CN103965251A - Red organic electroluminescent material and its preparation method and application - Google Patents
Red organic electroluminescent material and its preparation method and application Download PDFInfo
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- CN103965251A CN103965251A CN201310034827.XA CN201310034827A CN103965251A CN 103965251 A CN103965251 A CN 103965251A CN 201310034827 A CN201310034827 A CN 201310034827A CN 103965251 A CN103965251 A CN 103965251A
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- CGJHMXMNCXUQAD-UHFFFAOYSA-N C=[Br]c(nc1)ccc1Br Chemical compound C=[Br]c(nc1)ccc1Br CGJHMXMNCXUQAD-UHFFFAOYSA-N 0.000 description 1
- BGRCUIGNXXXCTN-UHFFFAOYSA-N C=[Br]c1ccc(-c(cc2)ccc2N(C2=CC=CCC2)c2ccccc2)nc1 Chemical compound C=[Br]c1ccc(-c(cc2)ccc2N(C2=CC=CCC2)c2ccccc2)nc1 BGRCUIGNXXXCTN-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the organic electroluminescent material, and discloses a red organic electroluminescent material and a preparation method and application thereof. The material has a general structural formula as follows, wherein R represents phenyl, naphthyl-1-yl or naphthyl-2-yl. The red organic electroluminescent phosphorescent material provided by the invention uses 2-(triphenylamine-4'-yl)-5-aryl formyl pyridine as a main structure of a ring metal ligand, and the introduction of phenyl, naphthyl-1-yl and naphthyl-2-yl formyl realizes acquisition of satisfactory red emission wavelength; the presence of large groups such as triphenylamine, phenyl or naphthyl can produce a certain space steric effect, thereby reducing the direct interaction between metal atoms, and reducing self quenching phenomenon of triplet exciton; at the same time, aromatic groups can effectively control the energy levels of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the material, and facilitate the balance of charge transfer in a device, so as to improve the luminescent properties of the device.
Description
Technical field
The present invention relates to electroluminescent organic material, relate in particular to a kind of ruddiness electroluminescent organic material and its preparation method and application.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay 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 due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been 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, 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, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
In order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Generally speaking, the development of blue phosphorescent material always lags behind ruddiness and green glow, and with regard to single, from this index of purity of color, blue phosphorescent material seldom can be accomplished the purity of color of the dark red light of picture and dark green light so far.For produce gratifying white light OLED, select at present or take the phosphor material of sky blue light as main, as FIrpic, just that this just requires arranged in pairs or groups red phosphorescence material will be connected to saturated red scarlet is passable.So the ruddiness electroluminescent organic material of developing high color purity is still a large focus of OLED research field.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of ruddiness electroluminescent organic material.
Technical scheme of the present invention is as follows:
A ruddiness electroluminescent organic material, its general structure is as follows:
Wherein, R is phenyl, naphthalene-1-base or naphthalene-2-base.
The preparation method of above-mentioned ruddiness electroluminescent organic material, comprises the steps:
Under protection of inert gas, by structural formula, be
compd A and structural formula be
compd B be dissolved in the organic solvent that contains tetrakis triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium catalyst and alkali, Suzuki linked reaction 6～10h subsequently refluxes at 63～120 ℃ of temperature, after question response stops, separating-purifying reaction solution, obtains structural formula and is
compound C; Wherein, the mol ratio of compd A and compd B is 1:1.2; The mol ratio of catalyzer and compd A is 0.05:1; The mol ratio of alkali and compd A is 10:3;
Under protection of inert gas, described Compound C is dissolved in tetrahydrofuran (THF) or ether, under whipped state, temperature of reaction system is down to-78 ℃, then to reaction system, drips successively n-Butyl Lithium and normal hexane, after dripping, at-78 ℃ of temperature, continue stirring reaction 35min; Then by structural formula, be
tetrahydrofuran (THF) or the diethyl ether solution of Compound D be added dropwise to reaction system, and keep-78 ℃ of temperature to continue stirring reaction 60min, question response completely after, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature, separating-purifying reaction solution, obtains structural formula and is
compd E; The mol ratio of Compound C, n-Butyl Lithium, Compound D is 1:1.6:1.5;
Under protection of inert gas, it is in the cellosolvo of 3:1 and the mixed solvent of water that described compd E is dissolved in to volume ratio, then adds three hydration iridous chloride and distilled water again, stirring reaction mixed solution, heating mixed solution to 120 ℃ reaction 24h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
compound F 17-hydroxy-corticosterone; Wherein, compd E and three hydration iridous chloride mol ratios are 2.2:1;
Under protection of inert gas; described compound F 17-hydroxy-corticosterone and compd E are dissolved in to cellosolvo, the 2-methyl cellosolve, 1 that contains alkali; in 2-ethylene dichloride, trichloromethane or methylene dichloride; stirring reaction mixed solution is heated to 40～135 ℃ of reaction 8～24h; be cooled to room temperature; separating-purifying, obtains structural formula and is
ruddiness electroluminescent organic material; Wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 1:3;
In above-mentioned formula, R is phenyl, naphthalene-1-base or naphthalene-2-base.
