CN103965255A - Red light-emitting organic electrophosphorescent material iridium complex, its preparation method and organic electroluminescent device - Google Patents
Red light-emitting organic electrophosphorescent material iridium complex, its preparation method and organic electroluminescent device Download PDFInfo
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- 0 Cc1ccc(*)cc1 Chemical compound Cc1ccc(*)cc1 0.000 description 4
- WXXRWYRZLBAERW-UHFFFAOYSA-N C1CB1c1ccccc1 Chemical compound C1CB1c1ccccc1 WXXRWYRZLBAERW-UHFFFAOYSA-N 0.000 description 1
- AMXIRIUXSPTQCN-UHFFFAOYSA-N CC(CCC1)C=C1C(F)(F)F Chemical compound CC(CCC1)C=C1C(F)(F)F AMXIRIUXSPTQCN-UHFFFAOYSA-N 0.000 description 1
- BGJXEXJSMPZQLH-UHFFFAOYSA-N Cc(cccc1)c1-c(nn1)c(cccc2)c2c1Oc1ccccc1 Chemical compound Cc(cccc1)c1-c(nn1)c(cccc2)c2c1Oc1ccccc1 BGJXEXJSMPZQLH-UHFFFAOYSA-N 0.000 description 1
- RNXJIWHLCOFZAT-UHFFFAOYSA-N Clc([nH]1)c(cccc2)c2c1Oc1ccccc1 Chemical compound Clc([nH]1)c(cccc2)c2c1Oc1ccccc1 RNXJIWHLCOFZAT-UHFFFAOYSA-N 0.000 description 1
- PTGXMBPJFXPBQV-UHFFFAOYSA-N c(cc1)ccc1-c(nn1)c(cccc2)c2c1Oc1ccccc1 Chemical compound c(cc1)ccc1-c(nn1)c(cccc2)c2c1Oc1ccccc1 PTGXMBPJFXPBQV-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a red light-emitting organic electrophosphorescent material iridium complex having a structure shown in the formula (1), and in the formula, R represents hydrogen or methyl. A preparation method of the red light-emitting organic electrophosphorescent material iridium complex comprises the following steps that a ring metal main ligand is prepared by a Suzuki coupling reaction, the ring metal main ligand and IrCl3.3H2O undergo a polymerization reaction in a 2-ethoxyethanol-water mixed solvent to produce a chlorine-bridged bipolymer, and the chlorine-bridged bipolymer and diacetone undergo a ligand exchange reaction to produce the red light-emitting organic electrophosphorescent material iridium complex. The red light-emitting organic electrophosphorescent material iridium complex is prepared by synthesis of 1-phenoxy-4-phenylphthalazine or its derivative as the ring metal main ligand and diacetone as an assistant ligand, and can adjust luminescence wavelength and produce approximately-standard red light. An organic electroluminescent device prepared from the red light-emitting organic electrophosphorescent material iridium complex can emit high-purity red light and has high luminescence efficiency. The preparation method has simple processes and is suitable for industrial production.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex and preparation method thereof and organic electroluminescence device.
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, and organic electroluminescence device (OLED) is taking such organic materials as luminescent material, the energy conversion device that is luminous energy by electric energy conversion.There is the defects such as driving voltage is too high, luminous efficiency is very low in early stage organic electroluminescence device, research is stayed cool.To 1987, the human hairs such as the Tang of Kodak understood with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, thereby make that operating voltage is low, high brightness, high efficiency organic electroluminescence device, pull open the new prelude of electroluminescent organic material research.
According to different principle of luminosity, electroluminescent organic material can be divided into fluorescent material and phosphor material, according to spin statistical theory, the device theoretical internal quantum efficiency limit that fluorescent material is made is 25%, how to make full use of residue 75% phosphorescence and realizes higher luminous efficiency and become the hot research direction in this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of the device that phosphor material is made breaks through 25%, makes the research of electroluminescent organic material enter another new period.
Wherein, small molecules doping type transition metal complex, as the title complex of iridium, ruthenium, platinum etc., thereby can utilize triplet exciton to obtain very high emitted energy to improve the quantum yield of organic electroluminescence device, becomes the research emphasis in phosphor material field.Cyclometalated iridium (III) title complex is to have relatively short lifetime of excited state, high luminous quantum efficiency and excellent glow color adjustability, and the phosphor material of good stability, synthetic reaction condition gentleness is accounting for dominant position in corresponding research always.
For the full color realizing based on OLED device shows, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously, in general, the development of blue phosphorescent material always lags behind red and green phosphorescent material, single from this index of purity of color, the luminous purity of color that seldom can reach so far dark red light and dark green light of blue phosphorescent material.Current blue phosphorescent material is taking the phosphor material of sky blue light as main, as two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), and for producing gratifying white light OLED, requiring the luminous of red phosphorescence material of collocation is to approach saturated red scarlet, both carry out the compensation of purity of color, thereby obtain the white light OLED of high color purity, therefore, the ruddiness phosphorescent organic electroluminescent material of research and development high color purity is still a large focus of OLED research field.
