CN103965889A - Red light organic electrophosphorescence material metal iridium coordination compound and preparation method thereof, and organic electroluminescent device - Google Patents
Red light organic electrophosphorescence material metal iridium coordination compound and preparation method thereof, and organic electroluminescent device Download PDFInfo
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- CN103965889A CN103965889A CN201310037767.7A CN201310037767A CN103965889A CN 103965889 A CN103965889 A CN 103965889A CN 201310037767 A CN201310037767 A CN 201310037767A CN 103965889 A CN103965889 A CN 103965889A
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- PYWDJZPORKXUOZ-UHFFFAOYSA-N CC1(C)c(cc(C)cc2)c2C2=C(C=C)C(C=C)=C(C)[N-][NH+]2C1Cl Chemical compound CC1(C)c(cc(C)cc2)c2C2=C(C=C)C(C=C)=C(C)[N-][NH+]2C1Cl PYWDJZPORKXUOZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a red light organic electrophosphorescence material metal iridium coordination compound, which has a structure formula represented by a formula (1), wherein R is hydrogen or methyl. The preparation method comprises that: a Suzuki coupling reaction is performed to prepare a ring metal ligand, the ring metal ligand and IrCl3.3H2O are subjected to a polymerization reaction in a 2-ethoxyethanol and water mixed solvent to obtain a chloro-bridge dimer, and the chloro-bridge dimer and the ring metal ligand are subjected to a ligand exchange reaction to obtain the red light organic electrophosphorescence material metal iridium coordination compound. According to the present invention, 1-methyl-4-phenyl phthalazine or a derivative thereof is adopted as the ring metal ligand to synthesize to obtain the material, wherein the emission wavelength can be adjusted so as to obtain the red light near the standard red color; and the organic electroluminescent device prepared from the material can emit high purity red light, the luminescence efficiency is high, and the preparation method is simple 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 to take 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%, and the phosphorescence that how to make full use of residue 75% is realized the hot research direction that higher luminous efficiency becomes 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 the quantum yield that very high emitted energy improves 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 be take 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 be take 1-methyl 4-phenyl phthalazines or derivatives thereof and is obtained as cyclic metal complexes is synthetic, and the method for introducing methyl on the different C by phenyl ring in part realizes the adjusting of glow color, obtain the 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, it is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, structural formula as the formula (1):
Wherein, R is hydrogen or methyl.
Wherein, preferably, the position of substitution when R is methyl comprises 4,5 or 6 of phenyl, and described cyclic metal complexes is the compound with following structural formula:
It is cyclic metal complexes agent structure that ruddiness organic electromechanical phosphorescent material metal iridium complex of the present invention be take 1-methyl 4-phenyl phthalazines or derivatives thereof, can introduce methyl at the different positions of phenyl ring, make metal iridium complex there is suitable red light-emitting wavelength, methyl can produce certain space steric effect simultaneously, reduce the direct effect between atoms metal, 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, thereby the excitation energy of molecule is difficult for discharging with heat energy form because of vibration, and be beneficial to the coplanarity that increases molecule, thereby the mobility of electronics in increase molecule, all be beneficial to the generation of phosphorescence, methyl on phenyl ring may make emission wavelength red shift on the other hand, be beneficial to the ruddiness that obtains high color purity, can make the HOMO energy level of title complex decline simultaneously, be conducive to the injection in hole, thereby 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 catalyzer, alkaline solution and organic solvent, compd A and compd B 1:1 ~ 1:2 mixing in molar ratio post-heating are carried out to Suzuki linked reaction, obtain cyclic metal complexes, the temperature of described Suzuki linked reaction is 80 ~ 100 ℃, reaction times is 5 ~ 10h, and reaction formula is:
(2) cyclic metal complexes obtaining in step (1) and three hydration iridous chlorides are carried out to polyreaction for 2:1 ~ 3:1 adds after mixing in the mixed solvent of cellosolvo and water in molar ratio, obtain chlorine bridge dipolymer, reaction formula is:
(3) under protection of inert gas; chlorine bridge dipolymer in step (2), the cyclic metal complexes of step (1) and alkali carry out ligand exchange reaction in solvent; obtain ruddiness organic electromechanical phosphorescent material metal iridium complex; the mol ratio of described chlorine bridge dipolymer and cyclic metal complexes is 1:2 ~ 1:4; temperature of reaction is 40～135 ℃; time is 5 ~ 10h, and reaction formula is:
It is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, 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 cyclic metal complexes 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 1 ~ 5% of compd A mole dosage.