Described ruddiness electroluminescent organic material, described organic solvent is that volume ratio is the toluene of 2:1 and the mixed solvent of ethanol; Described alkali is sodium carbonate or salt of wormwood.
Described ruddiness electroluminescent organic material, wherein, the separating-purifying of described Compound C comprises:
Question response stops being chilled to impouring distilled water after room temperature, then ethyl acetate extraction, anhydrous magnesium sulfate drying organic phase, filter, rotation is steamed and is desolventized to obtain crude product, the ethyl acetate that the volume ratio of take is 3:1 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described Compound C solid.
Described ruddiness electroluminescent organic material, wherein, the separating-purifying of described compd E comprises:
Question response stops being chilled to after room temperature, and ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying, filters, concentrated except desolventizing, the ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described compd E solid.
Described ruddiness electroluminescent organic material, wherein, the separating-purifying of described compound F 17-hydroxy-corticosterone comprises:
Question response stops being chilled to after room temperature, collects the throw out in reaction solution, with methyl alcohol, normal hexane washing, obtains corresponding compound F 17-hydroxy-corticosterone after vacuum-drying successively.
Described ruddiness electroluminescent organic material, wherein, the separating-purifying of described compound ruddiness electroluminescent organic material comprises:
Question response stops being chilled to after room temperature, filter the throw out of collecting in reaction solution, successively with ethanol and normal hexane washing, obtain solid, solid is dissolved in methylene dichloride again, removes by filter insolubles, concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify, product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains ruddiness electroluminescent organic material.
The present invention also provides a kind of organic electroluminescence device, and the dopant material of its luminescent layer is above-mentioned ruddiness electroluminescent organic material.
Ruddiness organic electromechanical phosphorescent material provided by the invention, 2-(triphenylamine-4'-yl)-5-aryl formyl radical pyridine of take is cyclic metal complexes agent structure, the introducing of phenyl, naphthalene-1-base, naphthalene-2-base formyl radical can obtain and be satisfied with red light-emitting wavelength; Macoradical can produce certain space steric effect as the existence of triphenylamine, phenyl or naphthyl, thereby reduces the direct effect between atoms metal, reduces the self-quenching phenomenon of triplet exciton; Meanwhile, aromatic group can effectively be controlled highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, is conducive to the electric charge transmission in balancing device, thereby improves the electroluminescent properties of device.
Accompanying drawing explanation
Fig. 1 is the utilizing emitted light spectrogram of the electroluminescent organic material that makes in embodiment 1;
Fig. 2 is the structural representation of the organic electroluminescence device that makes in embodiment 4.
Embodiment
The invention reside in and select take 2-(triphenylamine-4'-yl)-5-aryl formyl radical pyridine as the synthetic a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex of cyclic metal complexes; and by the chemically modified of aryl formyl radical on cyclic metal complexes is realized to the adjusting to material glow color, thereby obtain the phosphorescent emissions of different red emission wavelengths.The general structure of ruddiness organic electromechanical phosphorescent material metal iridium complex of the present invention is as follows:
Wherein, R is phenyl, naphthalene-1-base or naphthalene-2-base.