Summary of the invention
For overcoming the problem of above-mentioned prior art, the invention provides a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex and preparation method thereof and organic electroluminescence device.Ruddiness organic electromechanical phosphorescent material metal iridium complex provided by the invention is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, synthetic the obtaining taking methyl ethyl diketone as assistant ligand, and the method for introducing methyl on C by phenyl ring in part realizes the adjusting of glow color, obtain the ruddiness phosphor material with different red emission wavelengths.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 of the present invention can be launched high purity ruddiness, and has the excellent properties such as luminous efficiency is high, good stability.
On the one hand, the invention provides a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex, described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl.
Preferably, R is hydrogen or methyl, and the position of substitution when R is methyl comprises 4,5 or 6 of phenyl, and described ring master metal part is the compound with following structural formula:
Ruddiness organic electromechanical phosphorescent material metal iridium complex of the present invention is taking 1-phenoxy group-4-phenyl phthalazines and derivative thereof as ring metal master part, taking methyl ethyl diketone as assistant ligand, on the one hand, phenoxy group group on phthalazines ring is conducive to increase the solvability of title complex, and phenoxy group group volume is larger, sterically hindered larger, be beneficial to the interaction reducing between complex molecule, be conducive to luminous, and this title complex is special-shaped title complex, with the comparison of equal type title complex, have advantages of that synthetic difficulty is little, it is easier to purify, and there is equally excellent luminescent properties.On the other hand, can on phenyl ring, introduce methyl, make title complex have suitable red light-emitting wavelength, simultaneously methyl produces certain sterically hinderedly, reduces the direct effect between iridium atom, reduce the self-quenching probability of triplet exciton, and the phthalazines group in title complex with larger planar rigidity makes the vibration weakening of molecule, the excitation energy of molecule is difficult for because vibration discharges with heat energy form, and is beneficial to the coplanarity that increases molecule, increase electronics mobility in molecule, be all beneficial to the generation of phosphorescence; The red shift of methyl substituted phenyl ring emission wavelength, is beneficial to the ruddiness that obtains high color purity, can make the HOMO energy level of title complex decline simultaneously, is beneficial to the injection in hole, thus the transmission of the electric charge in balance organic electroluminescence device, the electroluminescent properties of raising device.
Second aspect, the invention provides a kind of preparation method of ruddiness organic electromechanical phosphorescent material metal iridium complex, comprises the following steps:
(1) compd A and the compd B that provide respectively following structural formula to represent:
Wherein, R is hydrogen or methyl, and compd B is
Under the condition of protection of inert gas and catalyzer, alkaline solution and organic solvent; compd A and compd B 1: 1 in molar ratio ~ 1:2 mixing post-heating to 80 ~ 100 DEG C are carried out to Suzuki linked reaction; time is 8 ~ 15h, obtains encircling master metal part, and reaction formula is:
(2) under protection of inert gas; by the ring master metal part obtaining in step (1) and three hydration iridous chlorides in molar ratio 2.2:1 ~ 3:1 after mixing, add in the mixed solvent of cellosolvo and water and carry out polyreaction; obtain chlorine bridge dipolymer, reaction formula is:
(3) under protection of inert gas; chlorine bridge dipolymer, methyl ethyl diketone and alkali in step (2) carry out ligand exchange reaction in solvent; obtain ruddiness organic electromechanical phosphorescent material metal iridium complex; the amount ratio of described chlorine bridge dipolymer and methyl ethyl diketone is 1mol:(2～4) L; the temperature of ligand exchange reaction is 62 ~ 100 DEG C; reaction times is 6 ~ 12h, and reaction formula is:
Described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl.
Preferably, R is hydrogen or methyl, and the position of substitution when R is methyl comprises 4,5 or 6 of phenyl, and described ring master metal part is the compound with following structural formula:
In step (1), the mol ratio of described compd A and compd B is 1: 1 ~ 1:2.Preferably, the mol ratio of described compd A and compd B is 1:1.2.Can carry out proportioning according to the metering ratio shown in chemical equation, can be also that partial reaction thing is excessive, can carry out described Suzuki linked reaction, and do not affect reaction carry out.
In step (1), preferably, described catalyzer is organic palladium catalyzer.More preferably, described catalyzer is that four (triphenyl phosphorus) close palladium (Pd (PPh
3)
4) or two (triphenylphosphine) palladium (Pd (PPh of dichloro
3)
2cl
2).Preferably, the consumption of described catalyzer is 3 ~ 5% of compd A mole dosage.
