CN101200477A - Compound for preparing organic electromechanical phosphorescent material and preparation method thereof - Google Patents
Compound for preparing organic electromechanical phosphorescent material and preparation method thereof Download PDFInfo
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- CN101200477A CN101200477A CNA2007100445310A CN200710044531A CN101200477A CN 101200477 A CN101200477 A CN 101200477A CN A2007100445310 A CNA2007100445310 A CN A2007100445310A CN 200710044531 A CN200710044531 A CN 200710044531A CN 101200477 A CN101200477 A CN 101200477A
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Abstract
The invention relates to a compound for preparing red electrophosphorescent materials. The invention is characterized in that the compound is a complex of Iridium and arylethenyl quinolie, more specifically a complex of iridium and bis(2-arylethenyl-1-quinoline) and acetylacetone. By introduction of Iridium of heavy atom, the phosphorescence is smoothly emitted, the limitation of the external quantum efficiency at 25 percent is broken and the luminous efficiency is greatly promoted. The complex formed by the organic ligand and Iridium has better chemical stability and thermal stability. The aryl group is connected with quinoline double dipole group by the ethylenic bond, therefore the luminous efficiency is promoted, the wave length is moved to the red area and the luminescence chromaticity is better. The good electronic flow in the molecule causes the material to have the better performance of transfer.
Description
Technical field
The invention belongs to the luminous organic material field, be specifically related to a kind of aromatic ethylene base quinoline that contains and close organic electromechanical phosphorescent material of complex of iridium and preparation method thereof.
Background technology
Organic light emitting display (be Organic Light Emitting Display, be called for short OLED), it belongs to the kind of new emergence on mobile phone screen, MP3, MP4 screen, be described as " dreamlike indicating meter ".The OLED technique of display is different with traditional LCD display mode, need not backlight, adopt extremely thin coating of organic material and glass substrate, when electric current passes through, these organic materialss will be luminous, therefore the OLED screen can be done lighter and thinnerly, and visible angle is bigger, and can significantly save electric energy.
In order to realize the full-color demonstration of OLED, must obtain the luminescent material of excellent property.Present electroluminescent organic material is divided into two kinds of fluorescent material and phosphor materials, wherein phosphor material than fluorescent material owing to broken through the limit of external quantum efficiency 25%, often have higher luminous efficiency, thereby by scientists extensive studies and exploitation.Wherein, metal iridium complex is a class research organic electromechanical phosphorescent material the most widely, because the introducing of heavy metal atom iridium, improved the molecule spin orbit coupling, shortened phosphorescent lifetime, strengthened the ability of the intersystem crossing of molecule, made phosphorescence be able to smooth emission.And, not only can regulate the emission wavelength of molecule by changing the structure of organic ligand in the title complex, can also adjust the fluorescence quantum yield of molecule, thereby obtain the organic electromechanical phosphorescent material of excellent performance.
In order to obtain full-color demonstration, must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.And than green glow and blue light material, the development of red light material relatively lags behind always, is difficult to obtain efficient and all very excellent red light material of chroma.We are by introducing a pair of key in the part aryl quinoline that closes complex of iridium at aryl quinoline, make the emission wavelength red shift of molecule, colourity is tending towards full and closes, the flowability of intramolecularly electronics has been strengthened in the introducing of simultaneously two keys, luminous efficiency is increased, thereby obtained all excellent red phosphorescence material of efficient, colourity.
Summary of the invention
There is the low and not high shortcoming of fullness of shade of luminous efficiency in the red light material of prior art.The object of the present invention is to provide and a kind ofly be applied to organic elctroluminescent device, contain aromatic ethylene base quinoline and close organic electromechanical phosphorescent material of complex of iridium and preparation method thereof.