The cyclic metal complexes of ruddiness organic electromechanical phosphorescent material iridium metal complex can be following structure:
This type of ruddiness organic electromechanical phosphorescent material metal iridium complex of the present invention can be used as the luminescent material in ruddiness or white light organic electroluminescent device.
The feature of this class ruddiness organic electromechanical phosphorescent material metal iridium complex provided by the invention is take that 2-(triphenylamine-4'-yl)-5-aryl formyl radical pyridine is cyclic metal complexes agent structure, and the introducing of phenyl, naphthalene-1-base, naphthalene-2-base formyl radical can obtain and be satisfied with red light-emitting wavelength.Macoradical can produce certain space steric effect as the existence of triphenylamine, phenyl or naphthyl, thereby reduces the direct effect between atoms metal, reduces the self-quenching phenomenon of triplet exciton; Meanwhile, aromatic group can effectively be controlled highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, is conducive to the electric charge transmission in balancing device, thereby improves the electroluminescent properties of device.
This type of ruddiness organic electromechanical phosphorescent material metal iridium complex provided by the invention; after pyridine ring and triphenylamine Suzuki linked reaction with two bromine atoms; again with aryl carboxamides generation permutoid reaction synthesizing ring metal part 2-(triphenylamine-4'-yl)-5-aryl formyl radical pyridine, then with IrCl
33H
2o reaction generates chlorine bridge dipolymer, finally reacts with cyclic metal complexes and makes target iridium metal complex.
The preparation method of above-mentioned ruddiness electroluminescent organic material, comprises the steps:
Under S1, rare gas element (at least one in nitrogen, argon gas, lower same) protection, by structural formula, be
compd A (2,5-dibromo pyridine) and structural formula be
compd B (4-triphenylamine boric acid) be dissolved in and contain tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) or dichloro bi triphenyl phosphine palladium (Pd (PPh
3)
2cl
2) in the organic solvent of catalyzer and alkali, the Suzuki linked reaction 6～10h that refluxes at 63～120 ℃ of temperature subsequently, after question response stops, separating-purifying reaction solution, obtains structural formula and is
compound C (2-(triphenylamine-4'-yl)-5-bromopyridine); Wherein, the mol ratio of compd A and compd B is 1:1.2; The mol ratio of catalyzer and compd A is 0.05:1; The mol ratio of alkali and compd A is 10:3; Reaction formula is as follows:
Preferably, organic solvent is that volume ratio is the toluene of 2:1 and the mixed solvent of ethanol; Described alkali is sodium carbonate or salt of wormwood;
More preferably, described alkali is that concentration is sodium carbonate or the wet chemical of 2M;
The separating-purifying of described Compound C comprises:
Question response stops being chilled to impouring distilled water after room temperature, then ethyl acetate extraction, anhydrous magnesium sulfate drying organic phase, filter, rotation is steamed and is desolventized to obtain crude product, the ethyl acetate that the volume ratio of take is 3:1 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described Compound C solid.
Under S2, protection of inert gas, described Compound C is dissolved in tetrahydrofuran (THF) (THF) or ether, under whipped state, temperature of reaction system is down to-78 ℃, then to reaction system, drip successively n-Butyl Lithium (t-BuLi) and normal hexane, after dripping, at-78 ℃ of temperature, continue stirring reaction 35min; Then by structural formula, be
compound D (substituting group of R is different, name different, refer to each embodiment) tetrahydrofuran (THF) or diethyl ether solution be added dropwise to reaction system, and keep-78 ℃ of temperature to continue stirring reaction 60min, after question response is complete, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature, separating-purifying reaction solution, obtains structural formula and is
compd E; The mol ratio of Compound C (2-(triphenylamine-4'-yl)-5-benzoyl pyridine), n-Butyl Lithium, Compound D is 1:1.6:1.5; Reaction formula is as follows:
In formula, R is phenyl, naphthalene-1-base or naphthalene-2-base;
Preferably, the separating-purifying of described compd E comprises:
Question response stops being chilled to after room temperature, and ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying, filters, concentrated except desolventizing, the ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described compd E solid.