In step (1), the aqueous solution that described alkaline solution is alkali-metal carbonate.Preferably, described alkaline solution is sodium carbonate or wet chemical.Preferably, the concentration of described alkaline solution is 1～2mol/L, and the consumption of described alkaline solution is 2 ~ 5 times of calculating of compd A mole dosage according to the mole dosage of solute wherein.
In step (1), described organic solvent is low-pole or aprotic, polar organic solvent or its mixed solvent, can be 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.
In step (1), preferably, after completing, described Suzuki linked reaction carries out separating-purifying, obtain encircling master metal part, being operating as of described separating-purifying: question response liquid cooling is to room temperature, and the extraction that adds diethyl ether, obtains organic phase, with anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether solvent, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain encircling master metal part.
In step (1); preferably; the detailed process of described Suzuki linked reaction is as follows: under protection of inert gas; compd A, compd B, catalyzer and alkaline solution are added in organic solvent and mixed; stir and be heated to 100 DEG C; back flow reaction 10h, obtains encircling master metal part after separating-purifying.
In step (2), preferably, in described mixed solvent, the volume ratio of cellosolvo and water is 3:1.Described polyreaction is the back flow reaction of carrying out in mixed solvent generation boiling situation, is about 100 DEG C, and the reaction times is 24h.The temperature of polyreaction approaches the boiling point of mixed solvent.
In step (2), preferably, the concentration range of described ring master metal part in mixed solvent is 0.1 ~ 0.2mol/L.The ratio that encircles the amount of substance of master metal part and the volume of mixed solvent is 0.1 ~ 0.2mol/L.
In step (3), the amount ratio of described chlorine bridge dipolymer and methyl ethyl diketone is 1mol:(2～4) L, preferable amount is than being 1mol:4L, in reaction, the consumption of methyl ethyl diketone is excessive, little on reacting impact itself, and the consumption of methyl ethyl diketone is larger, be beneficial to and while by volume taking, reduce error.
In step (3), preferably, described alkali is sodium carbonate or salt of wormwood, but is not limited to this.Preferably, the mol ratio of described alkali and chlorine bridge dipolymer is (6 ~ 10): 1.
In step (3), the temperature of described ligand exchange reaction is 62 ~ 100 DEG C, and the reaction times is 6 ~ 12h, and temperature of reaction is higher, and the reaction times is shorter.
In step (3), preferably, described solvent is cellosolvo, 2-methyl cellosolve, trichloromethane or 1,2-ethylene dichloride, but is not limited to this.
In step (3), preferably, after described ligand exchange reaction completes, carry out separating-purifying, obtain ruddiness organic electromechanical phosphorescent material iridium metal complex, the concrete operations of described separating-purifying are: reaction mixture is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent are elutriant, and surplus materials is carried out to silica gel column chromatography, and chromatographic solution is revolved to steaming, dry, obtain ruddiness organic electromechanical phosphorescent material metal iridium complex.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, ruddiness organic electromechanical phosphorescent material metal iridium complex adulterates in described luminescent layer, described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl.
Preferably, R is hydrogen or methyl, and the position of substitution when R is methyl comprises 4,5 or 6 of phenyl, and described ring master metal part is the compound with following structural formula:
The material of the luminescent layer of described organic electroluminescence device is that described ruddiness organic electromechanical phosphorescent material metal iridium complex is doped to the mixing material forming in material of main part.Described material of main part can be but be not limited to N, two carbazyl-4 of N'-, 4'-dipyridyl (CBP).
The invention provides a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex and preparation method thereof and organic electroluminescence device, described ruddiness organic electromechanical phosphorescent material metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines and derivative thereof as ring metal master part, taking methyl ethyl diketone as assistant ligand, on the one hand, phenoxy group group on phthalazines ring is conducive to increase the solvability of title complex, and phenoxy group group volume is larger, sterically hindered larger, be beneficial to the interaction reducing between complex molecule, be conducive to luminous, and this title complex is special-shaped title complex, with the comparison of equal type title complex, there is synthetic difficulty little, the easier advantage of purifying, and there is equally excellent luminescent properties.On the other hand, different positions on phenyl ring is introduced a methyl, the red light-emitting wavelength of adjustable metal iridium complex also reduces the self-quenching probability of triplet exciton, thereby transmitting high purity ruddiness, and the material of main part in described metal iridium complex and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare ruddiness or white-light phosphor photoelectricity electroluminescence device, make organic electroluminescence device there is good electroluminescent properties.
In addition, the preparation method of described ruddiness organic electromechanical phosphorescent material metal iridium complex is simple, and technique is easy to control, and is beneficial to the suitability for industrialized production of organic electroluminescence device, greatly reduces the cost of manufacturing, and has very wide commercialized development prospect.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural formula of the ruddiness organic electromechanical phosphorescent material metal iridium complex of the embodiment of the present invention;
Fig. 2 is the electroluminescent spectrum figure of ruddiness organic electromechanical phosphorescent material metal iridium complex in the embodiment of the present invention 1;
Fig. 3 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.
