CN104119858A - Iridium-metal-complex organic electrophosphorescent material, preparation method thereof and organic electroluminescent device - Google Patents
Iridium-metal-complex organic electrophosphorescent material, preparation method thereof and organic electroluminescent device Download PDFInfo
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- 0 CCC=C(*)[C@]1C=NC(c(cc2)ccc2-c2ccccc2)=CC1 Chemical compound CCC=C(*)[C@]1C=NC(c(cc2)ccc2-c2ccccc2)=CC1 0.000 description 2
- GSJKDPVESKNZLR-UHFFFAOYSA-N CC1[O]=C(C)C=C(C)O1 Chemical compound CC1[O]=C(C)C=C(C)O1 GSJKDPVESKNZLR-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides an iridium-metal-complex organic electrophosphorescent material with the structural formula (1), and in the formula (1), R is methyl, phenyl, naphthalen-1-yl or naphthalen-2-yl. According to the iridium metal complex, 2-(4'-biphenyl)-5-substituted formylpyridine is taken as a cyclometalating ligand main structure, also an auxiliary ligand acetylacetone is employed, firstly the cyclometalating ligand and Iridium(III) chloride hydrate are subjected to polymerization reaction in a mixed solvent of 2-ethoxyethanol and water so as to obtain a chlorine-bridged dipolymer, and then the obtained chlorine-bridged dipolymer and acetylacetone are subjected to complexing reaction in an organic solvent, so that the iridium-metal-complex organic electrophosphorescent material with the structural formula (1) is obtained. The material has good energy transmission efficiency and proper orange-light or red-light emission wavelength, is widely applicable to prepare orange-light, red-light or white-light phosphorescent electroluminescent devices, and helps to realize the purposes of reducing device power dissipation and improving device performances and prolonging service life.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of iridium metal complex organic electromechanical phosphorescent material and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescence device (OLED) is a kind ofly to take organic materials as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, luminous, response are fast, reduce power consumption, in fields such as demonstration, illuminations, has application prospect very widely.
Electroluminescent organic material can be divided into two kinds of fluorescent material and phosphor materials.In fluorescence electroluminescent device, due to the restriction that is subject to spinning and prohibiting, the excited singlet state that produces fluorescence only accounts for whole 25% of the sum that excites, and makes the luminous efficiency of device not high.And using phosphor material as electroluminescent material, can make singlet state and triplet exciton all be utilized effectively, external quantum efficiency is improved.Conventionally, in organic phosphorescent material, introduce heavy metal atom and strengthen spin orbit coupling effect, improve the transition rate constant of electron spinning upset, thereby improve phosphorescence rate constant and phosphorescence quantum yield, finally improve the luminescent properties of organic electroluminescence device.
At present, metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and has very high electroluminescent properties, is widely applied.And 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.But when research and development red phosphorescence material, sometimes molecular designing can cause phosphorescence wavelength to be slightly shorter than ruddiness (<620nm) one-tenth orange-colored light.So, concerning the research in a sense of orange-colored light phosphor material, can grow the research field of phosphorescent light-emitting materials.
Summary of the invention
For overcoming the problem of above-mentioned prior art, the invention provides a kind of iridium metal complex organic electromechanical phosphorescent material and preparation method thereof and organic electroluminescence device.Iridium metal complex organic electromechanical phosphorescent material provided by the invention has good energy transmission efficiency and suitable orange light or red light-emitting wavelength.Preparation technology of the present invention is easy to control, and is conducive to the suitability for industrialized production of device, and low processing cost, has very wide commercialized development prospect.Organic electroluminescence device prepared by the present invention can be launched high purity orange light or ruddiness, and has the excellent performances such as luminous efficiency is high, good stability.
First aspect; the invention provides a kind of iridium metal complex organic electromechanical phosphorescent material; as the formula (1), in formula, R is methyl to the structural formula of described iridium metal complex organic electromechanical phosphorescent material; phenyl; naphthalene-1-base or naphthalene-2-base, the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes, also comprises assistant ligand; described assistant ligand is methyl ethyl diketone
The feature of iridium metal complex organic electromechanical phosphorescent material provided by the invention is to take the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine is cyclic metal complexes; take methyl ethyl diketone as assistant ligand, then by introducing methyl, phenyl, naphthalene-1-base or naphthalene-2-base to obtain satisfied orange red or red light-emitting wavelength.Macoradical can produce certain space steric effect as the existence of phenyl, naphthyl (naphthalene-1-base, naphthalene-2-yl), 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.