Under S3, protection of inert gas, it is in the cellosolvo of 3:1 and the mixed solvent of water that described compd E is dissolved in to volume ratio, then adds three hydration iridous chloride and distilled water again, stirring reaction mixed solution, heating mixed solution to 120 ℃ reaction 24h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
compound F 17-hydroxy-corticosterone (2-(triphenylamine-4'-yl)-5-benzoyl pyridine containing iridium dichloro dimer); Wherein, compd E and three hydration iridous chloride (IrCl
33H
2o) mol ratio is 2.2:1; Reaction formula is as follows:
Preferably, the separating-purifying of described compound F 17-hydroxy-corticosterone comprises:
Question response stops being chilled to after room temperature, collects the throw out in reaction solution, with methyl alcohol, normal hexane washing, obtains corresponding compound F 17-hydroxy-corticosterone after vacuum-drying successively.
Under S4, protection of inert gas; described compound F 17-hydroxy-corticosterone and compd E are dissolved in to cellosolvo, the 2-methyl cellosolve, 1 that contains alkali; in 2-ethylene dichloride, trichloromethane or methylene dichloride; stirring reaction mixed solution is heated to 40～135 ℃ of reaction 8～24h; be cooled to room temperature; separating-purifying, obtains structural formula and is
ruddiness electroluminescent organic material; Wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 1:3; Reaction formula is:
Preferably, described alkali is sodium carbonate or salt of wormwood;
More preferably, described alkali is that concentration is the sodium carbonate of 2M or the aqueous solution of salt of wormwood;
The separating-purifying of described compound ruddiness electroluminescent organic material comprises:
Question response stops being chilled to after room temperature, filter the throw out of collecting in reaction solution, successively with ethanol and normal hexane washing, obtain solid, solid is dissolved in methylene dichloride again, removes by filter insolubles, concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify, product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains ruddiness electroluminescent organic material.
In addition, be also necessary to provide a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex organic electroluminescence device.
An organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer includes the compound that following structural formula represents:
Wherein, R is phenyl, naphthalene-1-base, naphthalene-2-base.
Material of main part in above-claimed cpd and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare ruddiness or white-light phosphor photoelectricity electroluminescence device.Electroluminescent device, owing to containing the ruddiness organic electromechanical phosphorescent material metal iridium complex of high color purity in luminescent layer, can be launched high purity ruddiness and good device performance thereby it has advantages of.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex two [2-(triphenylamine-4'-yl)-5-benzoyl pyridine-N, C
2'] (methyl ethyl diketone) close the synthetic of iridium
(1) 2-(triphenylamine-4'-yl)-5-bromopyridine is synthetic
0.71g (3.0mmol) 2,5-dibromo pyridine, 1.04g (3.6mmol) 4-triphenylamine boric acid, 0.17g (0.15mmol) tetrakis triphenylphosphine palladium, 25mL toluene, sodium carbonate (10.0mmol) aqueous solution that 12.5mL ethanol and 5mL concentration are 2M, back flow reaction 6h at 120 ℃ of temperature.Question response is chilled to the appropriate distilled water of impouring after room temperature, ethyl acetate extraction.Anhydrous magnesium sulfate drying organic phase.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 3:1 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain 0.90g white solid, and yield is 74.8%.
Structural Identification:
Mass spectrum (MS m/z): 402.1 (M
+)
Ultimate analysis: C23H17BrN2
Theoretical value: C, 68.84; H, 4.27; Br, 19.91; N, 6.98;
Measured value: C, 68.81; H, 4.29; Br, 19.88; N, 7.02.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(triphenylamine-4'-yl)-5-bromopyridine.
(2) 2-(triphenylamine-4'-yl)-5-benzoyl pyridine is synthetic
Under argon shield, 1.60g (4.0mmol) 2-(triphenylamine-4'-yl)-5-bromopyridine is dissolved in 20mL and newly steams in THF, under whipped state, temperature of reaction system is down to-78 ℃.With syringe, dropwise adding 4mL concentration is n-Butyl Lithium (6.4mmol) hexane solution of 1.6M, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.0.90g (6.0mmol) N, N-dimethyl benzamide is dissolved in the new THF steaming of 20mL, in 5min, dropwise adds in reaction system.Keep-78 ℃ of temperature to continue stirring reaction 60min, after reacting completely, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature.Ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying.Filter, concentrated except desolventizing.The ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain 1.04g white solid, and yield is 61.0%.
