in the first mixed solution after the Suzuki linked reaction, repeatedly extract rear merging organic phase with ethyl acetate; Then use anhydrous MgSO
4Dry organic phase is filtered and 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.
S2, in the reaction system take cellosolvo as solvent, compd A and three hydration iridous chlorides were according to 3: 1～5: 1 molar ratio, in oxygen free condition, reaction generates two endo compound B under the reflux state, reaction formula is as follows:
Two endo compound B can be designated as (dfpyRpy)
2Ir (μ-Cl)-(dfpyRpy)
2
In a preferred embodiment, also comprise purification procedures to two endo compound B: 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 S3, with 1,2-ethylene dichloride, glycerine, cellosolvo or tetrahydrofuran (THF) are in the reaction system of solvent, with the Compound C of two endo compound B and 5-by name (2 '-pyridyl) the tetrazolium mol ratio according to 1: 2.5～1: 3.5, under the co-catalyst effect of sodium methylate and silver triflate composition, carry out ligand exchange reaction under the back flow reaction temperature, obtain having the above-mentioned iridium electroluminescent organic material that contains of following structural formula I, reaction formula is as follows:
Present embodiment contain the iridium electroluminescent organic material, have molecular formula (dfpyRpy)
2IrN
4Wherein, 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; N4 represents assistant ligand 5-in the title complex (2 '-pyridyl) tetrazolium.
In a preferred embodiment, also comprise the purification procedures to Compound I: after at first the question response mixed solution is chilled to room temperature naturally, concentrates and remove a part of solvent, an amount of distilled water of impouring is to separate out solid; Then filter, behind the collection crude product, solid with deionized water, ether washing for several times; At last take the mixed solution of ethyl acetate and normal hexane as elutriant crude product being carried out silica gel column chromatography separates and obtains pure target product I.
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
Preparation flow synoptic diagram as shown in Figure 1, title complex two (2 ', 6 '-two fluoro-4-methyl-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl) tetrazolium) close iridium [(dfpyMepy)
2IrN
4] synthetic specifically comprise the steps:
Synthesizing of (1) 2,6-two fluoro-3-boric acid pyridines.
Under the protection of nitrogen, the N-Lithiodiisopropylamide THF solution of 7.5mL (12mmol) 1.6M is slowly dropped to-78 ℃ contain 0.91mL (10mmol) 2, in the mixed solution of 6-difluoro pyridine and 40mL ether, keep-78 ℃ of temperature stirring reaction 1h.In reaction system, add 1.40mL (12.5mmol) trimethyl borate, naturally be warming up to room temperature, continue stirring reaction 1h.Slowly adding the 20mL massfraction to reaction mixture is 5% NaOH aqueous solution termination reaction, stir 10min after, dropwise add the HCl aqueous solution adjust pH of an amount of 3M to neutral.Ethyl acetate repeatedly extracts rear merging organic phase, and the rotary evaporation desolventizing obtains white solid thing 1.43g, and yield is 90%.
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 protection of nitrogen, with (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
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 volume ratio as 1: 3 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography, get colorless solid product 0.53g, yield is 64.3%.
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 nitrogen protection, with 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%.
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)
2IrN
4Synthetic.
Under nitrogen protection, with 0.44g (3mmol) 5-(2 '-pyridyl) tetrazolium and 1.28g (1mmol) two endo compounds (dfpyMepy)
2Ir (the Ir (dfpyMepy) of μ-Cl)
2Be dissolved in 60mL1, in the 2-ethylene dichloride, 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, concentrate and remove a part of solvent, the an amount of distilled water of impouring, filter after separating out solid, collect solid crude product, successively with after deionized water, the ether washing for several times, take volume ratio as 1: 3 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography to it, get 0.76g, pure products (dfpyMepy)
2IrN
4, yield is 50.8%.
1H?NMR(400MHz，CDCl
3，ppm)：δ9.10(d，1H)，8.75(d，1H)，8.69(d，1H)，8.33(d，1H)，8.10(m，1H)，7.72(m，1H)，7.60(s，1H)，7.57(s，1H)，7.40(d，1H)，7.37(d，1H)，6.37(s，1H)，6.28(s，1H)，2.66(s，6H)。
Concentration as shown in Figure 2 is about 10
-5(dfpyMepy) of M
2IrN
4CH
2Cl
2The emmission spectrum maximum emission peak of solution under the 298K temperature has an acromion at the 462nm place simultaneously at the 442nm 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 0.1N quinoline sulfate
2SO
4Solution is standard Φ
PL=0.54, record concentration and be about 10
-5(dfpyMepy) of M
2IrN
4CH
2Cl
2The Φ of solution
PL=0.64, (dfpyMepy) of visible present embodiment
2IrN
4Have higher internal quantum efficiency and electroluminescent efficiency.
