CN102649800A - 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 a general formula shown in the specification, wherein R is an alkyl group of C1-C8. A molecule of the iridium-containing organic electroluminescent material contains a benzimidazolyl group with an electron transport function; the benzimidazolyl group also has an alkyl group and a fluorophenyl group; the electron injection and transport capacity of the electroluminescent material can be improved; and the iridium-containing organic electroluminescent material has higher internal quantum efficiency and electroluminescent efficiency. In addition, the invention also relates to a preparation method of the iridium-containing organic electroluminescent material and an organic electroluminescent device using 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 that contains, and adopt this to contain the organic electroluminescence device of iridium electroluminescent organic material.
[background technology]
Organic electroluminescent is meant organic materials under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Reason such as too high owing to made device drive voltage in early days, that luminous efficiency is low makes that the research to organic electroluminescent stays cool.Up to 1987, people such as the Tang of Kodak invented with oxine aluminium (Alq
3) be luminescent material, process the high-quality thin film of even compact with aromatic diamine, made than the relative higher brightness under the low-work voltage, high efficiency organic electroluminescence device, opened new prelude to electroluminescent organic material research.But owing to receive the restriction of spin statistical theory, the fluorescent material internal quantum efficiency limit in theory is merely 25%, how to make full use of all the other phosphorescence of 75% and obtains higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found the phosphorescence electro optical phenomenon, and the internal quantum efficiency of the electroluminescent organic material that obtains is subsequently broken through 25% restriction, made the research of electroluminescent organic material get into another new period.
In the electroluminescent organic material research now, the title complex of small molecules doped transition metal has become people's research emphasis, like the title complex of iridium, ruthenium, platinum etc.The advantage of this type title complex is that they can obtain very high emitted energy from the triplet of self; And metal iridium (III) compound wherein; Because the good stability of its compound; Reaction conditions is gentle in building-up process, and has very high electroluminescent properties, in research process subsequently, is accounting for dominant position always.Blue light obtains full-color demonstration in order to make device, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Compare with green light luminescent material with ruddiness, the development of blue light electroluminescent material lags behind comparatively speaking, improves the efficient of blue light electroluminescent material and the focus that fullness of shade becomes people's research.Two [2-(2,4 difluorobenzene base) pyridine-N, C
2] (VPP) to close iridium (FIrpic) be one of Ir (III) a metal-organic complex blue light electroluminescent material of reporting morely.People make FIrpic class luminescent material be greatly improved in the performance aspect efficient and the fullness of shade through methods such as ligand modified and element manufacturing.2005, it was that the electroluminescent organic material three (1-phenyl-3-tolimidazole) of part closes iridium (Ir (pmb) that people such as Holmes and Forrest have synthesized with 1-phenyl-3-tolimidazole first
3), its CIE is (0.17,0.06) (APPLIED PHYSICSLETTERS 2,005 87 243507).In general, the 2-VPP often is the more excellent assistant ligand of blue light metal Ir (III) luminous organic material, closes iridium [(EO-CVz-PhQ) like FIrpic, two (4-phenyl-2-(6-(N-(2-(2-methoxyl group) oxyethyl group) ethyl) carbazole) quinoline) (VPP)
2Ir (pic)] (Adv.Funct.Mater.2009,19,2205-2212) etc.; Contain fluorine-based substituted title complex on the part and compare its luminous blue shift of wanting with corresponding floride-free title complex, and as three [2-(4, the 6-difluorophenyl) pyridine) close iridium [Ir (F
2Ppy)
3] than three [the 2-phenylpyridine) close iridium [Ir (ppy)
3] photochromic at blue shift under the 77K temperature under 37nm, the 298K temperature blue shift 42nm, two [1-(4, the 6-difluorophenyl) pyrazoles]) (2-phenylpyridine) close iridium [(F
2Ppz)
2Ir (ppy)] close iridium [(ppz) than two (1-phenylpyrazole) (2-phenylpyridine)
2Ir (ppy)] photochromic at blue shift under the 77K temperature under 14nm, the 298K temperature blue shift 25nm (J.AM.CHEM.SOC.2009,131,9813-9822).
[summary of the invention]
Based on this, be necessary to provide a kind of iridium electroluminescent organic material and preparation method thereof that contains.