Structural Identification:
Mass spectrum (MS m/z): 426.2 (M
+)
Ultimate analysis: C30H22N2O
Theoretical value: C, 84.48; H, 5.20; N, 6.57; O, 3.75;
Measured value: C, 84.43; H, 5.25; N, 6.53; O, 3.79.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(triphenylamine-4'-yl)-5-benzoyl pyridine.
(3) main part is the dimeric synthetic containing iridium dichloro of 2-(triphenylamine-4'-yl)-5-benzoyl pyridine
Under nitrogen protection; it is in the cellosolvo of 3:1 and the mixed solvent of water that 0.94g (2.2mmol) 2-(triphenylamine-4'-yl)-5-benzoyl pyridine is dissolved in 9mL volume ratio, and 0.35g (1.0mmol) three hydration iridous chlorides and 3ml distilled water add in reaction system.Stirring reaction mixed solution, reacting by heating system to 120 ℃ reaction 24h.Be chilled to after room temperature, collect the throw out in mixed solution, successively with methyl alcohol, normal hexane washing.After vacuum-drying corresponding main part be 2-(triphenylamine-4'-yl)-5-benzoyl pyridine containing iridium dichloro dimer.Product can directly drop into next step reaction without further purification.
(4) title complex three [2-(triphenylamine-4'-yl)-5-benzoyl pyridine-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part making be 2-(triphenylamine-4'-yl)-5-benzoyl pyridine containing iridium dichloro dimer; 1.14mL (1.0mmol) 2-(triphenylamine-4'-yl)-5-benzoyl pyridine and 0.32g (3.0mmol) sodium carbonate are dissolved in 10mL2-ethoxy ethanol, and stirring reaction mixed solution is heated to 135 ℃ of reaction 8h.Be chilled to after room temperature, filter the throw out of collecting in mixed solution, successively with ethanol and normal hexane washing.Solid is dissolved in methylene dichloride again, removes by filter insolubles.Concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify.Product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.56g pure products, and yield is 38.1%.
Structural Identification:
Mass spectrum (MS m/z): 1468.5 (M
+)
Ultimate analysis: C90H63IrN6O3
Theoretical value: C, 73.60; H, 4.32; Ir, 13.09; N, 5.72; O, 3.27;
Measured value: C, 73.63; H, 4.30; Ir, 13.05; N, 5.73; O, 3.29.
The resulting material of the above-mentioned reaction of above data acknowledgement is three [2-(triphenylamine-4'-yl)-5-benzoyl pyridine-N, C
2'] close iridium.
As shown in Figure 1, transverse axis is emission wavelength (Wavelength, the nm of unit), and the longitudinal axis is the photoluminescence intensity (Normalized PL Intensity a.u.) after normalization method, and end product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum M), at 626nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.16, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: title complex two [2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine-N, C
2'] (methyl ethyl diketone) close the synthetic of iridium
(1) synthesis step of 2-(triphenylamine-4'-yl)-5-bromopyridine is with embodiment 1, the difference Suzuki linked reaction 9h that is to reflux at 80 ℃ of temperature;
(2) 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine is synthetic
Under argon shield, 1.60g (4.0mmol) 2-(triphenylamine-4'-yl)-5-bromopyridine is dissolved in 20mL and newly steams in ether, under whipped state, temperature of reaction system is down to-78 ℃.With syringe, dropwise adding 4mL concentration is n-Butyl Lithium (6.4mmol) hexane solution of 1.6M, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.1.20g (6.0mmol) N, N-dimethyl-naphthalene-1'-base methane amide is dissolved in the new ether steaming of 20mL, in 5min, dropwise adds in reaction system.Keep-78 ℃ of temperature to continue stirring reaction 60min, after reacting completely, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature.Ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying.Filter, concentrated except desolventizing.The ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain 1.10g white solid, and yield is 57.7%.
Structural Identification:
Mass spectrum (MS m/z): 476.2 (M
+)
Ultimate analysis: C34H24N2O
Theoretical value: C, 85.69; H, 5.08; N, 5.88; O, 3.36;
Measured value: C, 85.62; H, 5.13; N, 5.86; O, 3.41.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine.