Iridium metal complex organic electromechanical phosphorescent material of the present invention can be used as the luminescent material in orange light, ruddiness or white light organic electroluminescent device.
Second aspect, the invention provides a kind of preparation method of iridium metal complex organic electromechanical phosphorescent material, comprises the following steps:
(1) cyclic metal complexes of preparing or providing following structural formula to represent:
In formula, R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base;
(2) under protection of inert gas, after described cyclic metal complexes and hydration iridous chloride are mixed for 2: 1 in molar ratio～3: 1, in the mixed solvent of cellosolvo and water, be heated to 120 ℃ of backflows and carry out polyreaction 24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is as follows:
(3) under protection of inert gas and alkaline condition; the chlorine bridge dipolymer obtaining in step (2) and methyl ethyl diketone are heated to 60～135 ℃ in organic solvent and carry out complex reaction 12 hours; obtain iridium metal complex organic electromechanical phosphorescent material; the structural formula of described iridium metal complex as the formula (1); the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes; also comprise assistant ligand; described assistant ligand is methyl ethyl diketone; in formula; R is methyl; phenyl, naphthalene-1-base or naphthalene-2-base
For described cyclic metal complexes, when R is respectively methyl, phenyl, when naphthalene-1-base or naphthalene-2-base, the structural formula of described cyclic metal complexes is respectively:
The reaction formula of the polyreaction of step (2) is as follows:
Wherein, R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base.
In step (2), in described mixed solvent, the volume ratio of cellosolvo and water is preferably 3:1, and the volumetric usage of described cellosolvo (mL) can be 6～10 times of cyclic metal complexes mole dosage (mmol).Described polyreaction is carried out under agitation condition.Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described step (2) further comprises following purification procedures: after described polyreaction, cooling reaction solution is to room temperature, filter, obtain chlorine bridge dipolymer crude product, more successively with methyl alcohol, normal hexane washing, after being dried, obtain the chlorine bridge dipolymer after purifying.
Preferably, described being dried as vacuum-drying.
The reaction formula of the complex reaction of step (3) is as follows:
Step (3) is heated to 60～135 ℃ by resulting chlorine bridge dipolymer and methyl ethyl diketone in step (2) and carries out complex reaction 12 hours in organic solvent, generates the different type complex of iridium of joining, i.e. iridium metal complex organic electromechanical phosphorescent material.
In step (3), the mol ratio of described chlorine bridge dipolymer and methyl ethyl diketone is 1:2～1:4.The concentration of described chlorine bridge dipolymer in organic solvent is 0.01～0.02mol/L.
Described alkaline condition is: adding molar weight is the solid alkali of 6～12 times of chlorine bridge dipolymers.Described solid alkali can be but be not limited to sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood etc., be preferably sodium carbonate.
Preferably, organic solvent is cellosolvo, 2-methyl cellosolve, methylene dichloride, 1,2-ethylene dichloride or trichloromethane.
Described complex reaction carries out under agitation condition.
Preferably, described step (3) further comprises following purification procedures: after completion of the reaction described, cooling reaction solution is to room temperature, filtration is precipitated thing, successively with ethanol and normal hexane washing, obtain iridium metal complex crude product, again described crude product is dissolved in methylene dichloride, filter, collect filtrate the concentrated methylene dichloride of removing, obtain the elementary purified product of iridium metal complex, take methylene dichloride and normal hexane mixing solutions is eluent again, adopt the silica gel column chromatography partition method elementary purified product of described iridium metal complex of purifying, obtain the iridium metal complex after purifying.
More preferably, described purification procedures further comprises: adopt the mixed solvent of methylene dichloride and ethanol to carry out recrystallization the iridium metal complex after described purifying.