In step (1), the aqueous solution that described alkaline solution is alkaline 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 cyclic metal complexes, 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, with methyl alcohol, crude product is carried out to recrystallization, obtain cyclic metal complexes.
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 80 ~ 100 ℃; back flow reaction 5 ~ 10h, obtains cyclic metal complexes thing 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 ℃, 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 cyclic metal complexes in mixed solvent is 0.1 ~ 0.2mol/L.The ratio that is the amount of substance of cyclic metal complexes and the volume of mixed solvent is 0.1 ~ 0.2mol/L.
In step (3), preferably, described alkali is sodium carbonate, salt of wormwood, sodium methylate, sodium ethylate or sodium hydroxide.Preferably, the consumption of described chlorine bridge dipolymer and the mol ratio of alkali are 1:8 ~ 1: 12.
In step (3), described ligand exchange reaction is to be the back flow reaction of carrying out at 40～135 ℃ in temperature,, the reaction times is 5 ~ 10h, the temperature of reaction approaches the boiling point of mixed solvent.
In step (3), preferably, described solvent is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, cellosolvo or 2-methoxyl group methyl alcohol.
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, the normal hexane that the volume ratio of take is 3:1 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, it is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, 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 cyclic metal complexes 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 be take 1-methyl 4-phenyl phthalazines as cyclic metal complexes agent structure, and the 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, on the other hand, 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.
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 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, it is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, 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 cyclic metal complexes is the compound with following structural formula:
Embodiment 1
Ruddiness organic electromechanical phosphorescent material metal iridium complex three [1-methyl 4-phenyl phthalazines-N, C
2'] 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) cyclic metal complexes 1-methyl 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-methyl-4-chlorine phthalazines, and compound B-11, i.e. phenylo boric acid:
Under nitrogen protection; 0.72g (4.0mmol) compd A, 0.59g (4.8mmol) compound B-11 and 0.23g (0.20mmol) tetrakis triphenylphosphine palladium are mixed and be dissolved in 15mL DMF; drip the wet chemical that 15mL concentration is 1mol/L; be heated to 80 ℃ 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; with methyl alcohol, crude product is carried out to recrystallization, obtain 0.44g cyclic metal complexes 1-methyl 4-phenyl phthalazines, yield is 49.9%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 220.1 (M
+);
Ultimate analysis: C
15h
12n
2
Theoretical value: C:81.79; H:5.49; N:12.72;
Measured value: C:81.72; H:5.55; N:12.73.
Above data acknowledgement gained material is 1-methyl 4-phenyl phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-methyl 4-phenyl phthalazines, and reaction formula is:
Under lucifuge and nitrogen protection condition; 0.55g (2.5mmol) 1-methyl 4-phenyl phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in the mixed solvent of 12mL2-ethoxy ethanol and the formation of 4ml distilled water; be uniformly mixed; be heated to 100 ℃ 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 0.51g is the chlorine bridge dipolymer of 1-methyl 4-phenyl phthalazines; yield is 76.6%; this product, without further purification, directly drops into next step reaction.
(3) title complex three [1-methyl 4-phenyl phthalazines-N, C
2'] closing the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.33g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-methyl 4-phenyl phthalazines, 1-methyl 4-phenyl phthalazines prepared by 0.22g (1mmol) step (1) and the mixing of 0.21g (2mmol) sodium carbonate are dissolved in 15mL methylene dichloride, be uniformly mixed, be heated to 40 ℃ of back flow reaction 10h, reaction solution is cooled to after room temperature, remove methylene dichloride under reduced pressure, the normal hexane that the volume ratio of take is 3:1 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 0.13g tri-[1-methyl 4-phenyl phthalazines-N, C
2'] closing iridium, yield is 30.6%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 850.2 (M
+);
Ultimate analysis: C
45h
33irN
6
Theoretical value: C:63.59; H:3.91; Ir:22.61; N:9.89;
Measured value: C:63.53; H:3.98; Ir:22.64; N:9.85.
Above data acknowledgement gained material is three [1-methyl 4-phenyl phthalazines-N, C
2'] 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, take methylene dichloride as reference, scanning ultra-violet absorption spectrum, and 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, by the concentration of spectrophotofluorometer scanning metal iridium complex, be 1 * 10
-5the CH of mol/L
2cl
2the luminescent spectrum of solution, excitation wavelength adopts 400nm, and scanning wavelength scope is 400 ~ 800nm, according to luminescent spectrum, obtains sending out most emission wavelength and chromaticity coordinates.