To achieve the object of the present invention, the technical scheme of employing is:
Be used to prepare the compound of red organic electromechanical phosphorescent material, it closes complex of iridium for aromatic ethylene base quinoline, and general structure is as follows:
Wherein Ar is phenyl, pyridyl, naphthyl, quinolyl, pyrazolyl, thiazolyl, thienyl, pyrryl, phenanthryl, anthryl, N-ethyl carbazole base, 9,9 '-diethyl fluorenyl;
Aromatic ethylene base quinoline closes complex of iridium and specifically comprises following several:
Prepare the method for aforesaid compound, wherein step is as follows:
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
In reactor, add 1 part of 2-chloromethyl quinoline, 5 parts of triethyl-phosphites, logical stirring of inert gas, reflux 3-5 hour complete to raw material reaction, excessive triethyl-phosphite is removed in underpressure distillation then, and standing over night gets 2-(diethyl phosphoric acid)-1-quinoline;
(2) 2-aromatic ethylene base-1-quinoline is synthetic
In reactor, add 1 part of 2-(diethyl phosphoric acid)-1-quinoline, aromatic aldehyde 0.8-1.0 part, aprotic, polar type solvent 50-60 part, catalyzer 3-5 part was stirred 8-12 hour under the room temperature; Remove aprotic, polar type solvent under reduced pressure, add 100ml methyl alcohol again, filtration, respectively with washing, recrystallization is crossed and is got 2-aromatic ethylene base-1-quinoline after post is purified;
Synthesizing of (3) two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closing iridium)
In reactor, add 1 part of iridic compound, 2-aromatic ethylene base-1-quinoline 2-3 part, mixing solutions 20-30 part of organic solvent and water, under the protection of inert gas back flow reaction 20-40 hour, TCL monitor to raw material reaction fully after, cooling, add 100 parts of water, have precipitation to generate, suction filtration gets two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closes iridium);
(4) two (2-aromatic ethylene bases-1-quinoline) close the synthetic of acetyl acetone iridium
In reactor, add 1 part of two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closes iridium), yellow soda ash 3-5 part, 200 parts of alcoholic solvents, 6 parts of methyl ethyl diketones, under the inert gas conditions back flow reaction 24-30 hour complete to raw material reaction, add entry after the cooling product separated out, suction filtration, get crude product, crude product is crossed post and is got solid pure product;
Above-mentioned reactant is molar part.
Method as mentioned above; wherein aromatic aldehyde comprises in the step (2): phenyl aldehyde, 4-formyl radical pyridine, 4-formyl radical quinoline, 4-formyl radical pyrazoles, 4-formyl thiazole, 3-formyl radical thiophene, 3-formyl radical pyrroles, 5-formyl radical phenanthrene, 9-formyl radical anthracene, 3-formyl radical-N-ethyl carbazole, 3-formyl radical 9,9 '-diethyl carbazole.
Method as mentioned above, wherein the non-proton type solvent of step (2) Semi-polarity comprises tetrahydrofuran (THF), toluene, N, dinethylformamide; Catalyzer comprises potassium tert.-butoxide, sodium tert-butoxide, sodium hydride.
Method as mentioned above, wherein iridic compound comprises in the step (3): three hydration iridous chlorides, iridous chloride, hexabromo tripotassium iridium.
Method as mentioned above, wherein:
The organic solvent in the step (3) and the mixing solutions of water comprise: 3: 1 cellosolvo: water mixed solution, 3: 1 2-methyl cellosolve: water mixed solution, 3: 11,2-propylene glycol: water mixed solution, 3: 11,3 butyleneglycols: water mixed solution, 3: 1 2-n-Octanol: water mixed solution, 3: 1 2-glycerol: water mixed solution; Alcoholic solvent in the step (4) comprises: cellosolvo, methyl cellosolve, 1,2-propylene glycol, 1,3 butyleneglycol, 2-n-Octanol, 2-glycerol.
As above-mentioned compound in the application of preparation aspect the red organic electromechanical phosphorescent material.
Because adopted the complex of iridium of said structure, major advantage of the present invention is:
1. introduce heavy atom iridium, make phosphorescence be able to smooth emission, broken through the restriction of external quantum efficiency 25%, luminous efficiency is improved greatly.
2. organic ligand and metal iridium have better chemical stability and thermostability after forming title complex.
3. by ethylene linkage aryl is linked to each other with quinoline quadripole group, its luminous efficiency is improved, red shift of wavelength, luminescent chromaticity is better.
4. because intramolecular electronics good fluidity makes material have better carrier transmission performance.Cost of material is cheap, and reaction is simple, is fit to mass production.