A kind of iridium electroluminescent organic material that contains has general formula H:
Wherein, R is C
1～C
8Alkyl.
This contains the iridium electroluminescent organic material and at room temperature has stronger blue phosphorescent emission characteristics, and research range that can the efficient extn blue light material is for the blue-light device of high-luminous-efficiency or the research of white light parts provide further technical support.In addition; This contains the benzimidazolyl-that contains the electric transmission function in the iridium electroluminescent organic material molecule; And also have fluorophenyl on the benzimidazolyl-, the electronics that can improve luminescent material injects and transmittability, has higher internal quantum efficiency and electroluminescent efficiency; In addition, the 1-that also contains in the molecule (2,4 difluorobenzene base)-3-substituting group benzoglyoxaline ylidene ligands, the solvability that can regulate compound through the length of 3-position substituted alkyl chain is improved processing characteristics.
A kind of preparation method who contains the iridium electroluminescent organic material comprises the steps:
Preparation or the compd A and the compd B that provide following structural formula to represent,
Wherein, R is C
1～C
8Alkyl;
Under anaerobic and catalyzer condition, with said compd A and compd B reacting by heating in solvent, obtain containing the mixture of compound H, reaction formula is following:
After the cooling, the said mixture of separation and purification obtains compound H.
Preferably, said catalyzer is a basic cpd, and said solvent is a cellosolvo, 1, a kind of in 2-ethylene dichloride, methylene dichloride and the trichloromethane, and said reacting by heating is a back flow reaction.
Preferably, said basic cpd is sodium methylate, yellow soda ash, salt of wormwood, sodium phosphate and potassiumphosphate.
Preferably; The said mixture of separation and purification comprises the steps: that at first mixture being carried out concentrating under reduced pressure handles the solids that obtains containing compound H; Then said solids is used deionized water, normal hexane and ether washing successively; Use the ETHYLE ACETATE and the mixed solvent of normal hexane to make eluent at last and solids is carried out silica gel column chromatography separate, obtain the said compound H of purifying.
Preferably, the preparation process of compd A comprises the steps:
Step 1, the Compound C and the D that provide following structural formula to represent,
Step 3, the compd E that makes reacted in solvent with alkyl iodide generate said compound G, reaction formula is following:
R-I is an alkyl iodide, and R is C
1～C
8Alkyl.
Step 4: under anaerobic and catalyzer condition, compound G is reacted the said compd A of generation with three hydration iridous chlorides in solvent, reaction formula is following:
Preferably, in the said step 2, the temperature of reaction of Ullmann linked reaction is 100～180 ℃, and catalyzer is a cupric iodide, 1, the mixed catalyst that 10-phenanthrolene and cesium carbonate are formed, and solvent is N, dinethylformamide; In the said step 3, solvent is a toluene, and temperature of reaction is 25～45 ℃; In the said step 4, catalyzer is a silver suboxide, and solvent is a cellosolvo, and temperature of reaction is 100～150 ℃.
Preferably, further comprise purification procedures after the said step 2: at first the mixed solution after the Ullmann linked reaction is carried out vacuum concentration and handle to compd E; In liquid concentrator, add ethyl acetate solution then, produce throw out; The filtering separation throw out, and use the ETHYLE ACETATE washing precipitate, collect filtrating; Last concentrated filtrate, the mixed solvent that uses ETHYLE ACETATE and normal hexane carry out silica gel column chromatography as elutriant to filtrating to be separated and obtains compd E;
Further comprise purification procedures after the said step 3 to compound G: the reacting coarse product of filtration step three, use the filtering throw out of toluene wash again, promptly obtain the compound G of purifying after the drying; Further comprise purification procedures after the said step 4: at first the compound G reacted mixed solution of three hydration iridous chlorides is together carried out concentrating under reduced pressure and handle to compd A; Be that elutriant carries out silica gel column chromatography separation 2～3 times to liquid concentrator then with the methylene dichloride, obtain the said compd A of purifying.