Refer to Fig. 1, the invention provides a kind of ruddiness organic electromechanical phosphorescent material metal iridium complex, described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl.
Preferably, R is hydrogen or methyl, and the position of substitution when R is methyl comprises 4,5 or 6 of phenyl, and described ring master metal part is the compound with following structural formula:
Embodiment 1
A kind of ruddiness organic electromechanical phosphorescent material metal iridium complex two [1-phenoxy group-4-phenyl phthalazines-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, comprises the steps:
(1) ring master metal ligand 1-phenoxy group-4-phenyl phthalazines is synthetic, and reaction formula is:
Concrete operations are:
The compd A that provides respectively following structural formula to represent, i.e. 1-phenoxy group-4-chlorine phthalazines, and compound B-11, i.e. phenylo boric acid:
Under nitrogen protection, by 1.03g (4.0mmol) compd A, 0.59g (4.8mmol) compound B-11 and the mixing of 0.23g (0.20mmol) tetrakis triphenylphosphine palladium are dissolved in 15mL DMF, drip the wet chemical that 15mL concentration is 1mol/L, be heated to 100 DEG C of stirring reaction 10h, question response liquid is cooled to after room temperature, by extracted with diethyl ether, separation obtains organic phase, add anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain 0.48g ring master metal ligand 1-phenoxy group-4-phenyl phthalazines, yield is 40.2%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 298.1 (M
+)
Ultimate analysis: C
20h
14n
2o
Theoretical value: C:80.52; H:4.73; N:9.39; O:5.36;
Measured value: C:80.55; H:4.75; N:9.32; O:5.38.
Above data acknowledgement gained material is 1-phenoxy group-4-phenyl phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-phenoxy group-4-phenyl phthalazines, and reaction formula is:
Under nitrogen protection; it is in the cellosolvo of 3:1 and the mixed solvent of water that 0.75g (2.5mmol) 1-phenoxy group-4-phenyl phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in to 15mL volume ratio; under lucifuge condition, be uniformly mixed; be heated to 100 DEG C of back flow reaction 24h; reaction solution filters after being cooled to room temperature; absolute ethanol washing 3 times of gained precipitation; after vacuum-drying, obtaining the main part of 0.41g is the chlorine bridge dipolymer of 1-phenoxy group-4-phenyl phthalazines; yield 49.9%; this product, without further purification, directly drops into next step reaction.
(3) two [1-phenoxy group-4-phenyl phthalazines-N, C of metal iridium complex
2'] (methyl ethyl diketone) close the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.41g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-phenoxy group-4-phenyl phthalazines, the mixing of 1mL methyl ethyl diketone and 0.21g (2mmol) sodium carbonate is dissolved in 25mL2-ethoxy ethanol, be uniformly mixed, be heated to 100 DEG C of thermotonus 6h, reaction solution is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent carry out silica gel column chromatography to surplus materials as elutriant, steam except the solvent in chromatographic solution, dry, obtain the two [1-phenoxy group-4-phenyl phthalazines-N of 0.15g, C
2'] (methyl ethyl diketone) close iridium, yield is 33.9%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 886.2 (M
+)
Ultimate analysis: C
45h
33irN
4o
4
Theoretical value: C:61.00; H:3.75; Ir:21.70; N:6.32; O:7.22;
Measured value: C:61.06; H:3.71; Ir:21.65; N:6.37; O:7.21.
Above data acknowledgement gained material is two [1-phenoxy group-4-phenyl phthalazines-N, C
2'] (methyl ethyl diketone) close iridium.
Gained metal iridium complex is dissolved in to methylene dichloride (CH
2cl
2) to obtain concentration be 1 × 10
-5the solution of mol/L, taking methylene dichloride as reference, scanning ultra-violet absorption spectrum, the maximum absorption wavelength that obtains metal iridium complex is 400nm, then tests the luminescent spectrum of gained metal iridium complex, maximum emission wavelength and chromaticity coordinates CIE
x,y, method is as follows:
At 298K, the concentration that scans metal iridium complex with spectrophotofluorometer is 1 × 10
-5the CH of mol/L
2cl
2the luminescent spectrum of solution, excitation wavelength adopts 400nm, and scanning wavelength scope is 400 ~ 800nm, is sent out emission wavelength and chromaticity coordinates most according to luminescent spectrum.
Two [1-phenoxy group-4-phenyl phthalazines-N, C prepared by test the present embodiment
2'] (methyl ethyl diketone) close the luminescent spectrum of iridium, as shown in Figure 2, obtaining maximum emission wavelength is 626nm, chromaticity coordinates CIE
x,y=(0.70,0.30).Known gained metal iridium complex sends saturated red, can be used as ruddiness electroluminescent material and is widely used in being prepared with organic electroluminescence devices.