Preferably, the cyclic metal complexes in described step (1) adopts following manner preparation:
(a) compd A and the compd B that provide respectively following structural formula to represent:
(b) under the condition of catalyzer, alkali and organic solvent, by after compd A and compd B mixing in 1: 1 in molar ratio～1: 1.5, be heated to 80～110 ℃ of backflows and carry out Suzuki linked reaction 6～10 hours, obtain the Compound C that following structural formula represents:
(c) under protection of inert gas, by Compound C and n-Butyl Lithium in tetrahydrofuran (THF) or ether, at-78 ℃, stirring reaction is 35 minutes, again to the tetrahydrofuran (THF) or the diethyl ether solution that add Compound D in above-mentioned reaction system, continue stirring reaction 60 minutes, after reacting completely, add ammonium chloride saturated solution termination reaction, obtain described cyclic metal complexes; The structural formula of described Compound D is:
In formula, R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base.
The reaction formula of the Suzuki linked reaction of step (b) is:
Preferably, the catalyzer that described Suzuki linked reaction adopts is organic palladium catalyzer.More preferably, described catalyzer is that four (triphenyl phosphorus) close palladium (Pd (PPh
3)
4) or two (triphenylphosphine) palladium chloride (II) (Pd (PPh
3)
2cl
2).Preferably, the consumption of described organic palladium catalyzer is 3%～5% of compd A mole dosage.
The alkaline solution that described Suzuki linked reaction adopts can be inorganic alkali solution or organic bases solution, inorganic alkali solution can be the aqueous solution of alkali metal hydroxide or alkaline carbonate, such as being but be not limited to sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, solution of potassium carbonate etc., be preferably sodium carbonate solution, organic bases solution can be tetrabutyl phosphonium bromide aqueous ammonium; The consumption of above-mentioned alkaline solution can be 1～10 times of compd A mole dosage.
The organic solvent that described Suzuki linked reaction adopts is low-pole or aprotic, polar organic solvent or its mixed solvent, can be for example but be not limited to chloroform, methylene dichloride, glycol dimethyl ether, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), tetrahydrofuran (THF) (THF), toluene, dimethylbenzene or its similar compound, being preferably toluene; The consumption of organic solvent is enough, so that each reactants dissolved fully reaction.
Preferably, described in step (b) after Suzuki linked reaction, cooling reaction solution, to room temperature, adds distilled water, adopts and is extracted with ethyl acetate, get organic phase, dry, obtain Compound C crude product after steaming solvent, then to take ethyl acetate and the normal hexane mixed solution that volume ratio is 1:3 be eluent, with the silica gel column chromatography partition method described Compound C crude product of purifying, obtain the Compound C after purifying.
Preferably, described dry employing anhydrous magnesium sulfate.
The reaction formula of step (c) is:
Described n-Butyl Lithium is dissolved in normal hexane; in step (c); in oxygen-free environment, under low temperature (78 ℃), there is substitution reaction, the bromine on the lithium substituted benzene ring in n-Butyl Lithium with n-Butyl Lithium in Compound C elder generation; then; to the tetrahydrofuran solution that adds Compound D in reaction system, continue to stir and acylation reaction occurred in 60 minutes, after reacting completely; add ammonium chloride saturated solution termination reaction, obtain described cyclic metal complexes.
Preferably, Compound C and n-Butyl Lithium with mole dosage than being 1:1～1:2.Preferably, the mol ratio of Compound C and Compound D is 1:1～1:2.
The add-on of described ammonium chloride saturated solution is appropriate.
Preferably, described in step (c), after reaction terminating, question response liquid rises to room temperature, adopts repeatedly extraction product of ether, merge organic phase, dry, filter, concentrate and remove described ether, obtain cyclic metal complexes crude product, the ethyl acetate that the volume ratio of take is again 1:6～1:8 and normal hexane mixed solution are eluent, with the silica gel column chromatography partition method described cyclic metal complexes crude product of purifying, obtain the cyclic metal complexes after purifying.
Preferably, described dry employing anhydrous sodium sulphate.
The third aspect, the invention provides a kind of organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode; the described luminescent layer iridium metal complex organic electromechanical phosphorescent material that adulterated; as the formula (1), in formula, R is methyl to the structural formula of described iridium metal complex; phenyl; naphthalene-1-base or naphthalene-2-base, the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes, also comprises assistant ligand; described assistant ligand is methyl ethyl diketone
In above-mentioned iridium metal complex organic electromechanical phosphorescent material; the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes; take methyl ethyl diketone as assistant ligand, then by introducing methyl, phenyl, naphthalene-1-base or naphthalene-2-base to obtain satisfied orange red or red light-emitting wavelength.Macoradical can produce certain space steric effect as the existence of phenyl, naphthyl (naphthalene-1-base, naphthalene-2-yl), 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.