Description of drawings
Fig. 1 is the formula of The compounds of this invention;
Fig. 2 closes the synthesis path of acetyl acetone iridium for two (the 2-styryls-1-quinoline) of embodiment 1;
Fig. 3 closes the synthesis path of acetyl acetone iridium for two (the 2-naphthalene vinyls-1-quinoline) of embodiment 2;
Fig. 4 closes the synthesis path of acetyl acetone iridium for two (the luxuriant and rich with fragrance vinyl of 1--2-quinoline) of embodiment 3;
Fig. 5 closes the synthesis path of acetyl acetone iridium for two [2-(N-ethyl carbazole-3-ethene) bases-1-quinoline] of embodiment 4;
Fig. 6 is the synthesis path that two [2-(9, the 9 '-diethyl fluorenes-3-ethene) bases-1-quinoline] of embodiment 5 close acetyl acetone iridium;
Fig. 7 closes the synthesis path of acetyl acetone iridium for two (the 2-thiofuran ethylene bases-1-quinoline) of embodiment 6.
Embodiment
Following examples are used for that the invention will be further described.Should be appreciated that these embodiment do not cause any restriction to the present invention, the Ar group of general molecular formula (I) can be phenyl, naphthyl, phenanthryl, N-ethyl carbazole base, 9,9 '-diethyl fluorenyl, groups such as thiophene.These all should be included in the spirit scope of the present invention.
In following examples, solvent for use, the catalyzer agent is Chemical Reagent Co., Ltd., Sinopharm Group's commodity, analytical pure AR level; Reaction raw materials and intermediate are then buied by Aldrich company, analytical pure AR level.
Product performance test event and testing tool: absorption spectrum is measured by Hitach 330 ultraviolet-visible absorption spectroscopy instrument; Fluorescence spectrum and fluorescence quantum yield are by Hitach F-4500 type fluorescent spectrophotometer assay.
Embodiment 1: two (2-styryl-1-quinoline) closes the synthesis path of acetyl acetone iridium: (as shown in Figure 2)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
In flask, add 1 part of chloromethyl quinoline of 2-(10mmol), 5 parts of triethyl-phosphites (50mmol), logical nitrogen stirs, reflux 4 hours is complete to raw material reaction, excessive triethyl-phosphite is removed in underpressure distillation then, standing over night gets white 2-(diethyl phosphoric acid)-quinoline, productive rate 70%.
(2) 2-styryl-1-quinoline is synthetic
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), 1 part of phenyl aldehyde (10mmol), tetrahydrofuran THF 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove THF under reduced pressure,, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, must light yellow 2-styryl-1-quinoline after crude product is crossed post and purified, productive rate 35%.
Synthesizing of (3) two (u-chlorine bridge-2-styryl-1-quinoline closing iridium).
In flask, add three hydration iridous chlorides (1 part, 5mmol), (2 parts of 2-styryls-1-quinoline, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, thin-layer chromatography TCL monitor to raw material reaction fully after, cooling, add 200ml water, have precipitation to generate suction filtration, get two (u-chlorine bridge-2-styryl-1-quinoline closes iridium), productive rate 65.2%.
(4) two (2-styryls-1-quinoline) close the synthetic of acetyl acetone iridium.
In flask, add two (u-chlorine bridge-2-styryl-1-quinoline closes iridium) 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 56.5%.
(5) two (2-styryls-1-quinoline) close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=348nm
Fluorescence spectrum λ max=622nm
Fluorescence quantum yield Ф=0.76
Embodiment 2: two (2-naphthalene vinyl-1-quinoline) closes the synthesis path of acetyl acetone iridium: (as shown in Figure 3)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
The synthetic method of 2-(diethyl phosphoric acid)-1-quinoline is identical with embodiment 1.
(2) 2-naphthalene vinyl-1-quinoline is synthetic.
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), 1 part of 1-naphthaldehyde (10mmol), tetrahydrofuran (THF) 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove tetrahydrofuran (THF) under reduced pressure, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, must light yellow 2-naphthalene vinyl-1-quinoline after crude product is crossed post and purified, and productive rate 34%.
Synthesizing of (3) two (u-chlorine bridge-2-naphthalene vinyl-1-quinoline closing iridium).
In flask, add three hydration iridous chlorides (1 part, 5mmol), (2 parts of 2-naphthalene vinyls-1-quinoline, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, TCL monitor to raw material reaction fully after, cooling, add 200 water, have precipitation to generate suction filtration, get two (u-chlorine bridge-2-naphthalene vinyl-1-quinoline closes iridium), productive rate 56.2%.