(3) main part is the dimeric synthetic containing iridium dichloro of 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine
Under nitrogen protection; it is in the cellosolvo of 3:1 and the mixed solvent of water that 1.05g (2.2mmol) 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine is dissolved in 9mL volume ratio, and 0.35g (1.0mmol) three hydration iridous chlorides and 3ml distilled water add in reaction system.Stirring reaction mixed solution, reacting by heating system to 120 ℃ reaction 24h.Be chilled to after room temperature, collect the throw out in mixed solution, successively with methyl alcohol, normal hexane washing.After vacuum-drying corresponding main part be 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine containing iridium dichloro dimer.Product can directly drop into next step reaction without further purification.
(4) title complex three [2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part making be 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine containing iridium dichloro dimer; 1.62g (1.0mmol) 2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine and 0.41g (3.0mmol) salt of wormwood are dissolved in 30mL trichloromethane, and stirring reaction mixed solution is heated to 62 ℃ of reaction 24h.Be chilled to after room temperature, filter the throw out of collecting in mixed solution, successively with ethanol and normal hexane washing.Solid is dissolved in methylene dichloride again, removes by filter insolubles.Concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify.Product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.48g pure products, and yield is 29.6%.
Structural Identification:
Mass spectrum (MS m/z): 1618.5 (M
+)
Ultimate analysis: C102H69IrN6O3
Theoretical value: C, 75.67; H, 4.30; Ir, 11.87; N, 5.19; O, 2.96;
Measured value: C, 75.61; H, 4.33; Ir, 11.86; N, 5.21; O, 2.98.
The resulting material of the above-mentioned reaction of above data acknowledgement is that three [2-(triphenylamine-4'-yl)-5-(naphthalene-1'-formyl radical) pyridine-N, C2'] close iridium.
End product is CH at 298K temperature
2cl
2the maximum emission peak of the middle emmission spectrum of solution (～10-5M) is at 636nm place.In addition the CH of 10-5M end product,
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.20.
Embodiment 3: title complex two [2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine-N, C
2'] (methyl ethyl diketone) close the synthetic of iridium
(1) synthesis step of 2-(triphenylamine-4'-yl)-5-bromopyridine is with embodiment 1, and difference is: catalyzer is selected dichloro bi triphenyl phosphine palladium, the Suzuki linked reaction that refluxes at 63 ℃ of temperature 10h;
(2) 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine is synthetic
Under argon shield, 1.60g (4.0mmol) 2-(triphenylamine-4'-yl)-5-bromopyridine is dissolved in 20mL and newly steams in THF, under whipped state, temperature of reaction system is down to-78 ℃.With syringe, dropwise adding 4mL concentration is n-Butyl Lithium (6.4mmol) hexane solution of 1.6M, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.1.20g (6.0mmol) N, N-dimethyl-naphthalene-2'-base methane amide is dissolved in the new THF steaming of 20mL, in 5min, dropwise adds in reaction system.Keep-78 ℃ of temperature to continue stirring reaction 60min, after reacting completely, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature.Ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying.Filter, concentrated except desolventizing.The ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain 1.05g white solid, and yield is 55.0%.
Structural Identification:
Mass spectrum (MS m/z): 476.2 (M
+)
Ultimate analysis: C34H24N2O
Theoretical value: C, 85.69; H, 5.08; N, 5.88; O, 3.36;
Measured value: C, 85.63; H, 5.10; N, 5.89; O, 3.39.
The resulting material of the above-mentioned reaction of above data acknowledgement is 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine.
(3) main part is the dimeric synthetic containing iridium dichloro of 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine
Under nitrogen protection; it is in the cellosolvo of 3:1 and the mixed solvent of water that 1.05g (2.2mmol) 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine is dissolved in 9mL volume ratio, and 0.35g (1.0mmol) three hydration iridous chlorides and 3ml distilled water add in reaction system.Stirring reaction mixed solution, reacting by heating system to 120 ℃ reaction 24h.Be chilled to after room temperature, collect the throw out in mixed solution, successively with methyl alcohol, normal hexane washing.After vacuum-drying corresponding main part be 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine containing iridium dichloro dimer.Product can directly drop into next step reaction without further purification.