Three [1-methyl 4-phenyl phthalazines-N, C prepared by test the present embodiment
2'] close the luminescent spectrum of iridium, as shown in Figure 2, obtaining maximum emission wavelength is 615nm, chromaticity coordinates CIE
x,y=(0.68,0.32).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, and 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
By above method test, obtain three [1-methyl 4-phenyl phthalazines-N, C
2'] close the Φ of iridium
pL=0.25, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 2
Ruddiness organic electromechanical phosphorescent material metal iridium complex three [1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] 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) cyclic metal complexes 1-methyl-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-methyl-4-chlorine phthalazines, and compd B 2, i.e. 2-methylphenylboronic acid:
Under nitrogen protection, by 0.72g (4.0mmol) compd A, two (triphenylphosphine) palladiums mixing of 0.68g (5mmol) compd B 2 and 0.11g (0.16mmol) dichloro are dissolved in 15mL toluene, drip the aqueous sodium carbonate that 10mL concentration is 2mol/L, be heated to 85 ℃ 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, with methyl alcohol, crude product is carried out to recrystallization, obtain 0.31g cyclic metal complexes 1-methyl-4-(2'-aminomethyl phenyl) phthalazines, yield is 33.1%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 234.1 (M
+);
Ultimate analysis: C
16h
14n
2
Theoretical value: C:82.02; H:6.02; N:11.96;
Measured value: C:82.07; H:5.96; N:11.97.
Above data acknowledgement gained material is 1-methyl-4-(2'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-methyl-4-(2'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection; 0.70g (3mmol) 1-methyl-4-(2'-aminomethyl phenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in cellosolvo/water mixed solvent that 20mL volume ratio is 3:1; under lucifuge condition, be uniformly mixed; be heated to 100 ℃ 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 0.38g is the chlorine bridge dipolymer of 1-methyl-4-(2'-aminomethyl phenyl) phthalazines; yield is 54.7%; this product, without further purification, directly drops into next step reaction.
(3) title complex three [1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] closing the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.35g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-methyl-4-(2'-aminomethyl phenyl) phthalazines, 1-methyl-4-prepared by 0.18g (0.75mmol) step (1) (2'-aminomethyl phenyl) phthalazines and the mixing of 0.26g (2.5mmol) sodium carbonate are dissolved in 15mL trichloromethane, be uniformly mixed, be heated to 62 ℃, back flow reaction 8h, reaction solution is cooled to after room temperature, remove trichloromethane under reduced pressure, the normal hexane that the volume ratio of take is 3:1 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 0.10g tri-[1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] closing iridium, yield is 22.4%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 829.3 (M
+);
Ultimate analysis: C
48h
39irN
6
Theoretical value: C:64.63; H:4.41; Ir:21.55; N:9.42;
Measured value: C:64.68; H:4.32; Ir:21.59; N:9.41.
Above data acknowledgement gained material is three [1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C
2'] close iridium.
According to testing method in the same manner as in Example 1, it is 620nm that test obtains the maximum emission wavelength that three [1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C2'] close iridium, chromaticity coordinates CIEx, 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 three [1-methyl-4-(6'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] close the Φ of iridium
pL=0.15, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 3
Ruddiness organic electromechanical phosphorescent material metal iridium complex three [1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] 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) cyclic metal complexes 1-methyl-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-methyl-4-chlorine phthalazines, and compd B 3, i.e. 3-methylphenylboronic acid:
Under nitrogen protection, by 0.72g (4.0mmol) compd A, two (triphenylphosphine) palladiums mixing of 0.65g (4.8mmol) compd B 3 and 0.08g (0.12mmol) dichloro are dissolved in 20mL DMF, drip the wet chemical that 8mL concentration is 1mol/L, be heated to 95 ℃ of stirring reaction 6h, 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, with methyl alcohol, crude product is carried out to recrystallization, obtain 0.37g cyclic metal complexes 1-methyl-4-(3'-aminomethyl phenyl) phthalazines, yield is 39.5%.
Structural Identification data are as follows:
Mass spectrum (MS m/z): 234.1 (M
+);
Ultimate analysis: C
16h
14n
2
Theoretical value: C, 82.02; H, 6.02; N, 11.96;
Measured value: C, 82.10; H, 5.95; N, 11.95.