(4) two (2-naphthalene vinyls-1-quinoline) close the synthetic of acetyl acetone iridium.
In flask, add two (u-chlorine bridge-2-naphthalene vinyl-1-quinoline closes iridium) 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 56.5%.
(5) two (2-naphthalene vinyls-1-quinoline) close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=352nm
Fluorescence spectrum λ max=626nm
Fluorescence quantum yield Ф=0.36
Embodiment 3: two (the luxuriant and rich with fragrance vinyl of 1--2-quinoline) closes the synthesis path of acetyl acetone iridium: (as shown in Figure 4)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
The synthetic method of 2-(diethyl phosphoric acid)-1-quinoline is identical with embodiment 1.
(2) the luxuriant and rich with fragrance vinyl of 2--1-quinoline is synthetic.
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), luxuriant and rich with fragrance 1 part (10mmol) of 9-formyl radical, tetrahydrofuran (THF) 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove tetrahydrofuran (THF) under reduced pressure, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, after crude product is crossed post and is purified light yellow 2-phenanthrene vinyl-1-quinoline, productive rate 23%.
Synthesizing of (3) two (the luxuriant and rich with fragrance vinyl of u-chlorine bridge-2--1-quinoline closing iridium).
In flask, add three hydration iridous chlorides (1 part, 5mmol), (2 parts of the luxuriant and rich with fragrance vinyl of 2--1-quinoline, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, TCL monitor to raw material reaction fully after, cooling, add 200ml water, have precipitation to generate suction filtration, get two (the luxuriant and rich with fragrance vinyl of u-chlorine bridge-2--1-quinoline closes iridium), productive rate 66.2%.
(4) two (the luxuriant and rich with fragrance vinyl of 2--1-quinoline) close the synthetic of acetyl acetone iridium.
In flask, add two (the luxuriant and rich with fragrance vinyl of u-chlorine bridge-2--1-quinoline closes iridium) 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 69.5%.
(5) two (the luxuriant and rich with fragrance vinyl of 2--1-quinoline) close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=363nm
Fluorescence spectrum λ max=631nm
Fluorescence quantum yield Ф=0.078
Embodiment 4: two [2-(N-ethyl carbazole-3-ethene) base-1-quinoline] closes the synthesis path of acetyl acetone iridium: (as shown in Figure 5)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
The synthetic method of 2-(diethyl phosphoric acid)-1-quinoline is identical with embodiment 1.
(2) 2-(N-ethyl carbazole-3-ethene)-Ji-1-quinoline is synthetic.
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), 9-ethyl-1 part of 3-formyl radical carbazole (10mmol), tetrahydrofuran (THF) 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove tetrahydrofuran (THF) under reduced pressure, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, must light yellow 2-(N-ethyl carbazole-3-vinyl)-1-quinoline after crude product is crossed post and purified, and productive rate 21%.
Synthesizing of (3) two [u-chlorine bridge-2-(N-ethyl carbazole-3-vinyl)-1-quinoline closing iridium].
In flask, add three hydration iridous chlorides (1 part, 5mmol), (2 parts of 2-(N-ethyl carbazole-3-vinyl)-1-quinoline, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, TCL monitor to raw material reaction fully after, cooling, add 200ml water, have precipitation to generate suction filtration, get two [u-chlorine bridge-2-(N-ethyl carbazole-3-vinyl)-1-quinoline closes iridium], productive rate 45.2%.
(4) two [2-(N-ethyl carbazole-3-ethene) bases-1-quinoline] close the synthetic of acetyl acetone iridium.
In flask, add two [u-chlorine bridge-2-(N-ethyl carbazole-3-vinyl)-1-quinoline closes iridium] 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 46.5%.
(5) two [2-(N-ethyl carbazole-3-ethene) bases-1-quinoline] close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=366nm
Fluorescence spectrum λ max=633nm
Fluorescence quantum yield Ф=0.76
Embodiment 5: two [2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline] closes the synthesis path of acetyl acetone iridium: (as shown in Figure 6)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
The synthetic method of 2-(diethyl phosphoric acid)-1-quinoline is identical with embodiment 1.
(2) 2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline is synthetic.
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), 2-formyl radical-9,1 part of 9 '-diethyl fluorenes (10mmol), tetrahydrofuran (THF) 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove tetrahydrofuran (THF) under reduced pressure, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, must light yellow 2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline after crude product is crossed post and purified, and productive rate 27%.