The phosphorescence quantum yield of another test gained metal iridium complex under solution state
, phosphorescence quantum yield is to weigh the parameter of the characteristics of luminescence of material own, measuring method is:
(1), in order to eliminate solvent and the deoxidation treatment tests affect to title complex quantum yield, adopt face formula-tri-(2-phenylpyridine) iridium (fac-Ir (ppy)
3) make reference material, distinguish preparing metal complex of iridium and fac-Ir (ppy)
3dichloromethane solution, it is 1 × 10 that concentration is
-6mol/L;
(2) scan respectively fac-Ir (ppy)
3and the methylene dichloride (CH of metal iridium complex
2cl
2) ultra-violet absorption spectrum of solution, obtain the absorbancy (< 0.05) at 400nm place, be respectively A
x, A
r;
(3) adopt spectrophotofluorometer to scan respectively the luminescent spectrum of two kinds of solution, excitation wavelength is 400nm, and scanning wavelength scope is 400 ~ 800nm, is calculated the phosphorescence integrated intensity of metal iridium complex and reference material by luminescent spectrum, is respectively F
x, F
r;
(4) fac-Ir (ppy)
3quantum yield in methylene dichloride
be 0.40, because solution is extremely rare, metal iridium complex and fac-Ir (ppy)
3the refractive index nx of dichloromethane solution, nr all calculates with the refractive index of dichloromethane solution;
(5) above data substitution formula is calculated to phosphorescence quantum yield
Obtain two [1-phenoxy group-4-phenyl phthalazines-N, C by above method test
2'] (methyl ethyl diketone) close the Φ of iridium
pL=0.28, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 2
A kind of ruddiness organic electromechanical phosphorescent material metal iridium complex two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, comprises the steps:
(1) ring master metal ligand 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines is synthetic, and reaction formula is:
Concrete operations are:
The compd A that provides respectively following structural formula to represent, i.e. 1-phenoxy group-4-chlorine phthalazines, and compd B 2, i.e. 2-methylphenylboronic acid:
Under nitrogen protection, by 1.03g (4.0mmol) compd A, 0.81g (6mmol) compd B 2 and the mixing of 0.18g (0.16mmol) tetrakis triphenylphosphine palladium are dissolved in 12mL toluene, drip the aqueous sodium carbonate that 8mL concentration is 1mol/L, be heated to 80 DEG C of stirring reaction 12h, question response liquid is cooled to after room temperature, by extracted with diethyl ether, separation obtains organic phase, add anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain 0.38g ring master metal ligand 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines, yield is 30.4%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 312.1 (M+)
Ultimate analysis: C
21h
16n
2o
Theoretical value: C:80.75; H:5.16; N:8.97; O:5.12;
Measured value: C:80.71; H:5.22; N:8.92; O:5.15.
Above data acknowledgement gained material is 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection, 0.94g (3mmol) 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in cellosolvo/water mixed solvent that 30mL volume ratio is 3:1, under lucifuge condition, be uniformly mixed, be heated to 100 DEG C of back flow reaction 24h, reaction solution filters after being cooled to room temperature, absolute ethanol washing 3 times of gained precipitation, after vacuum-drying, obtaining the main part of 0.34g is the chlorine bridge dipolymer of 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines, yield is 40.0%, this product is without further purification, directly drop into next step reaction.
(3) two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N, C of metal iridium complex
2'] (methyl ethyl diketone) close the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.43g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-phenoxy group-4-(2'-aminomethyl phenyl) phthalazines, the mixing of 1mL methyl ethyl diketone and 0.34g (2.5mmol) salt of wormwood is dissolved in 20mL2-methyl cellosolve, be uniformly mixed, be heated to 90 DEG C of reaction 8h, reaction solution is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent carry out silica gel column chromatography to surplus materials as elutriant, steam except the solvent in chromatographic solution, dry, obtain two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N of 0.09g, C
2'] (methyl ethyl diketone) close iridium, yield is 19.7%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 914.2 (M
+)
Ultimate analysis: C
47h
37irN
4o
4
Theoretical value: C:61.76; H:4.08; Ir:21.03; N:6.13; O:7.00;
Measured value: C:61.72; H:4.11; Ir:21.07; N:6.11; O:6.99.
Above data acknowledgement gained material is two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium.