Above data acknowledgement gained material is 1-methyl-4-(3'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-methyl-4-(3'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection, 0.66g (2.8mmol) 1-methyl-4-(3'-aminomethyl phenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in the mixed solvent of 12mL2-ethoxy ethanol and the formation of 4ml distilled water, under lucifuge condition, be uniformly mixed, be heated to 100 ℃ 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 0.40g is the chlorine bridge dipolymer of 1-methyl-4-(3'-aminomethyl phenyl) phthalazines, yield is 57.6%, this product is without further purification, directly drop into next step reaction.
(3) title complex three [1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] synthetic, reaction formula is:
Under nitrogen protection, main part prepared by 0.35g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-methyl-4-(3'-aminomethyl phenyl) phthalazines, 1-methyl-4-prepared by 0.12g (0.5mmol) step (1) (3'-aminomethyl phenyl) phthalazines and the mixing of 0.31g (2.25mmol) salt of wormwood are dissolved in 15mL methylene dichloride, be uniformly mixed, be heated to 84 ℃ of back flow reaction 6h, reaction solution is cooled to after room temperature, remove methylene dichloride under reduced pressure, the normal hexane that the volume ratio of take is 3:1 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 0.11g tri-[1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] closing iridium, yield is 24.7%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 829.3 (M
+);
Ultimate analysis: C
48h
39irN
6
Theoretical value: C:64.63; H:4.41; Ir:21.55; N:9.42;
Measured value: C:64.55; H:4.47; Ir:21.58; N:9.40.
Above data acknowledgement gained material is that three [1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C2'] close iridium.
According to testing method in the same manner as in Example 1, test obtains three [1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C
2'] the maximum emission wavelength that closes iridium is 611nm, chromaticity coordinates CIE
x,y=(0.66,0.30).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.Record three [1-methyl-4-(5'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] close the Φ of iridium
pL=0.10, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 4
Ruddiness organic electromechanical phosphorescent material metal iridium complex three [1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] 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) cyclic metal complexes 1-methyl-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-methyl-4-chlorine phthalazines, and compd B 4, i.e. 4-methylphenylboronic acid:
Under nitrogen protection, by 0.72g (4.0mmol) compd A, 1.09g (8mmol) compd B 4 and the mixing of 0.05g (0.04mmol) tetrakis triphenylphosphine palladium are dissolved in 20mL toluene, drip the aqueous sodium carbonate that 8mL concentration is 2mol/L, be heated to 100 ℃ of stirring reaction 5h, 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, with methyl alcohol, crude product is carried out to recrystallization, obtain 0.39g cyclic metal complexes 1-methyl-4-(4'-aminomethyl phenyl) phthalazines, yield is 41.6%, Structural Identification data are as follows:
Mass spectrum (MS m/z): 234.1 (M
+),
Ultimate analysis: C
16h
14n
2
Theoretical value: C:82.02; H:6.02; N:11.96;
Measured value: C:82.11; H:5.92; N:11.97;
Above data acknowledgement gained material is 1-methyl-4-(4'-aminomethyl phenyl) phthalazines.
(2) main part is chlorine bridge dipolymer synthetic of 1-methyl-4-(4'-aminomethyl phenyl) phthalazines, and reaction formula is:
Under nitrogen protection; 0.47g (2mmol) 1-methyl-4-(4'-aminomethyl phenyl) phthalazines and 0.35g (1.0mmol) three hydration iridous chlorides are dissolved in cellosolvo/water mixed solvent that 20mL volume ratio is 3:1; under lucifuge condition, be uniformly mixed; be heated to 100 ℃ 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 0.42g is the chlorine bridge dipolymer of 1-methyl-4-(4'-aminomethyl phenyl) phthalazines; yield is 60.5%; this product, without further purification, directly drops into next step reaction.
(3) title complex three [1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] closing the synthetic of iridium, reaction formula is:
Under nitrogen protection, main part prepared by 0.35g (0.25mmol) step (2) is the chlorine bridge dipolymer of 1-methyl-4-(4'-aminomethyl phenyl) phthalazines, 1-methyl-4-prepared by 0.23g (1mmol) step (1) (4'-aminomethyl phenyl) phthalazines and the mixing of 0.41g (3mmol) salt of wormwood are dissolved in 20mL2-ethoxy ethanol, be uniformly mixed, heat 135 ℃ of back flow reaction 5h, reaction solution is cooled to after room temperature, remove cellosolvo under reduced pressure, the normal hexane that the volume ratio of take is 3:1 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 0.12g tri-[1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] closing iridium, yield is 26.9%.