Preferably, the preparation process of compd B comprises the steps:
At first in reactor drum, add toluene and hydrochloric acid soln; Under agitation condition, in reactor drum, add triethylamine, 2-cyanopyridine and sodium azide more successively, mix post-heating to refluxing stirring reaction 10～30 hours; After the cooling, use zero(ppm) water extractive reaction liquid, separatory; Regulate the water potential of hydrogen to pH4.5～5.5; Produce white precipitate, be said compd B, reaction formula is following:
Above-mentioned preparing method's principle is simple, easy and simple to handle, low for equipment requirements, but wide popularization and application.
In addition, also be necessary to provide a kind of internal quantum efficiency and the higher organic electroluminescence device of electroluminescent efficiency.
A kind of organic electroluminescence device comprises luminescent layer, contains the compound H that formula is represented in the said luminescent layer:
Material of main part in above-claimed cpd H and the organic electroluminescence device luminescent layer has consistency preferably, can be widely used in preparation blue light or white-light phosphor photoelectricity electroluminescence device.Electroluminescent device since contain in the luminescent layer higher internal quantum efficiency and electroluminescent efficiency blue light contain the iridium electroluminescent organic material, thereby it has higher effciency of energy transfer and luminous efficiency.
[description of drawings]
Fig. 1 is the preparation flow synoptic diagram that contains the iridium electroluminescent organic material of an embodiment;
Fig. 2 is the emmission spectrum figure of electroluminescent organic material among the embodiment 8;
Fig. 3 is the structural representation of organic electroluminescence device among the embodiment 8.
[embodiment]
Mainly combine accompanying drawing and specific embodiment to do further detailed explanation with organic electroluminescence device below to containing iridium electroluminescent organic material and preparation method thereof.
Iridium (Ir) a metal-organic complex is a kind of phosphorescent light-emitting materials with shorter phosphorescent lifetime (1～14 μ s).This embodiment contain the iridium electroluminescent organic material, have following general formula H:
Wherein, R is C
1～C
8Alkyl, can be straight chained alkyl, also can be for containing the alkyl of side chain, like methyl, ethyl, propyl group, normal-butyl, isobutyl-, amyl group, isopentyl, neo-pentyl, hexyl, heptyl and octyl group etc.
This embodiment contain the benzimidazolyl-that contains the electric transmission function in the iridium electroluminescent organic material molecule; And also have alkyl, fluorophenyl on the benzimidazolyl-; The electronics that can improve luminescent material injects and transmittability, has higher internal quantum efficiency and electroluminescent efficiency; In addition, the 1-that also contains in the molecule (2,4 difluorobenzene base)-3-substituting group benzoglyoxaline ylidene ligands, the solvability that can regulate compound through the length of 3-position substituted alkyl chain is improved processing characteristics.
The material of main part that contains in iridium electroluminescent organic material and the organic electroluminescence device luminescent layer has consistency preferably, 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.
As shown in Figure 1, the above-mentioned preparation method who contains the iridium electroluminescent organic material can comprise the steps:
Below each step all under oxygen free condition (as at N
2Or atmosphere of inert gases is inferior) carry out, the solvent that solvent for use provided except that each step, can also adopt other and reactant to have the solvent of better intermiscibility.
Step S1: at N, in dinethylformamide (DMF) solvent, with Compound C (2,4-difluoro iodobenzene) and Compound D (benzoglyoxaline) at cupric iodide (CuI), 1,10-phenanthrolene and cesium carbonate (CeCO
3) under the mixed catalyst effect formed, carry out the Ullmann linked reaction in 100～180 ℃ of environment, make compd E (1-(2,4 difluorobenzene base) benzoglyoxaline), reaction formula is following:
Preferably, further comprise purification procedures after the step S1: at first the mixed solution after the Ullmann linked reaction is carried out vacuum concentration and handle to compd E; In liquid concentrator, add ethyl acetate solution then, produce throw out; The filtering separation throw out, and use the ETHYLE ACETATE washing precipitate, collect filtrating; Last concentrated filtrate, the mixed solvent that uses ETHYLE ACETATE and normal hexane carry out silica gel column chromatography as elutriant to filtrating to be separated and obtains compd E.To the adsorptivity of compd E and silica gel, can adopt the ETHYLE ACETATE of different volumes ratio and the mixed solvent of normal hexane, preferred, the volume ratio of ETHYLE ACETATE and normal hexane can be 2: 3.