According to testing method in the same manner as in Example 1, test obtains two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) maximum emission wavelength of closing iridium is 631nm, chromaticity coordinates CIEx, y=(0.71,29).Known gained metal iridium complex sends saturated red, can be used as ruddiness electroluminescent material and is widely used in being prepared with organic electroluminescence devices.Record two [1-phenoxy group-4-(6'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] (methyl ethyl diketone) close the Φ of iridium
pL=0.18, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 3
A kind of ruddiness organic electromechanical phosphorescent material metal iridium complex two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, comprises the steps:
(1) ring master metal ligand 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines is synthetic, and reaction formula is:
Concrete operations are:
The compd A that provides respectively following structural formula to represent, i.e. 1-phenoxy group-4-chlorine phthalazines, and compd B 3, i.e. 3-methylphenylboronic acid:
Under nitrogen protection, by 1.03g (4.0mmol) compd A, two (triphenylphosphine) palladiums mixing of 0.81g (6mmol) compd B 3 and 0.09g (0.12mmol) dichloro are dissolved in 20mL DMF, drip the wet chemical that 12mL concentration is 1mol/L, be heated to 90 DEG C of stirring reaction 15h, question response liquid is cooled to after room temperature, by extracted with diethyl ether, separation obtains organic phase, add anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain 0.41g ring master metal ligand 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines, yield is 32.8%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 312.1 (M
+)
Ultimate analysis: C
21h
16n
2o
Theoretical value: C:80.75; H:5.16; N:8.97; O:5.12;
Measured value: C:80.70; H:5.25; N:8.91; O:5.14.
Above data acknowledgement gained material is 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection, it is in the cellosolvo of 3:1 and the mixed solvent of water that 0.69g (2.2mmol) 1-phenoxy group-4-(3'-Phenoxyphenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in to 20mL volume ratio, under lucifuge condition, be uniformly mixed, be heated to 100 DEG C of back flow reaction 24h, reaction solution filters after being cooled to room temperature, absolute ethanol washing 3 times of gained precipitation, after vacuum-drying, obtaining the main part of 0.36g is the chlorine bridge dipolymer of 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines, yield is 42.3%, this product is without further purification, directly drop into next step reaction.
(3) two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C of metal iridium complex
2'] (methyl ethyl diketone) close the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.43g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-phenoxy group-4-(3'-aminomethyl phenyl) phthalazines, the mixing of 1mL methyl ethyl diketone and 0.16g (1.5mmol) sodium carbonate is dissolved in 15mL1, in 2-ethylene dichloride, be uniformly mixed, be heated to 84 DEG C of back flow reaction 8h, reaction solution is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent carry out silica gel column chromatography to surplus materials as elutriant, steam except the solvent in chromatographic solution, dry, obtain two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N of 0.10g, C
2'] (methyl ethyl diketone) close iridium, yield is 21.9%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 914.2 (M+)
Ultimate analysis: C
47h
37irN
4o
4
Theoretical value: C:61.76; H:4.08; Ir:21.03; N:6.13; O:7.00;
Measured value: C:61.71; H:4.13; Ir:21.05; N:6.10; O:7.01.
Above data acknowledgement gained material is two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium.
According to testing method in the same manner as in Example 1, test obtains two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) maximum emission wavelength of closing iridium is 622nm, chromaticity coordinates CIE
x,y=(0.69,0.29).Known gained metal iridium complex sends saturated red, can be used as ruddiness electroluminescent material and is widely used in being prepared with organic electroluminescence devices.Record two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] (methyl ethyl diketone) close the Φ of iridium
pL=0.12, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 4
A kind of ruddiness organic electromechanical phosphorescent material metal iridium complex two [1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium, as shown in following structural formula:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material metal iridium complex, comprises the steps:
(1) ring master metal ligand 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines is synthetic, and reaction formula is:
Concrete operations are:
The compd A that provides respectively following structural formula to represent, i.e. 1-phenoxy group-4-chlorine phthalazines, and compd B 4, i.e. 4-methylphenylboronic acid:
Under nitrogen protection, by 1.03g (4.0mmol) compd A, two (triphenylphosphine) palladiums mixing of 1.09g (8mmol) compd B 4 and 0.14g (0.20mmol) dichloro are dissolved in 30mL toluene, drip the aqueous sodium carbonate that 10mL concentration is 2mol/L, be heated to 100 DEG C of stirring reaction 8h, question response liquid is cooled to after room temperature, by extracted with diethyl ether, separation obtains organic phase, add anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain 0.45g ring master metal ligand 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines, yield is 36.0%, Structural Identification data are as follows:
Mass spectrum (MS m/z): 312.1 (M+)
Ultimate analysis: C
21h
16n
2o
Theoretical value: C:80.75; H:5.16; N:8.97; O:5.12;
Measured value: C:80.68; H:5.20; N:8.99; O:5.13.