Synthesizing of (3) two [u-chlorine bridge-2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline closing iridium].
Adding three hydration iridous chlorides in flask (1 part, 5mmol), 2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline (2 parts, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, TCL monitor to raw material reaction fully after, cooling, add 200ml water, have precipitation to generate, suction filtration gets two [u-chlorine bridge-2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline closes iridium], productive rate 69.5%.
(4) two [2-(9,9 '-diethyl fluorenes-3-ethene) bases-1-quinoline] close the synthetic of acetyl acetone iridium.
In flask, add two [u-chlorine bridge-2-(9,9 '-diethyl fluorenes-3-ethene) base-1-quinoline closes iridium] 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 46.5%.
(5) two [2-(9,9 '-diethyl fluorenes-3-ethene) bases-1-quinoline] close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=363nm
Fluorescence spectrum λ max=635nm
Fluorescence quantum yield Ф=0.42
Embodiment 6: two (2-thiofuran ethylene base-benzoglyoxaline) closes the synthesis path of acetyl acetone iridium: (as shown in Figure 7)
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
The synthetic method of 2-(diethyl phosphoric acid)-1-quinoline is identical with embodiment 1.
(2) 2-thiofuran ethylene base-1-quinoline is synthetic.
In flask, add 2-(diethyl phosphoric acid)-1 part in 1-quinoline (10mmol), 1 part in 3-formyl radical thiophene (10mmol), tetrahydrofuran (THF) 50ml, 3 parts of potassium tert.-butoxides (30mmol) stirred 8 hours under the room temperature.Remove THF under reduced pressure, add 100ml methyl alcohol again, filter, water and methyl alcohol are given a baby a bath on the third day after its birth time respectively, get crude product with the toluene recrystallization again, must light yellow 2-thiofuran ethylene base-1-quinoline after crude product is crossed post and purified, and productive rate 37%.
Synthesizing of (3) two (u-chlorine bridge-2-thiofuran ethylene base-1-quinoline closing iridium).
In flask, add three hydration iridous chlorides (1 part, 5mmol), (2 parts in 2-thiofuran ethylene base-1-quinoline, 10mmol), the mixing solutions of cellosolvo and water (ethoxy ethanol: 200ml water=3: 1), back flow reaction is 40 hours under the nitrogen atmosphere, TCL monitor to raw material reaction fully after, cooling, add 200 water, have precipitation to generate suction filtration, get two (u-chlorine bridge-2-thiofuran ethylene base-1-quinoline closes iridium), productive rate 73.2%.
(4) two (2-thiofuran ethylene bases-1-quinoline) close the synthetic of acetyl acetone iridium.
In flask, add two (u-chlorine bridge-2-thiofuran ethylene base-1-quinoline closes iridium) 1 part (5mmol), 4 parts in yellow soda ash (25mmol), cellosolvo 200ml, 6 parts of methyl ethyl diketones (30mmol), back flow reaction 24 hours is complete to raw material reaction under the nitrogen atmosphere.Add entry after the cooling product is separated out, suction filtration gets crude product.Crude product is crossed post and is got the yellow-green colour solid pure product, productive rate 56.5%.