(4) title complex three [2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine-N, C
2'] close synthesizing of iridium
Under nitrogen protection; by the main part making be 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine containing iridium dichloro dimer; 1.24g (1.0mmol) 2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine and 0.32g (3.0mmol) sodium carbonate are dissolved in 20mL1; in 2-ethylene dichloride, stirring reaction mixed solution is heated to 84 ℃ of reaction 18h.Be chilled to after room temperature, filter the throw out of collecting in mixed solution, successively with ethanol and normal hexane washing.Solid is dissolved in methylene dichloride again, removes by filter insolubles.Concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify.Product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.45g pure products, and yield is 27.8%.
Structural Identification:
Mass spectrum (MS m/z): 1618.5 (M
+)
Ultimate analysis: C102H69IrN6O3
Theoretical value: C, 75.67; H, 4.30; Ir, 11.87; N, 5.19; O, 2.96;
Measured value: C, 75.62; H, 4.34; Ir, 11.85; N, 5.18; O, 3.00.
The resulting material of the above-mentioned reaction of above data acknowledgement is three [2-(triphenylamine-4'-yl)-5-(naphthalene-2'-formyl radical) pyridine-N, C
2'] close iridium.
End product is CH at 298K temperature
2cl
2the maximum emission peak of the middle emmission spectrum of solution (～10-5M) is at 631nm place.In addition the CH of 10-5M end product,
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3cH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.35.
Embodiment 4
The present embodiment is organic electroluminescence device, three [2-(triphenylamine-4'-yl)-5-benzoyl pyridine-N, the C that it makes with embodiment 1
2'] close iridium (P1 of usining represents) as luminescent layer doping guest materials; As shown in Figure 2, the structure of organic electroluminescence device comprises transparent anode 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electronic injection buffer layer 307, the negative electrode 308 stacking gradually.
The preparation technology of this organic electroluminescence device:
On a glass-based plate, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/ is as transparent anode 301, by vacuum evaporation, on anode 301, prepare successively the m-MTDATA(4 that a layer thickness is 60nm, 4 ', 4 ' '-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, N '-bis-(1-naphthyl)-N, N '-phenylbenzene benzidine) hole mobile material is as hole transmission layer 303, a layer thickness is the CBP (N doped with 8wt%P1 of 30nm, two carbazyl-4 of N'-, 4'-dipyridyl) mixing and doping material is as luminescent layer 304, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 305 again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 305, thickness is that the Alq3 (three (oxine) aluminium) of 20nm is as electron transfer layer 306, thickness is that the Liq of 2nm is as electronic injection buffer layer 307, finally on buffer layer, adopt the metal A l that vacuum plating techniques of deposition thickness is 100nm, negative electrode 308 as device.Therefore, the structure of this organic electroluminescence device can be also ITO/m-MTDATA/NPB/CBP:P1/BCP/Alq3/Liq/Al; Wherein, CBP:P1 represents that P1 is doped in CBP, and slash "/" represents laminate structure.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a ruddiness electroluminescent organic material, is characterized in that, its general structure is as follows:
Wherein, R is phenyl, naphthalene-1-base or naphthalene-2-base.