Step S2: with compd E and alkyl iodide in toluene solvant, 25～45 ℃ of following reacting generating compound G (1-(2,4 difluorobenzene base)-3-alkyl benzimidazole iodine), reaction formula is following:
Preferably, further comprise the purification procedures to compound G after the step S2: the reacting coarse product of filtration step three again with the throw out of washing and filterings such as toluene, promptly obtains the compound G of purifying after the drying.
Step S3: be in the reaction system of solvent with the cellosolvo, with the above-mentioned compound G that makes (1-(2,4 difluorobenzene base)-3-alkyl benzimidazole iodine) and three hydration iridous chlorides at silver suboxide (Ag
2O) under the effect, (two endo compounds (46dfpmb) of reacting generating compound A in 100～150 ℃ of environment
2Ir (μ-Cl)
2Ir (46dfpmb)
2), reaction formula is following:
Preferably, further comprise purification procedures after the step S3: at first the compound G reacted mixed solution of three hydration iridous chlorides is together carried out concentrating under reduced pressure and handle to compd A; Be that elutriant carries out silica gel column chromatography separation 2～3 times to liquid concentrator then with the methylene dichloride, obtain the compd A of purifying.
Step S4: do under the condition of catalyzer in anaerobic and basic cpd, with compd A (two endo compounds (46dfpmb)
2Ir (μ-Cl)
2Ir (46dfpmb)
2) and compd B (5-(2 '-pyridyl) tetrazolium) reacting by heating in organic solvent, generation contains iridium electroluminescent organic material, i.e. compound H (two (1-(4, the 6-difluorophenyl)-3-alkyl benzimidazole-C, C
2) (5-(2 '-pyridyl) tetrazolium) close iridium, also is [(46dfpmb)
2IrN4], wherein: 6df represents 4 of phenyl on the specific function group, the 6-position with two fluorine-based, pmb represents specific function group 1-(4, the 6-difluorophenyl)-3-alkyl benzimidazole base, N4 represents assistant ligand 5-(2 '-pyridyl) tetrazolium), reaction formula is following:
Wherein, basic cpd can be sodium methylate, yellow soda ash, sodium phosphate, salt of wormwood or potassiumphosphate etc.Solvent can adopt 1,2-ethylene dichloride, cellosolvo, methylene dichloride, trichloromethane etc. and two endo compounds (46dfpmb)
2Ir (μ-Cl)
2Ir (46dfpmb)
2Reach the organic solvent that 5-(2 '-pyridyl) tetrazolium has better consistency.The temperature of reaction is controlled at carries out back flow reaction about solvent boiling point.Compd A can adopt the method preparation of above-mentioned steps S1～step S4, also can adopt other traditional method preparations.
Step S5: the separation and purification operation through follow-up can obtain the higher compound H of purity.
At first mixture is carried out concentrating under reduced pressure and handle the solids that obtains containing compound H; Then said solids is used deionized water, normal hexane and ether washing successively; Use the ETHYLE ACETATE and the mixed solvent of normal hexane to make eluent at last and solids is carried out silica gel column chromatography separate, obtain the said compound H of purifying.Preferably, the volume ratio of ETHYLE ACETATE and normal hexane is 2: 3 in the mixed solvent.