Iridium metal complex organic electromechanical phosphorescent material of the present invention can be used as the luminescent material in orange light, ruddiness or white light organic electroluminescent device.
In the preparation method of above-mentioned iridium metal complex organic electromechanical phosphorescent material, adopt better simply synthetic route, technique is easy to control, and is conducive to the suitability for industrialized production of device, greatly reduces the cost of manufacturing, and has very wide commercialized development prospect.In above-mentioned organic electroluminescence device, above-mentioned iridium metal complex organic electromechanical phosphorescent material is doped in the material of main part in organic electroluminescence device luminescent layer as guest materials, can prevent the quenching phenomenon of triplet exciton, and both have good consistency, can be widely used in preparation orange light, ruddiness or white-light phosphor photoelectricity electroluminescence device, reach reduction device power consumption, improve the object of device performance prolongs life.The organic electroluminescence device of above-mentioned iridium metal complex organic electromechanical phosphorescent material of having adulterated in luminescent layer can be launched high purity orange light or ruddiness, and has good device performance.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural formula of the iridium metal complex organic electromechanical phosphorescent material of the embodiment of the present invention;
Fig. 2 is the preparation feedback schema of the iridium metal complex organic electromechanical phosphorescent material of the embodiment of the present invention 1;
Fig. 3 is the utilizing emitted light spectrogram of iridium metal complex organic electromechanical phosphorescent material in the embodiment of the present invention 1;
Fig. 4 is the structural representation of organic electroluminescence device in the embodiment of the present invention 5.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of iridium metal complex organic electromechanical phosphorescent material; the structural formula of described iridium metal complex as the formula (1); in formula; R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base; the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes; also comprise assistant ligand, described assistant ligand is methyl ethyl diketone
Embodiment 1: a kind of iridium metal complex organic electromechanical phosphorescent material two [2-(4'-xenyl)-5-acetylpyridine-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned iridium metal complex organic electromechanical phosphorescent material, comprises the steps:
(1) compd A and the compd B that provide respectively following structural formula to represent:
(2) Compound C 2-(4'-xenyl)-5-bromopyridine is synthetic
By 0.71g (3.0mmol) 2,5-dibromo pyridine, 0.71g (3.6mmol) 4-biphenyl boric acid, 0.17g (0.15mmol) tetrakis triphenylphosphine palladium, sodium carbonate (10.0mmol) aqueous solution that 30mL toluene and 10mL concentration are 1mol/L, back flow reaction 8h at 110 ℃ of temperature.Question response is chilled to the appropriate distilled water of impouring after room temperature, ethyl acetate extraction, and anhydrous magnesium sulfate drying organic phase, filters, and rotation is steamed and is desolventized to obtain crude product.Ethyl acetate/normal hexane mixed solution that the volume ratio of take is again 1:3 is eluent, with silica gel column chromatography partition method purifying crude product, obtains 0.63g white solid, and yield is 67.7%.
Structural Identification:
Mass spectrum (MS m/z): 309.0 (M
+)
Ultimate analysis: C17H12BrN
Theoretical value: C, 65.83; H, 3.90; Br, 25.76; N, 4.52;
Measured value: C, 65.77; H, 3.97; Br, 25.72; N, 4.54.
The resulting white solid matter of the above-mentioned reaction of above data acknowledgement is 2-(4'-xenyl)-5-bromopyridine.
(3) 2-(4'-xenyl)-5-acetylpyridine is synthetic
Under argon shield, 1.24g (4.0mmol) 2-(4 '-xenyl)-5-bromopyridine is dissolved in to 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 1.6mol/L, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.0.52g (6.0mmol) N,N-dimethylacetamide 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.Ethyl acetate/normal hexane mixed solution that the volume ratio of take is 1:6 is eluent, with silica gel column chromatography partition method purifying crude product, obtains 0.60g white solid, and yield is 54.9%.
Structural Identification:
Mass spectrum (MS m/z): 273.1 (M
+)
Ultimate analysis: C19H15NO
Theoretical value: C, 83.49; H, 5.53; N, 5.12; O, 5.85;
Measured value: C, 83.42; H, 5.57; N, 5.17; O, 5.84.