Title complex two (2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl) tetrazolium) close synthesizing of iridium.
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to case study on implementation 1.
(2) 2 ', 6 '-two fluoro-4-ethyls-2,3 '-dipyridyl synthetic.
Under the protection of nitrogen, with (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 volume ratio as 1: 4 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography, get colorless solid product 0.57g, yield is 60.8%.
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 protection of nitrogen, with 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%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.81(d，4H)，7.67(d，4H)，7.56(s，4H)，6.75(s，4H)，2.88(m，8H)，1.47(m，12H)。
(4) Complex synthesis.
Under the protection of nitrogen; 0.44g (3mmol) 5-(2 '-pyridyl) tetrazolium and 1.33g (1mmol) two endo compounds are dissolved in 60mL1; in the 2-ethylene dichloride; 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, concentrate and remove a part of solvent, the an amount of distilled water of impouring, filter after separating out solid, collect solid crude product, successively with after deionized water, the ether washing for several times, take volume ratio as 1: 3 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography to it, get the 0.74g pure products, yield is 47.6%.
1H?NMR(400MHz，CDCl
3，ppm)：δ9.11(d，1H)，8.74(d，1H)，8.69(d，1H)，8.35(d，1H)，8.11(m，1H)，7.73(m，1H)，7.58(s，1H)，7.54(s，1H)，7.36(d，1H)，7.33(d，1H)，6.34(s，1H)，6.28(s，1H)，2.78(m，4H)，1.41(m，6H)。
Embodiment 3
Title complex two (2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl) tetrazolium) close synthesizing of iridium.
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to case study on implementation 1.
(2) 2 ', 6 '-two fluoro-4-propyl group-2,3 '-dipyridyl synthetic.
Under the protection of nitrogen, with (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, repeatedly extract with an amount of ethyl acetate after adding an amount of distilled water.Merge organic phase, anhydrous MgSO
4Dry.Get crude product after removing solvent under reduced pressure.Take volume ratio as 1: 4 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography, get colorless solid product 0.57g, yield is 60.8%.
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 protection of nitrogen, with 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%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.68(d，4H)，7.57(s，4H)，6.76(s，4H)，2.78(m，8H)，1.78(m，8H)，0.99(m，12H)。
(4) Complex synthesis.
Under the protection of nitrogen; 0.44g (3mmol) 5-(2 '-pyridyl) tetrazolium and 1.39g (1mmol) two endo compounds are dissolved in 60mL1; in the 2-ethylene dichloride; 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, concentrate and remove a part of solvent, the an amount of distilled water of impouring, filter after separating out solid, collect solid crude product, successively with after deionized water, the ether washing for several times, take volume ratio as 1: 3 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography to it, get the 0.66g pure products, yield is 41.0%.
1H?NMR(400MHz，CDCl
3，ppm)：δ9.11(d，1H)，8.72(d，1H)，8.68(d，1H)，8.35(d，1H)，8.12(m，1H)，7.72(m，1H)，7.55(s，1H)，7.51(s，1H)，7.33(d，1H)，7.30(d，1H)，6.31(s，1H)，6.27(s，1H)，2.68(m，4H)，1.61(m，4H)，0.99(m，6H)。
Embodiment 4
Title complex two (2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl) tetrazolium) close synthesizing of iridium.
The synthesis step of (1) 2,6-two fluoro-3-boric acid pyridines is referring to case study on implementation 1.
(2) 2 ', 6 '-two fluoro-4-butyl-2,3 '-dipyridyl synthetic.
Under the protection of nitrogen, with (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 volume ratio as 1: 4 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography, get colorless solid product 0.61g, yield is 61.4%.
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 protection of nitrogen, with 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%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.77(d，4H)，7.67(d，4H)，7.55(s，4H)，6.76(s，4H)，2.61(m，8H)，1.76(m，8H)，1.33(m，8H)，0.98(m，12H)。
(4) Complex synthesis.
Under the protection of nitrogen; 0.44g (3mmol) 5-(2 '-pyridyl) tetrazolium and 1.44g (1mmol) two endo compounds are dissolved in 60mL1; in the 2-ethylene dichloride; 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, concentrate and remove a part of solvent, the an amount of distilled water of impouring, filter after separating out solid, collect solid crude product, successively with after deionized water, the ether washing for several times, take volume ratio as 1: 3 ethyl acetate and the mixed solution of normal hexane separate as elutriant carries out silica gel column chromatography to it, get the 0.65g pure products, yield is 39.0%.