Above-mentioned preparing 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: two (1-(4, the 6-difluorophenyl)-3-methyl-benzoglyoxaline-C, C
2) (2-(2 '-pyridyl) imidazoles) close the synthetic of iridium:
(1) the 3-bit substituent is two endo compounds synthetic of methyl on the benzimidazolyl-:
In the 50mL round bottom reaction flask that the aluminium foil parcel is arranged, add 0.16g (0.836mmol) CuI successively, behind 1.20g (10.15mmol) benzoglyoxaline and 5.70g (17.50mmol) cesium carbonate, logical nitrogen 15min.In nitrogen gas stream, add 1mL (8.36mmol) 2 successively, 4-difluoro iodobenzene, 0.30g (1.67mmol) 1,10-phenanthrolene, the anhydrous N of 25mL, dinethylformamide.Behind the logical nitrogen 30min of reaction mixture, oil bath is heated to 110 ℃ of stirring reaction 24h.After liquid to be mixed is cooled to room temperature, vacuum concentration.Liquid concentrator adds 10mL ETHYLE ACETATE, filters, and washs with 30mL ETHYLE ACETATE again.Concentrated filtrate, ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 are that eluent carries out silica gel column chromatography and separates, the 0.924g yellow liquid, yield is 48%.Reaction formula is following:
Under the nitrogen protection, the injection of 1.26g (8.830mmol) methyl iodide is joined in the 25mL round-bottomed flask that 0.924g (4.013mmol) 1-(2,4 difluorobenzene base)-benzoglyoxaline and 15mL toluene are housed, round-bottomed flask wraps up with aluminium foil.Stirring reaction 24h under 30 ℃ of temperature, the adularescent throw out generates.Filter 20mL toluene wash throw out.Get the 0.882g white solid after the thorough drying, yield is 59%.Reaction formula is following:
Under the nitrogen protection; In the 100mL round bottom reaction flask that the aluminium foil parcel is arranged, add 7.44g (20.0mmol) 1-(2 successively; The 4-difluorophenyl)-and 3-tolimidazole iodide, 5.56g (24mmol) silver suboxide, 1.77g (5mmol) three hydration iridous chlorides; 50mL cellosolvo, oil bath are heated to 120 ℃ of stirring reaction 24h.Liquid cooling to be mixed to room temperature, concentrating under reduced pressure.For the eluent silica gel column chromatography separates twice, obtain little yellow solid product 0.582g with the methylene dichloride, yield is 16.3%.Reaction formula is following:
It is following that product detects data:
1H NMR (400MHz, CDCl
3, ppm): 8.33 (s, 4H), 8.14 (d, 4H), 7.81 (d, 4H), 7.75 (m, 4H), 7.67 (m, 4H), 7.38 (d, 4H), 4.49 (s, 12H).
(2) 5-(2 '-pyridyl) tetrazolium is synthetic
The HCl that in the 100mL reaction flask, adds 50mL toluene and 2.1mL (23mmol) 33%; Stir and carefully add 3.2mL (23mmol) triethylamine, 1.9mL (20mmol) 2-cyanopyridine and 1.50g (23mmol) sodium azide down successively; Carefully be heated to backflow, stirring reaction 22h.After being chilled to room temperature, 100mL H
2O extractive reaction liquid, separatory, 10% HCl dropwise adds in the water layer, transfers its pH value to be about 5, has a large amount of white precipitates to generate, and suction filtration, cold water washing are for several times.The zero(ppm) water recrystallization gets the 2.10g white needle-like crystals, and yield is 71%.Reaction formula is following:
It is following that product detects data:
1H NMR (400MHz, DMSO-d
6, ppm): 8.78 (d, 1H), 8.32 (dd, 1H), 8.23 (d, 1H), 7.81 (dd, 1H).
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of methyl on 1.76g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction (reflux) 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.30g, yield is 64.1%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.38(d，1H)，8.07(d，1H)，7.93(t，1H)，7.82(t，1H)，6.93(s，1H)，6.91(s，1H)，6.81(s，1H)，6.78(s，1H)，6.63(t，1H)，6.61(t，1H)，6.53(t，1H)，6.50(t，1H)，6.43(d，1H)，6.41(d，1H)，6.31(d，1H)，6.27(d，1H)，3.23(s，3H)，3.21(s，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 394nm place simultaneously at the 374nm place.
Embodiment 2: two (1-(4, the 6-difluorophenyl)-3-ethyl-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is two endo compounds synthetic referring to embodiment 1 of ethyl on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of ethyl on 1.83g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.37g, yield is 65.3%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.40(d，1H)，8.09(d，1H)，7.95(t，1H)，7.84(t，1H)，6.94(s，1H)，6.93(s，1H)，6.85(s，1H)，6.80(s，1H)，6.64(t，1H)，6.63(t，1H)，6.54(t，1H)，6.51(t，1H)，6.43(d，1H)，6.42(d，1H)，6.34(d，1H)，6.29(d，1H)，3.62(m，2H)，3.60(m，2H)，1.26(t，3H)，1.23(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 394nm place simultaneously at the 374nm place.