(5) two (2-thiofuran ethylene bases-1-quinoline) close the spectrum property of acetyl acetone iridium:
Absorption spectrum λ max=358nm
Fluorescence spectrum λ max=629nm
Fluorescence quantum yield Ф=0.073
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (7)
1. be used to prepare the compound of red organic electromechanical phosphorescent material, it is characterized in that general structure is as follows for aromatic ethylene base quinoline closes complex of iridium:
Wherein Ar is phenyl, pyridyl, naphthyl, quinolyl, pyrazolyl, thiazolyl, thienyl, pyrryl, phenanthryl, anthryl, N-ethyl carbazole base, 9,9 '-diethyl fluorenyl;
Aromatic ethylene base quinoline closes complex of iridium and specifically comprises following several:
2. the method for preparing compound as claimed in claim 1 is characterized in that step is as follows:
(1) 2-(diethyl phosphoric acid)-1-quinoline is synthetic:
In reactor, add 1 part of 2-chloromethyl quinoline, 5 parts of triethyl-phosphites, logical stirring of inert gas, reflux 3-5 hour complete to raw material reaction, excessive triethyl-phosphite is removed in underpressure distillation then, and standing over night gets 2-(diethyl phosphoric acid)-1-quinoline;
(2) 2-aromatic ethylene base-1-quinoline is synthetic
In reactor, add 1 part of 2-(diethyl phosphoric acid)-1-quinoline, aromatic aldehyde 0.8-1.0 part, aprotic, polar type solvent 50-60 part, catalyzer 3-5 part was stirred 8-12 hour under the room temperature; Remove aprotic, polar type solvent under reduced pressure, add 100ml methyl alcohol again, filtration, respectively with washing, recrystallization is crossed and is got 2-aromatic ethylene base-1-quinoline after post is purified;
Synthesizing of (3) two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closing iridium)
In reactor, add 1 part of iridic compound, 2-aromatic ethylene base-1-quinoline 2-3 part, mixing solutions 20-30 part of organic solvent and water, under the protection of inert gas back flow reaction 20-40 hour, TCL monitor to raw material reaction fully after, cooling, add 100 parts of water, have precipitation to generate, suction filtration gets two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closes iridium);
(4) two (2-aromatic ethylene bases-1-quinoline) close the synthetic of acetyl acetone iridium
In reactor, add 1 part of two (u-chlorine bridge-2-aromatic ethylene base-1-quinoline closes iridium), yellow soda ash 3-5 part, 200 parts of alcoholic solvents, 6 parts of methyl ethyl diketones, under the inert gas conditions back flow reaction 24-30 hour complete to raw material reaction, add entry after the cooling product separated out, suction filtration, get crude product, crude product is crossed post and is got solid pure product;
Above-mentioned reactant is molar part.
3. as method as described in the claim 2; it is characterized in that aromatic aldehyde comprises in the step (2): phenyl aldehyde, 4-formyl radical pyridine, 4-formyl radical quinoline, 4-formyl radical pyrazoles, 4-formyl thiazole, 3-formyl radical thiophene, 3-formyl radical pyrroles, 5-formyl radical phenanthrene, 9-formyl radical anthracene, 3-formyl radical-N-ethyl carbazole, 3-formyl radical 9,9 '-diethyl carbazole.
4. as method as described in the claim 2, it is characterized in that the non-proton type solvent of step (2) Semi-polarity comprises tetrahydrofuran (THF), toluene, N, dinethylformamide; Catalyzer comprises potassium tert.-butoxide, sodium tert-butoxide, sodium hydride.
5. as method as described in the claim 2, it is characterized in that iridic compound comprises in the step (3): three hydration iridous chlorides, iridous chloride, hexabromo tripotassium iridium.
6. as method as described in the claim 2, it is characterized in that:
The organic solvent in the step (3) and the mixing solutions of water comprise: 3: 1 cellosolvo: water mixed solution, 3: 1 2-methyl cellosolve: water mixed solution, 3: 11,2-propylene glycol: water mixed solution, 3: 11,3 butyleneglycols: water mixed solution, 3: 1 2-n-Octanol: water mixed solution, 3: 1 2-glycerol: water mixed solution;
Alcoholic solvent in the step (4) comprises: cellosolvo, methyl cellosolve, 1,2-propylene glycol, 1,3 butyleneglycol, 2-n-Octanol, 2-glycerol.
7. the application of the described compound of claim 1 aspect the red organic electromechanical phosphorescent material of preparation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441377A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of iridium-containing multi-metal reforming catalyst |
| JP2012528853A (en) * | 2009-06-02 | 2012-11-15 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | Novel organic electroluminescent compound and organic electroluminescent device using the same |
| CN104109125A (en) * | 2014-06-26 | 2014-10-22 | 中山大学 | 4-substituted-2-arylvinyl quinoline derivative, and preparation method and application thereof |
-
2007
- 2007-08-03 CN CNA2007100445310A patent/CN101200477A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012528853A (en) * | 2009-06-02 | 2012-11-15 | ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド | Novel organic electroluminescent compound and organic electroluminescent device using the same |
| CN102441377A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of iridium-containing multi-metal reforming catalyst |
| CN102441377B (en) * | 2010-10-12 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of preparation method containing iridium multimetal reforming catalyst |
| CN104109125A (en) * | 2014-06-26 | 2014-10-22 | 中山大学 | 4-substituted-2-arylvinyl quinoline derivative, and preparation method and application thereof |
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