The resulting white solid matter of the above-mentioned reaction of above data acknowledgement is 2-(4'-xenyl)-5-acetylpyridine.
(4) 2-(4'-xenyl)-5-acetylpyridine is dimeric synthetic containing iridium dichloro
Under nitrogen protection, 0.60g (2.2mmol) 2-(4'-xenyl)-5-acetylpyridine is dissolved in 15mL2-ethoxy ethanol, then 0.35g (1.0mmol) three hydration iridous chlorides and 5ml distilled water are added 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 2-(4'-xenyl)-5-acetylpyridine containing iridium dichloro dimer.
(5) title complex two [2-(4'-xenyl)-5-acetylpyridine-N, C2'] (methyl ethyl diketone) closes the synthetic of iridium
Under nitrogen protection; by the main part making be 2-(4'-xenyl)-5-acetylpyridine containing iridium dichloro dimer; 1.5mL (1.5mmol) methyl ethyl diketone and 0.32g (3.0mmol) sodium carbonate are dissolved in 20mL2-ethoxy ethanol, and stirring reaction mixed solution is heated to 100 ℃ of reaction 12h.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/alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.34g pure products, and yield is 40.7%.
Structural Identification:
Mass spectrum (MS m/z): 836.2 (M
+)
Ultimate analysis: C43H35IrN2O4
Theoretical value: C, 61.78; H, 4.22; Ir, 22.99; N, 3.35; O, 7.66;
Measured value: C, 61.72; H, 4.29; Ir, 22.93; N, 3.38; O, 7.68.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [2-(4'-xenyl)-5-acetylpyridine-N, C
2'] (methyl ethyl diketone) close iridium.
As shown in Figure 3, 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 (concentration is～10 to end product title complex
-5mol/L) at CH
2cl
2the maximum emission peak of the middle emmission spectrum of solution, at 598nm place, can be used as the preparation field that orange photoelectricity electroluminescent material is widely used in organic electroluminescence device.
In addition, (concentration is～10 to title complex
-5mol/L) CH
2cl
2solution, at 298K temperature, with face formula-tri-under the same terms (2-(4 ', 6 '-difluorophenyl) pyridine-N, C
2') close iridium (fac-Ir (ppy)
3) CH
2cl
2solution is standard (Φ
ph=0.40), record the Φ of end product
pL=0.42, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: a kind of iridium metal complex organic electromechanical phosphorescent material two [2-(4'-xenyl)-5-benzoyl pyridine-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned iridium metal complex organic electromechanical phosphorescent material, comprises the steps:
(1) synthesis step of 2-(4'-xenyl)-5-bromopyridine is with embodiment 1;
(2) cyclic metal complexes 2-(4'-xenyl)-5-benzoyl pyridine is synthetic
Under argon shield, 1.24g (4.0mmol) 2-(4'-xenyl)-5-bromopyridine is dissolved in to 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 1.6mol/L, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.By 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.Ethyl acetate/normal hexane mixed solution that the volume ratio of take is 1:7 is eluent, with silica gel column chromatography partition method purifying crude product, obtains 0.68g white solid, and yield is 50.7%.
Structural Identification:
Mass spectrum (MS m/z): 335.1 (M
+)
Ultimate analysis: C24H17NO
Theoretical value: C, 85.94; H, 5.11; N, 4.18; O, 4.77;
Measured value: C, 85.85; H, 5.17; N, 4.16; O, 4.82.
The resulting white solid matter of the above-mentioned reaction of above data acknowledgement is 2-(4'-xenyl)-5-benzoyl pyridine.
(3) 2-(4'-xenyl)-5-benzoyl pyridine is dimeric synthetic containing iridium dichloro
Under nitrogen protection, 0.79g (2.2mmol) 2-(4'-xenyl)-5-benzoyl pyridine is dissolved in 15mL2-ethoxy ethanol, then 0.35g (1.0mmol) three hydration iridous chlorides and 5ml distilled water are added 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 2-(4'-xenyl)-5-benzoyl pyridine containing iridium dichloro dimer.
(4) two [2-(4'-xenyl)-5-benzoyl pyridine-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part making be 2-(4'-xenyl)-5-benzoyl pyridine containing iridium dichloro dimer; 1.5mL (1.5mmol) methyl ethyl diketone and 0.32g (3.0mmol) sodium carbonate are dissolved in 20mL2-ethoxy ethanol, and stirring reaction mixed solution is heated to 100 ℃ of reaction 12h.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/alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.32g pure products, and yield is 33.3%.