Embodiment 3: two (1-(4, the 6-difluorophenyl)-3-propyl group-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is two endo compounds synthetic referring to embodiment 1 of propyl group on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of propyl group on 1.89g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.34g, yield is 61.7%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.41(d，1H)，8.10(d，1H)，7.97(t，1H)，7.86(t，1H)，6.95(s，1H)，6.94(s，1H)，6.87(s，1H)，6.83(s，1H)，6.66(t，1H)，6.64(t，1H)，6.55(t，1H)，6.53(t，1H)，6.44(d，1H)，6.43(d，1H)，6.35(d，1H)，6.31(d，1H)，3.60(t，2H)，3.57(t，2H)，1.26(m，2H)，1.23(m，2H)，0.94(t，3H)，0.92(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 395nm place simultaneously at the 375nm place.
Embodiment 4: two (1-(4, the 6-difluorophenyl)-3-butyl-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is that the synthesis step of two endo compounds of butyl is referring to embodiment 1 on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of butyl on 1.96g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.29g, yield is 57.8%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.42(d，1H)，8.13(d，1H)，7.99(t，1H)，7.88(t，1H)，6.97(s，1H)，6.95(s，1H)，6.88(s，1H)，6.85(s，1H)，6.68(t，1H)，6.66(t，1H)，6.56(t，1H)，6.55(t，1H)，6.46(d，1H)，6.44(d，1H)，6.37(d，1H)，6.34(d，1H)，3.65(t，2H)，3.61(t，2H)，1.38(m，2H)，1.35(m，2H)，1.25(m，2H)，1.23(m，2H)，0.91(t，3H)，0.90(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 395nm place simultaneously at the 375nm place.
Embodiment 5: two (1-(4, the 6-difluorophenyl)-3-amyl group-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is that the synthesis step of two endo compounds of amyl group is referring to embodiment 1 on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of amyl group on 2.03g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.28g, yield is 55.4%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.43(d，1H)，8.15(d，1H)，8.01(t，1H)，7.89(t，1H)，6.99(s，1H)，6.97(s，1H)，6.89(s，1H)，6.86(s，1H)，6.68(t，1H)，6.67(t，1H)，6.58(t，1H)，6.56(t，1H)，6.48(d，1H)，6.46(d，1H)，6.39(d，1H)，6.36(d，1H)，3.64(t，2H)，3.61(t，2H)，1.38(m，2H)，1.35(m，2H)，1.31(m，2H)，1.29(m，2H)，1.24(m，2H)，1.22(m，2H)，0.92(t，3H)，0.90(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 396nm place simultaneously at the 376nm place.
Embodiment 6: two (1-(4, the 6-difluorophenyl)-3-hexyl-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is that the synthesis step of two endo compounds of hexyl is referring to embodiment 1 on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of hexyl on 2.10g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.34g, yield is 56.3%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.46(d，1H)，8.18(d，1H)，8.06(t，1H)，7.92(t，1H)，7.03(s，1H)，7.01(s，1H)，6.91(s，1H)，6.89(s，1H)，6.70(t，1H)，6.68(t，1H)，6.59(t，1H)，6.57(t，1H)，6.49(d，1H)，6.47(d，1H)，6.41(d，1H)，6.38(d，1H)，3.62(t，2H)，3.60(t，2H)，1.37(m，2H)，1.35(m，2H)，1.28(m，2H)，1.26(m，2H)，1.22(m，4H)，1.20(m，4H)，0.90(t，3H)，0.89(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 396nm place simultaneously at the 376nm place.
Embodiment 7: two (1-(4, the 6-difluorophenyl)-3-heptyl-benzoglyoxaline-C, C
2) (5-(2 '-pyridyl) tetrazolium) close the synthetic of iridium
(1) the 3-bit substituent is that the synthesis step of two endo compounds of heptyl is referring to embodiment 1 on the benzimidazolyl-;
(2) 5-(2 '-pyridyl) tetrazolium is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of heptyl on 2.17g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.25g, yield is 51.2%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.47(d，1H)，8.19(d，1H)，8.08(t，1H)，7.94(t，1H)，7.04(s，1H)，7.02(s，1H)，6.94(s，1H)，6.92(s，1H)，6.71(t，1H)，6.69(t，1H)，6.60(t，1H)，6.58(t，1H)，6.50(d，1H)，6.48(d，1H)，6.43(d，1H)，6.40(d，1H)，3.61(t，2H)，3.58(t，2H)，1.36(m，2H)，1.34(m，2H)，1.27(m，2H)，1.25(m，2H)，1.22(m，6H)，1.19(m，6H)，0.90(t，3H)，0.89(t，3H).