Above data acknowledgement gained material is 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection, 0.87g (2.8mmol) 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in cellosolvo/water mixed solvent that 14mL volume ratio is 3:1, under lucifuge condition, be uniformly mixed, be heated to 100 DEG C of back flow reaction 24h, reaction solution filters after being cooled to room temperature, absolute ethanol washing 3 times of gained precipitation, after vacuum-drying, obtaining the main part of 0.39g is the chlorine bridge dipolymer of 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines, yield is 45.9%, this product is without further purification, directly drop into next step reaction.
(3) two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C of metal iridium complex
2'] (methyl ethyl diketone) close the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.43g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-phenoxy group-4-(4'-aminomethyl phenyl) phthalazines, the mixing of 1mL methyl ethyl diketone and 0.21g (1.5mmol) salt of wormwood is dissolved in 20mL trichloromethane, be uniformly mixed, be heated to 62 DEG C of back flow reaction 12h, reaction solution is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent carry out silica gel column chromatography to surplus materials as elutriant, steam except the solvent in chromatographic solution, dry, obtain two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N of 0.12g, C
2'] (methyl ethyl diketone) close iridium, yield is 26.2%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 914.2 (M
+)
Ultimate analysis: C
47h
37irN
4o
4
Theoretical value: C:61.76; H:4.08; Ir:21.03; N:6.13; O:7.00;
Measured value: C:61.69; H:4.15; Ir:21.08; N:6.11; O:6.97.
Above data acknowledgement gained material is two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) close iridium.
According to testing method in the same manner as in Example 1, test obtains two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] (methyl ethyl diketone) maximum emission wavelength of closing iridium is 620nm, chromaticity coordinates CIE
x,y=(0.69,0.31).Known gained metal iridium complex sends saturated red, can be used as ruddiness electroluminescent material and is widely used in being prepared with organic electroluminescence devices.Record two [1-phenoxy group-4-(5'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] (methyl ethyl diketone) close the Φ of iridium
pL=0.11, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 5
The metal iridium complex making using embodiment is prepared with organic electroluminescence devices as luminescent layer doping guest materials, as shown in Figure 3, the structure of this device can be expressed as structure: ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt% metal iridium complex (30nm)/BCP (10nm)/Alq
3(20nm)/Liq (2nm)/Al (100nm), wherein, CBP:8wt% metal iridium complex represents that the luminescent layer material of organic electroluminescence device is taking CBP as main body, the mixing material of the metal iridium complex of the embodiment 1 of doping 8wt%.
The preparation method of above-mentioned organic electroluminescence device is: on glass-based plate, deposit thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10 Ω/mouths is as transparent anode 301, adopt the method for vacuum evaporation, on anode 301, preparing thickness is 4 of 60nm, 4', 4 " tri-(N-(naphthalene-2-yl) N-phenyl amino) triphenylamine (2-TNATA) is as hole injection layer 302, on hole injection layer, prepare the N that thickness is 20nm, N '-bis-(1-naphthyl)-N, N '-phenylbenzene benzidine (NPB) is as hole transmission layer 303, evaporation N on hole transmission layer 303, two carbazyl-4 of N'-, the mixture of metal iridium complex prepared by 4'-dipyridyl (CBP) and the embodiment of the present invention, obtaining thickness is 30nm luminescent layer 304, on luminescent layer 304, evaporation thickness is 10nm 2 successively, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene (BCP) is as hole blocking layer 305, thickness is three (oxine) aluminium (Alq of 20nm
3) the oxine lithium (Liq) that is 2nm as electron transfer layer 306 and thickness is as electron buffer layer 307, the condition of above vacuum evaporation is: evaporation pressure is 2 × 10
-3~ 5 × 10
-5pa, the evaporation speed of organic materials is 0.1 ~ 1nm/s, and the evaporation speed of metal and metallic compound is 1 ~ 10nm/s, and equipment is high vacuum coating system (scientific instrument development center, Shenyang company limited), finally in electron buffer layer 307, adopt the metal A l that vacuum plating techniques of deposition thickness is 100nm, as negative electrode 308, obtain organic electroluminescence device.The structure of organic electroluminescence device is not limited to this.
Prepare as stated above organic electroluminescence device with metal iridium complex prepared by embodiment 1 and embodiment 2 respectively, obtain device 1 and device 2.
The electroluminescent properties of test component 1 and device 2 respectively, method is as follows:
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. ocean optics Ocean Optics, with the Keithley2400 test electric property of Keithley company of the U.S., by CS-100A colourimeter test brightness and the colourity of Japanese Konica Minolta company.