Structural Identification:
Mass spectrum (MS m/z): 960.2 (M
+)
Ultimate analysis: C53H39IrN2O4
Theoretical value: C, 66.30; H, 4.09; Ir, 20.02; N, 2.92; O, 6.67;
Measured value: C, 66.33; H, 4.03; Ir, 20.10; N, 2.91; O, 6.63.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [2-(4'-xenyl)-5-benzoyl pyridine-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L), at 610nm place, can be used as the preparation field that orange photoelectricity electroluminescent material is widely used in organic electroluminescence device.In addition, 10
-5the CH of mol/L 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=0.23.
Embodiment 3: a kind of iridium metal complex organic electromechanical phosphorescent material two [2-(4'-xenyl)-5-benzoyl pyridine-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned iridium metal complex organic electromechanical phosphorescent material, comprises the steps:
(1) synthesis step of 2-(4'-xenyl)-5-bromopyridine is with embodiment 1;
(2) cyclic metal complexes 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine is synthetic
Under argon shield, 1.24g (4.0mmol) 2-(4'-xenyl)-5-bromopyridine is dissolved in to 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 1.6mol/L, in 10min, dropwises, and continues to stir 35min at-78 ℃ of temperature.By 1.20g (6.0mmol) N, N-dimethyl-naphthalene-1'-base methane amide is dissolved in the new THF steaming of 20mL, in 5min, dropwise adds in reaction system again.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.Ethyl acetate/normal hexane mixed solution that the volume ratio of take is 1:8 is eluent, with silica gel column chromatography partition method purifying crude product, obtains 0.74g white solid, and yield is 48.0%.
Structural Identification:
Mass spectrum (MS m/z): 385.2 (M
+)
Ultimate analysis: C28H19NO
Theoretical value: C, 87.25; H, 4.97; N, 3.63; O, 4.15;
Measured value: C, 87.31; H, 4.90; N, 3.65; O, 4.14.
The resulting white solid matter of the above-mentioned reaction of above data acknowledgement is 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine.
(3) 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine is dimeric synthetic containing iridium dichloro
Under nitrogen protection, 0.85g (2.2mmol) 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine is dissolved in 15mL2-ethoxy ethanol, 0.35g (1.0mmol) three hydration iridous chlorides and 5ml 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 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine containing iridium dichloro dimer.
(4) two [2-(4'-xenyl)-5-benzoyl pyridine-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part making be 2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine containing iridium dichloro dimer; 1.5mL (1.5mmol) methyl ethyl diketone and 0.32g (3.0mmol) sodium carbonate are dissolved in 20mL2-ethoxy ethanol, and stirring reaction mixed solution is heated to 100 ℃ of reaction 12h.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/alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.32g pure products, and yield is 30.2%.
Structural Identification:
Mass spectrum (MS m/z): 1060.3 (M
+)
Ultimate analysis: C61H43IrN2O4
Theoretical value: C, 69.10; H, 4.09; Ir, 18.13; N, 2.64; O, 6.04;
Measured value: C, 69.13; H, 4.02; Ir, 18.16; N, 2.68; O, 6.01.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [2-(4'-xenyl)-5-(naphthalene-1'-formyl radical) pyridine-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L), at 621nm 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 mol/L 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=0.21.
Embodiment 4: a kind of iridium metal complex organic electromechanical phosphorescent material two [2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned iridium metal complex organic electromechanical phosphorescent material, comprises the steps:
(1) synthesis step of 2-(4'-xenyl)-5-bromopyridine is with embodiment 1;
(2) cyclic metal complexes 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine is synthetic
Under argon shield, 1.24g (4.0mmol) 2-(4'-xenyl)-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-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.Ethyl acetate/normal hexane mixed solution that the volume ratio of take is 1:8 is eluent, with silica gel column chromatography partition method purifying crude product, obtains 0.69g white solid, and yield is 44.8%.
Structural Identification:
Mass spectrum (MS m/z): 385.2 (M
+)
Ultimate analysis: C28H19NO
Theoretical value: C, 87.25; H, 4.97; N, 3.63; O, 4.15;
Measured value: C, 87.29; H, 4.91; N, 3.68; O, 4.12.