1H?NMR(400MHz，CDCl
3，ppm)：δ9.11(d，1H)，8.70(d，1H)，8.67(d，1H)，8.35(d，1H)，8.13(m，1H)，7.73(m，1H)，7.53(s，1H)，7.48(s，1H)，7.30(d，1H)，7.28(d，1H)，6.30(s，1H)，6.27(s，1H)，2.60(m，4H)，1.65(m，4H)，1.32(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-N, C
2') (5-(2 '-pyridyl) tetrazolium) close iridium (hereinafter to be referred as (dfpyMepy)
2IrN
4) 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)
2IrN
4/ 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 (dfpymMepy) that the 7wt% present embodiment prepares at ITO preparation one deck PEDOT:PSS hole injections/transport material and one deck successively by spin coating technique
2IrN
4The PVK luminescent layer, more successively vacuum evaporation one deck BCP layer (as hole blocking layer), Alq on this luminescent layer
3(as electron transfer layer), LiF (as the electronic injection buffer layer) adopt vacuum coating technology metal refining Al at buffer layer, at last as the negative electrode of device.
Under the operating voltage of 9V, the blue light of device emission 444nm, device brightness is 2500cd/m
2
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 one or more embodiments 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, the compd A that provides following structural formula to represent:
Wherein, R is C
1～C
4Alkyl;
Step 2, under oxygen free condition, described compd A and three hydration iridous chlorides reacted in solvent according to 3: 1～5: 1 molar ratio generate two endo compound B, reaction formula is as follows:
Step 3, under oxygen free condition, the Compound C of described two endo compound B and 5-by name (2 '-pyridyl) tetrazolium is carried out ligand exchange reaction according to 1: 2.5～1: 3.5 mol ratio generate the described iridium electroluminescent organic material that contains with following structural formula I 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, solvent is cellosolvo;
In the step 3, solvent is 1,2-ethylene dichloride, glycerine, cellosolvo 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 the iridium electroluminescent organic material as claimed in claim 2 is characterized in that, two endo compound B and Compound C described in the step 3 are reacted under the co-catalyst effect of sodium methylate and silver triflate composition.
6. such as claim 2, the 3 or 5 described preparation methods that contain the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to Compound I after the step 3: at first in the reacted mixed solution of step 3, add distilled water, separate out solid, solid collected by filtration, obtain containing the crude product of Compound I, then wash with deionized water, ether successively that the mixed solution take ethyl acetate and normal hexane separates as elutriant carries out silica gel column chromatography to described crude product behind the described crude product, obtain the described Compound I of purifying.
7. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2 is characterized in that, described compd A prepares as follows:
At first, the Compound D and the compound F 17-hydroxy-corticosterone that provide following structural formula to represent:
Secondly, under anhydrous and oxygen-free ,-78 ℃ condition, Compound D and diisopropylamine lithium were reacted in solvent in 1: 1 in molar ratio～1: 1.5, then adding trimethyl borate at room temperature reacts and obtains compd E, wherein, the mol ratio of trimethyl borate and Compound D is 1: 1～1.5: 1, and reaction formula is as follows:
At last, described compd E and described compound F 17-hydroxy-corticosterone 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:
8. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 7, it is characterized in that, the solvent that uses in Compound D and the described diisopropylamine lithium reaction process is anhydrous diethyl ether, and described diisopropylamine lithium adopts the form of the tetrahydrofuran solution of diisopropylamine lithium to add;
The temperature of Suzuki linked reaction is the back flow reaction temperature, and solvent is the mixed solution of tetrahydrofuran (THF) and water, and the catalyzer that uses is K
2CO
3With Pd (PPh
3)
4Co-catalyst, K
2CO
3Molar weight is 10 times of described compound F 17-hydroxy-corticosterone, Pd (PPh
3)
4Molar weight be 0.5% of described compound F 17-hydroxy-corticosterone.
9. such as claim 7 or the 8 described preparation methods that contain the iridium electroluminescent organic material, it is characterized in that, also comprise the purification procedures to described compd E: at first be 5% NaOH aqueous solution termination reaction with massfraction; Then with concentration be pH of mixed value behind the HCl aqueous solution conditioned reaction of 3M to neutral, then repeatedly extract rear merging organic phase with ethyl acetate; Concentrate at last organic phase, obtain the described compd E of purifying;
Also comprise the purification procedures to compd A: at first add distilled water in the mixed solution after the Suzuki linked reaction, repeatedly extract rear merging organic phase with ethyl acetate; Then use anhydrous MgSO
4Dry organic phase is filtered and concentrated filtrate; Make eluent with ethyl acetate and the mixed solution of normal hexane at last and described 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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| CN104177437A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Blue phosphorescence iridium complexes, preparing method thereof and organic electroluminescent device |
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| CN104177425A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Blue light organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device |
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