The electroluminescent spectrum of test component 1 under 10V voltage drives, obtaining maximum emission wavelength is 625nm, chrominance C IEx, y=(0.70,0.30), luminous efficiency is 7.4lm/W; The electroluminescent spectrum of test component 2 under 10V voltage drives, obtaining maximum emission wavelength is 630nm, chrominance C IEx, y=(0.71,0.29), luminous efficiency is 6.3lm/W.The chromaticity coordinates that shows the device that the comprises metal iridium complex of the present invention redness that is near the mark, purity of color, more than 98%, can meet the requirement of panchromatic demonstration to red display, and device has higher luminous efficiency simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments 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. a ruddiness organic electromechanical phosphorescent material metal iridium complex, is characterized in that: described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
R is hydrogen or methyl, and described ring master metal part is the compound with following structural formula:
2. a preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, comprises the following steps:
(1) compd A and the compd B that provide respectively following structural formula to represent:
Wherein, R is hydrogen or methyl, and compd B is
Under the condition of protection of inert gas and catalyzer, alkaline solution and organic solvent, compd A and compd B are carried out to Suzuki linked reaction in 1:1 ~ 1:2 mixing post-heating to 80 ~ 100 DEG C in molar ratio, the time is 8 ~ 15h, obtains encircling master metal part;
(2) under protection of inert gas, by the ring master metal part obtaining in step (1) and three hydration iridous chlorides in molar ratio 2.2:1 ~ 3:1 after mixing, add in the mixed solvent of cellosolvo and water and carry out polyreaction, obtain chlorine bridge dipolymer;
(3) under protection of inert gas, chlorine bridge dipolymer, methyl ethyl diketone and alkali in step (2) carry out ligand exchange reaction in solvent, obtain ruddiness organic electromechanical phosphorescent material metal iridium complex, the amount ratio of described chlorine bridge dipolymer and methyl ethyl diketone is 1mol:(2～4) L, the temperature of ligand exchange reaction is 62 ~ 100 DEG C, and the reaction times is 6 ~ 12h;
Described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl, and described ring master metal part is the compound with following structural formula:
3. preparation method as claimed in claim 2, is characterized in that, in step (1), described catalyzer is that four (triphenyl phosphorus) close palladium or two (triphenylphosphine) palladiums of dichloro, and the consumption of described catalyzer is 3 ~ 5% of compd A mole dosage.
4. preparation method as claimed in claim 2, it is characterized in that, in step (1), described alkaline solution is sodium carbonate or wet chemical, the concentration of alkaline solution is 1～2mol/L, and the consumption of alkaline solution is 2 ~ 5 times of calculating of compd A mole dosage according to the mole dosage of solute wherein.
5. preparation method as claimed in claim 2, is characterized in that, in step (1), after described Suzuki linked reaction completes, carry out separating-purifying, obtain encircling master metal part, being operating as of described separating-purifying: question response liquid cooling is to room temperature, extraction adds diethyl ether, obtain organic phase, with anhydrous magnesium sulfate drying, filter, revolve to steam and remove ether solvent, obtain crude product, crude product is carried out to recrystallization with methyl alcohol, obtain encircling master metal part.
6. preparation method as claimed in claim 2, it is characterized in that, in step (2), in the mixed solvent of described cellosolvo and water, the volume ratio of cellosolvo and water is 3:1, and the concentration of described ring master metal part in mixed solvent is 0.1 ~ 0.2mol/L.
7. preparation method as claimed in claim 2, is characterized in that, in step (3), described alkali is sodium carbonate or salt of wormwood, and the mol ratio of described alkali and chlorine bridge dipolymer is (6 ~ 10): 1.
8. preparation method as claimed in claim 2, is characterized in that, in step (3), described solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, cellosolvo or 2-methoxyl group methyl alcohol.
9. preparation method as claimed in claim 2, it is characterized in that, in step (3), after completing, described ligand exchange reaction carries out separating-purifying, obtain ruddiness organic electromechanical phosphorescent material iridium metal complex, the concrete operations of described separating-purifying are: reaction mixture is cooled to after room temperature, remove solvent under reduced pressure, normal hexane taking volume ratio as 6:1 and methylene dichloride mixed solvent are elutriant, surplus materials is carried out to silica gel column chromatography, chromatographic solution is revolved to steaming, dry, obtain ruddiness organic electromechanical phosphorescent material metal iridium complex.
10. an organic electroluminescence device, it is characterized in that, comprise anode, functional layer, luminescent layer and negative electrode, ruddiness organic electromechanical phosphorescent material metal iridium complex adulterates in described luminescent layer, described metal iridium complex is taking 1-phenoxy group-4-phenyl phthalazines or derivatives thereof as ring master metal part, taking methyl ethyl diketone as assistant ligand, structural formula as the formula (1):
Wherein, R is hydrogen or methyl, and described ring master metal part is the compound with following structural formula:
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| KR20120050557A (en) * | 2010-11-11 | 2012-05-21 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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| CN102180909A (en) * | 2011-03-18 | 2011-09-14 | 南京邮电大学 | Iridium complex phosphor material taking phthalazine derivative as ligand and preparation method thereof |
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