The resulting white solid matter of the above-mentioned reaction of above data acknowledgement is 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine.
(3) 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine is dimeric synthetic containing iridium dichloro
Under nitrogen protection, 0.85g (2.2mmol) 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine is dissolved in 15mL2-ethoxy ethanol, and 0.35g (1.0mmol) three hydration iridous chlorides and 5mL 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 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine containing iridium dichloro dimer.
(4) two [2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine-N, C of title complex
2'] (methyl ethyl diketone) close the synthetic of iridium
Under nitrogen protection; by the main part making be 2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine containing iridium dichloro dimer; 1.5mL (1.5mmol) methyl ethyl diketone and 0.32g (3.0mmol) sodium carbonate are dissolved in 10mL2-ethoxy ethanol, and stirring reaction mixed solution is heated to 100 ℃ of reaction 12h.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/alcohol mixed solvent recrystallization further to purify, and after being dried, obtains 0.30g pure products, and yield is 28.3%.
Structural Identification:
Mass spectrum (MS m/z): 1060.3 (M
+)
Ultimate analysis: C61H43IrN2O4
Theoretical value: C, 69.10; H, 4.09; Ir, 18.13; N, 2.64; O, 6.04;
Measured value: C, 69.15; H, 4.01; Ir, 18.15; N, 2.66; O, 6.05.
The resulting material of the above-mentioned reaction of above data acknowledgement is two [2-(4'-xenyl)-5-(naphthalene-2'-formyl radical) pyridine-N, C
2'] (methyl ethyl diketone) close iridium.
End product is CH at 298K temperature
2cl
2solution (～10
-5the maximum emission peak of middle emmission spectrum mol/L) is at 616nm place.In addition, 10
-5the CH of mol/L 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=0.33.
Embodiment 5:
The title complex two [2-(4'-xenyl)-5-acetylpyridine-N, the C that with embodiment 1, make
2'] (methyl ethyl diketone) close iridium as the organic electroluminescence device of luminescent layer doping object, structure as shown in Figure 4:
This device is followed successively by ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq
3(20nm)/LiF (2nm)/Al (100nm), on a glass-based plate, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as transparent anode 301, by vacuum evaporation, on anode 301, prepare successively the 2-TNATA(4 that a layer thickness is 40nm, 4', 4 " tri-(N-(naphthalene-2-yl)-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, two [2-(4'-xenyl)-5-acetylpyridine-N with a layer thickness embodiment that is 8% doped with massfraction 1 preparation that is 30nm, C
2'] (methyl ethyl diketone) close the CBP (N of iridium, two carbazyl-4 of N'-, 4'-dipyridyl) as luminescent layer 304, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 304 again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) LiF that the Alq3 that material is 20nm as hole blocking layer 305, thickness (three (oxine) aluminium) is 2nm as electron transfer layer 306, thickness 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, as the negative electrode 308 of device.
Through performance test, know, the maximum emission wavelength of the volume electroluminescent spectrum of this device is positioned at 601nm, and maximum lumen efficiency is 19.6lm/W, and maximum external quantum efficiency is 11.1%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an iridium metal complex organic electromechanical phosphorescent material; it is characterized in that; as the formula (1), the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes, also comprises assistant ligand to the structural formula of described iridium metal complex organic electromechanical phosphorescent material; described assistant ligand is methyl ethyl diketone; in formula, R is methyl, phenyl; naphthalene-1-base or naphthalene-2-base
2. a preparation method for iridium metal complex organic electromechanical phosphorescent material, is characterized in that, comprises the following steps:
(1) cyclic metal complexes of preparing or providing following structural formula to represent:
In formula, R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base;
(2) under protection of inert gas, after described cyclic metal complexes and hydration iridous chloride are mixed for 2: 1 in molar ratio～3: 1, in the mixed solvent of cellosolvo and water, be heated to 120 ℃ of backflows and carry out polyreaction 24 hours, obtain chlorine bridge dipolymer; The structural formula of described chlorine bridge dipolymer is as follows:
(3) under protection of inert gas and alkaline condition; the chlorine bridge dipolymer obtaining in step (2) and methyl ethyl diketone are heated to 60～135 ℃ in organic solvent and carry out complex reaction 12 hours; obtain iridium metal complex organic electromechanical phosphorescent material; the structural formula of described iridium metal complex as the formula (1); the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes; also comprise assistant ligand; described assistant ligand is methyl ethyl diketone; in formula; R is methyl; phenyl, naphthalene-1-base or naphthalene-2-base
3. the preparation method of iridium metal complex as claimed in claim 2, it is characterized in that, described step (2) further comprises following purification procedures: after described polyreaction, cooling reaction solution is to room temperature, filter, obtain chlorine bridge dipolymer crude product, more successively with methyl alcohol, normal hexane washing, after being dried, obtain the chlorine bridge dipolymer after purifying.