Product is under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 396nm place simultaneously at the 376nm place.
Embodiment 8: two (1-(4, the 6-difluorophenyl)-3-octyl group-benzoglyoxaline-C, C
2) (2-(2 '-pyridyl) imidazoles) close the synthetic of iridium
(1) the 3-bit substituent is that the synthesis step of two endo compounds of octyl group is referring to embodiment 1 on the benzimidazolyl-;
(2) 2-(2 '-pyridyl) imidazoles is synthetic with embodiment 1;
(3) final product (46dfpmb)
2IrN4's is synthetic
Under the nitrogen protection,, the 250mL round bottom there-necked flask of aluminium foil parcel adds that the 3-bit substituent is two endo compounds, 0.556g (3.78mmol) 5-(2 '-pyridyl) tetrazolium, 80mL trichloromethane and 0.997g (18.45mmol) sodium methylate of octyl group on 2.24g (1.23mmol) benzimidazolyl-in being arranged successively.Stirring and refluxing reaction 12h.Cooled and filtered, concentrated mother liquor gets pale brown look solid.Solid is successively with after deionized water, normal hexane and the ether washing, and ETHYLE ACETATE and the normal hexane mixed solution that with volume ratio is 2: 3 is that elutriant carries out silica gel column chromatography and separates, highly purified light yellow solid 1.19g, yield is 47.5%.
Below detect data for final product:
1H?NMR(400MHz，DMSO-d
6，ppm)：8.48(d，1H)，8.20(d，1H)，8.10(t，1H)，7.96(t，1H)，7.06(s，1H)，7.04(s，1H)，6.95(s，1H)，6.94(s，1H)，6.72(t，1H)，6.70(t，1H)，6.62(t，1H)，6.60(t，1H)，6.52(d，1H)，6.508(d，1H)，6.45(d，1H)，6.43(d，1H)，3.60(t，2H)，3.57(t，2H)，1.34(m，2H)，1.32(m，2H)，1.26(m，2H)，1.25(m，2H)，1.21(m，8H)，1.20(m，8H)，0.90(t，3H)，0.88(t，3H).
As shown in Figure 2, under the 77K temperature in the 2-methyltetrahydrofuran solution (～10
-5The maximum emission peak of emmission spectrum mol/L) has an acromion at the 397nm place simultaneously at the 377nm place, can be used as the preparation field that the blue light electroluminescent material is widely used in organic electroluminescence device.
(4). two (1-(4, the 6-difluorophenyl)-3-octyl group-benzoglyoxaline-C, the C that make with present embodiment
2) (2-(2 '-pyridyl) imidazoles) close iridium (hereinafter to be referred as (46dfpmb)
2IrN4) as the organic electroluminescence device of the doping object of luminescent layer, structure is as shown in Figure 3:
This device is followed successively by ITO/46dfpmb)
2IrN4/LiF/Al, promptly on a glass substrate deposition one deck square resistance be the tin indium oxide (ITO) of 10-20 Ω/mouth as transparent anode, on ITO, prepare one deck through spin coating technique and contain the 46dfpmb that present embodiment prepares)
2The luminescent layer of IrN4 material, vacuum evaporation LiF on this luminescent layer as impact plies, adopts vacuum coating technology metal refining Al, as the negative electrode of device at last on impact plies again.This electroluminescent device since contain higher internal quantum efficiency and electroluminescent efficiency in the luminescent layer contain the iridium electroluminescent organic material, it has higher effciency of energy transfer and luminous efficiency, can be widely used in luminous fields such as blueness or white.
The above embodiment has only expressed several kinds of 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 under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (10)
1. one kind contains the iridium electroluminescent organic material, it is characterized in that, has general formula H:
Wherein, R is C
1～C
8Alkyl.