Structural Identification result is as follows:
Mass spectrum (MS m/z): 829.3 (M
+);
Ultimate analysis: C
48h
39irN
6
Theoretical value: C:64.63; H:4.41; Ir:21.55; N:9.42;
Measured value: C:64.70; H:4.35; Ir:21.52; N:9.43.
Above data acknowledgement gained material is three [1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] close iridium.
According to testing method in the same manner as in Example 1, test obtains three [1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C
2'] the maximum emission wavelength that closes iridium is 609nm, chromaticity coordinates CIE
x,y=(0.65,0.33).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 three [1-methyl-4-(4'-aminomethyl phenyl) phthalazines-N, C simultaneously
2'] close the Φ of iridium
pL=0.09, metal iridium complex prepared by visible the present embodiment has higher electroluminescent efficiency.
Embodiment 5
The metal iridium complex that the embodiment of usining makes 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 to take 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.
With the metal iridium complex of embodiment 1 and embodiment 2 preparations, prepare as stated above organic electroluminescence device respectively, obtain device 1 and device 2.
The electroluminescent properties of difference test component 1 and device 2, 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 U.S. Keithley company, 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 618nm, chrominance C IEx, y=(0.68,0.31), luminous efficiency is 7lm/W; The electroluminescent spectrum of test component 2 under 10V voltage drives, obtaining maximum emission wavelength is 622nm, chrominance C IEx, y=(0.69,0.29), luminous efficiency 6 is lm/W.The chromaticity coordinates of the device that shows the to comprise 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 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. a ruddiness organic electromechanical phosphorescent material metal iridium complex, is characterized in that: it is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, structural formula as the formula (1):
Wherein, R is hydrogen or methyl, and described cyclic metal complexes is:
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 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 ℃ in molar ratio, the reaction times is 5 ~ 10h, obtains cyclic metal complexes;
(2) cyclic metal complexes obtaining in step (1) and three hydration iridous chlorides are carried out to polyreaction for 2:1 ~ 3:1 adds after mixing in the mixed solvent of cellosolvo and water in molar ratio, obtain chlorine bridge dipolymer;
(3) under protection of inert gas, chlorine bridge dipolymer in step (2), the cyclic metal complexes of step (1) and alkali carry out ligand exchange reaction in solvent, the mol ratio of chlorine bridge dipolymer and cyclic metal complexes is 1:2 ~ 1:4, temperature of reaction is 40～135 ℃, time is 5 ~ 10h, obtains ruddiness organic electromechanical phosphorescent material metal iridium complex;
It is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, structural formula as the formula (1):
Wherein, R is hydrogen or methyl, and described cyclic metal complexes is:
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 1 ~ 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 cyclic metal complexes, 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, with methyl alcohol, crude product is carried out to recrystallization, obtain cyclic metal complexes.
6. preparation method as claimed in claim 2, it is characterized in that, in step (1), in the mixed solvent of described cellosolvo and water, the volume ratio of cellosolvo and water is 3:1, and the concentration of described cyclic metal complexes 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, salt of wormwood, sodium methylate, sodium ethylate or sodium hydroxide, and the mol ratio of described chlorine bridge dipolymer and alkali is 1:8 ~ 1:12.
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, the normal hexane that the volume ratio of take is 3:1 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, it is cyclic metal complexes that described metal iridium complex be take 1-methyl 4-phenyl phthalazines or derivatives thereof, structural formula as the formula (1):
Wherein, R is hydrogen or methyl, and described cyclic metal complexes is:
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| CN101200635A (en) * | 2007-11-27 | 2008-06-18 | 中山大学 | Phosphorescent iridium complex and organic electroluminescent device thereof |
| 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 |
| US20120004410A1 (en) * | 1999-12-27 | 2012-01-05 | Fujifilm Corporation | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
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|---|---|---|---|---|
| US20120004410A1 (en) * | 1999-12-27 | 2012-01-05 | Fujifilm Corporation | Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex |
| US20060261730A1 (en) * | 2005-05-20 | 2006-11-23 | City University Of Hong Kong | Red-emitting electrophosphorescent devices |
| CN101200635A (en) * | 2007-11-27 | 2008-06-18 | 中山大学 | Phosphorescent iridium complex and organic electroluminescent device thereof |
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