4. the preparation method of iridium metal complex as claimed in claim 2, it is characterized in that, described step (3) further comprises following purification procedures: after described complex reaction, cooling reaction solution is to room temperature, filtration is precipitated thing, successively with ethanol and normal hexane washing, obtain iridium metal complex crude product, again described crude product is dissolved in methylene dichloride, filter, collect filtrate the concentrated methylene dichloride of removing, obtain the elementary purified product of iridium metal complex, take methylene dichloride and normal hexane mixing solutions is eluent again, adopt the silica gel column chromatography partition method elementary purified product of described iridium metal complex of purifying, obtain the iridium metal complex after purifying.
5. the preparation method of iridium metal complex as claimed in claim 4, is characterized in that, described purification procedures further comprises: adopt the mixed solvent of methylene dichloride and ethanol to carry out recrystallization the iridium metal complex after described purifying.
6. the preparation method of iridium metal complex as claimed in claim 2, is characterized in that, the cyclic metal complexes in described step (1) adopts following manner preparation:
(a) compd A and the compd B that provide respectively following structural formula to represent:
(b) under the condition of catalyzer, alkali and organic solvent, by after compd A and compd B mixing in 1: 1 in molar ratio～1: 1.5, be heated to 80～110 ℃ of backflows and carry out Suzuki linked reaction 6～10 hours, obtain the Compound C that following structural formula represents:
(c) under protection of inert gas, by Compound C and n-Butyl Lithium in tetrahydrofuran (THF) or ether, at-78 ℃, stirring reaction is 35 minutes, again to the tetrahydrofuran (THF) or the diethyl ether solution that add Compound D in above-mentioned reaction system, continue stirring reaction 60 minutes, after reacting completely, add ammonium chloride saturated solution termination reaction, obtain described cyclic metal complexes; The structural formula of described Compound D is:
In formula, R is methyl, phenyl, naphthalene-1-base or naphthalene-2-base.
7. the preparation method of iridium metal complex as claimed in claim 6, it is characterized in that, described in step (b), after Suzuki linked reaction, cooling reaction solution is to room temperature, add distilled water, adopt and be extracted with ethyl acetate, get organic phase, dry, after steaming solvent, obtain Compound C crude product, the ethyl acetate that the volume ratio of take is again 1:3 and normal hexane mixed solution are eluent, with the silica gel column chromatography partition method described Compound C crude product of purifying, obtain the Compound C after purifying.
8. the preparation method of iridium metal complex as claimed in claim 6, is characterized in that, described in step (c) after reaction terminating, question response liquid rises to room temperature, adopt repeatedly extraction product of ether, merge organic phase, dry, filter, concentrated remove described ether, obtain cyclic metal complexes crude product, then to take ethyl acetate and the normal hexane mixed solution that volume ratio is 1:6～1:8 be eluent, with the silica gel column chromatography partition method described cyclic metal complexes crude product of purifying, obtain the cyclic metal complexes after purifying.
9. the preparation method of iridium metal complex as claimed in claim 6, is characterized in that, the catalyzer that described Suzuki linked reaction adopts is organic palladium catalyzer; The consumption of described organic palladium catalyzer is 3%～5% of compd A mole dosage.
10. an organic electroluminescence device, comprises anode, functional layer, luminescent layer and negative electrode, it is characterized in that; the described luminescent layer iridium metal complex organic electromechanical phosphorescent material that adulterated; as the formula (1), in formula, R is methyl to the structural formula of described iridium metal complex; phenyl; naphthalene-1-base or naphthalene-2-base, the agent structure that 2-(4'-xenyl)-5-substituting group formyl radical pyridine of take is cyclic metal complexes, also comprises assistant ligand; described assistant ligand is methyl ethyl diketone
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