2. a preparation method for ruddiness electroluminescent organic material, is characterized in that, comprises the steps:
Under protection of inert gas, by structural formula, be
compd A and structural formula be
compd B be dissolved in the organic solvent that contains tetrakis triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium catalyst and alkali, Suzuki linked reaction 6～10h subsequently refluxes at 63～120 ℃ of temperature, after question response stops, separating-purifying reaction solution, obtains structural formula and is
compound C; Wherein, the mol ratio of compd A and compd B is 1:1.2; The mol ratio of catalyzer and compd A is 0.05:1; The mol ratio of alkali and compd A is 10:3;
Under protection of inert gas, described Compound C is dissolved in tetrahydrofuran (THF) or ether, under whipped state, temperature of reaction system is down to-78 ℃, then to reaction system, drips successively n-Butyl Lithium and normal hexane, after dripping, at-78 ℃ of temperature, continue stirring reaction 35min; Then by structural formula, be
tetrahydrofuran (THF) or the diethyl ether solution of Compound D be added dropwise to reaction system, and keep-78 ℃ of temperature to continue stirring reaction 60min, question response completely after, add appropriate ammonium chloride saturated solution termination reaction, naturally rise to room temperature, separating-purifying reaction solution, obtains structural formula and is
compd E; The mol ratio of Compound C, n-Butyl Lithium, Compound D is 1:1.6:1.5;
Under protection of inert gas, it is in the cellosolvo of 3:1 and the mixed solvent of water that described compd E is dissolved in to volume ratio, then adds three hydration iridous chloride and distilled water again, stirring reaction mixed solution, heating mixed solution to 120 ℃ reaction 24h; Be cooled to room temperature, separating-purifying, obtains structural formula and is
compound F 17-hydroxy-corticosterone; Wherein, compd E and three hydration iridous chloride mol ratios are 2.2:1;
Under protection of inert gas; described compound F 17-hydroxy-corticosterone and compd E are dissolved in to cellosolvo, the 2-methyl cellosolve, 1 that contains alkali; in 2-ethylene dichloride, trichloromethane or methylene dichloride; stirring reaction mixed solution is heated to 40～135 ℃ of reaction 8～24h; be cooled to room temperature; separating-purifying, obtains structural formula and is
ruddiness electroluminescent organic material; Wherein, the mol ratio of compound F 17-hydroxy-corticosterone and compd E is 1:3;
In above-mentioned formula, R is phenyl, naphthalene-1-base or naphthalene-2-base.
3. ruddiness electroluminescent organic material according to claim 2, is characterized in that, described organic solvent is that volume ratio is the toluene of 2:1 and the mixed solvent of ethanol.
4. ruddiness electroluminescent organic material according to claim 2, is characterized in that, described alkali is sodium carbonate or salt of wormwood.
5. ruddiness electroluminescent organic material according to claim 2, is characterized in that, the separating-purifying of described Compound C comprises:
Question response stops being chilled to impouring distilled water after room temperature, then ethyl acetate extraction, anhydrous magnesium sulfate drying organic phase, filter, rotation is steamed and is desolventized to obtain crude product, the ethyl acetate that the volume ratio of take is 3:1 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described Compound C solid.
6. ruddiness electroluminescent organic material according to claim 2, is characterized in that, the separating-purifying of described compd E comprises:
Question response stops being chilled to after room temperature, and ether repeatedly extracts, and merges organic phase, anhydrous sodium sulfate drying, filters, concentrated except desolventizing, the ethyl acetate that the volume ratio of take is 1:10 and normal hexane mixed solution are eluent, with silica gel column chromatography partition method purifying crude product, obtain described compd E solid.
7. ruddiness electroluminescent organic material according to claim 2, is characterized in that, the separating-purifying of described compound F 17-hydroxy-corticosterone comprises:
Question response stops being chilled to after room temperature, collects the throw out in reaction solution, with methyl alcohol, normal hexane washing, obtains corresponding compound F 17-hydroxy-corticosterone after vacuum-drying successively.
8. ruddiness electroluminescent organic material according to claim 2, is characterized in that, the separating-purifying of described compound ruddiness electroluminescent organic material comprises:
Question response stops being chilled to after room temperature, filter the throw out of collecting in reaction solution, successively with ethanol and normal hexane washing, obtain solid, solid is dissolved in methylene dichloride again, removes by filter insolubles, concentrated remove crude product that solvent obtains to take methylene dichloride and normal hexane mixed solution be eluent, by silica gel column chromatography partition method, purify, product adopts methylene dichloride and alcohol mixed solvent recrystallization further to purify, and after being dried, obtains ruddiness electroluminescent organic material.
9. an organic electroluminescence device, is characterized in that, the dopant material of the luminescent layer of this device is ruddiness electroluminescent organic material claimed in claim 1.
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| CN110760305A (en) * | 2019-11-01 | 2020-02-07 | 吉林奥来德光电材料股份有限公司 | Phosphorescent compound, preparation method thereof and organic electroluminescent device comprising phosphorescent compound |
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