2. a preparation method who contains the iridium electroluminescent organic material is characterized in that, comprises the steps: to prepare or provide compd A and the compd B that following structural formula is represented,
Wherein, R is C
1～C
8Alkyl;
Under anaerobic and catalyzer condition, be in solvent, to carry out reacting by heating in 1: 2.5～1: 3.7 in molar ratio with said compd A and compd B, obtain containing the mixture of compound H, reaction formula is following:
After the cooling, the said mixture of separation and purification obtains compound H.
3. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2; It is characterized in that said catalyzer is a basic cpd, said solvent is a cellosolvo, 1; A kind of in 2-ethylene dichloride, methylene dichloride and the trichloromethane, said reacting by heating is a back flow reaction.
4. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 3 is characterized in that, said basic cpd is sodium methylate, yellow soda ash, sodium phosphate, salt of wormwood or potassiumphosphate.
5. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2; It is characterized in that; The said mixture of separation and purification comprises the steps: that at first mixture being carried out concentrating under reduced pressure handles the solids that obtains containing compound H; Then said solids is used deionized water, normal hexane and ether washing successively, use the ETHYLE ACETATE and the mixed solvent of normal hexane to make eluent at last and solids is carried out silica gel column chromatography separate, obtain the said compound H 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:
Step 1, the Compound C and the D that provide following structural formula to represent,
Step 2, under oxygen free condition, Compound C is carried out the Ullmann linked reaction with compound D under the condition of catalyzer, generate compd E, reaction formula is following:
Step 3, the compd E that makes reacted in solvent with alkyl iodide generate said compound G, reaction formula is following:
R-I is an alkyl iodide, and R is C
1～C
8Alkyl;
Step 4: under anaerobic and catalyzer condition, compound G is reacted the said compd A of generation with three hydration iridous chlorides in solvent, reaction formula is following:
7. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 6; It is characterized in that in the said step 2, the temperature of reaction of Ullmann linked reaction is 100～180 ℃; Catalyzer is a cupric iodide, 1; The mixed catalyst that 10-phenanthrolene and cesium carbonate are formed, solvent is N, dinethylformamide; In the said step 3, solvent is a toluene, and temperature of reaction is 25～45 ℃; In the said step 4, catalyzer is a silver suboxide, and solvent is a cellosolvo, and temperature of reaction is 100～150 ℃.
8. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 6 is characterized in that, further comprises the purification procedures to compd E after the said step 2: at first the mixed solution after the Ullmann linked reaction is carried out vacuum concentration and handle; In liquid concentrator, add ethyl acetate solution then, produce throw out; The filtering separation throw out, and use the ETHYLE ACETATE washing precipitate, collect filtrating; Last concentrated filtrate, the mixed solvent that uses ETHYLE ACETATE and normal hexane carry out silica gel column chromatography as elutriant to filtrating to be separated and obtains compd E;
Further comprise purification procedures after the said step 3 to compound G: the reacting coarse product of filtration step three, use the filtering throw out of toluene wash again, promptly obtain the compound G of purifying after the drying; Further comprise purification procedures after the said step 4: at first the compound G reacted mixed solution of three hydration iridous chlorides is together carried out concentrating under reduced pressure and handle to compd A; Be that elutriant carries out silica gel column chromatography separation 2～3 times to liquid concentrator then with the methylene dichloride, obtain the said compd A of purifying.
9. the preparation method who contains the iridium electroluminescent organic material as claimed in claim 2 is characterized in that, the preparation process of compd B comprises the steps:
At first in reactor drum, add toluene and hydrochloric acid soln; Under agitation condition, in reactor drum, add triethylamine, 2-cyanopyridine and sodium azide more successively, mix post-heating to refluxing stirring reaction 10～30 hours; After the cooling, use zero(ppm) water extractive reaction liquid, separatory; Regulate the water potential of hydrogen to pH4.5～5.5; Produce white precipitate, be said compd B, reaction formula is following:
10. an organic electroluminescence device comprises luminescent layer, it is characterized in that, contains the compound H that formula is represented in the said luminescent layer:
Wherein, R is C
1～C
8Alkyl.
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| CN104402936A (en) * | 2014-11-25 | 2015-03-11 | 宁波大学 | Iridium complex and preparation method thereof |
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