CN104650150A - Red phosphorescent iridium complex and preparation method thereof, and organic electroluminescence device - Google Patents

Red phosphorescent iridium complex and preparation method thereof, and organic electroluminescence device Download PDF

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CN104650150A
CN104650150A CN201310576974.XA CN201310576974A CN104650150A CN 104650150 A CN104650150 A CN 104650150A CN 201310576974 A CN201310576974 A CN 201310576974A CN 104650150 A CN104650150 A CN 104650150A
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red phosphorescent
metal complex
phosphorescent iridium
structural formula
isoquinoline
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周明杰
王平
张娟娟
冯小明
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

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Abstract

The invention relates to a red phosphorescent iridium complex and a preparation method thereof, and an organic electroluminescence device. The red phosphorescent iridium complex has a structural formula as described in the specification; and in the formula, R is hydrogen or a methyl group. The red phosphorescent iridium complex uses 1-(4'-trifluoroacetylphenyl)isoquinoline as the main structure of a cyclometalated ligand and 2,2,6,6-tetramethyl-3,5-heptadione as an ancillary ligand; an isoquinoline ring can emit light at red bands; the methyl groups on the isoquinoline ring produce different electronic effects at different C positions, thereby realizing emission of red light of different wave lengths, exerting steric hindrance effect, reducing direct action among metal atoms and self-quenching of triplet exciton and improving the luminous efficiency of materials; and relative to hydrogen atoms, introduction of a trifluoroacetyl group on a benzene ring enables molecular vibration energy to be reduced and the luminous efficiency and intensity of the red phosphorescent iridium complex to be improved. The red phosphorescent iridium complex can improve the luminescence performance of the organic electroluminescence device.

Description

Red phosphorescent iridium metal complex, its preparation method and organic electroluminescence device
Technical field
The present invention relates to electroluminescent material technical field, particularly relate to a kind of red phosphorescent iridium metal complex, its preparation method 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.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq 3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.
In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Generally speaking, the development of blue phosphor materials always lags behind ruddiness and green glow, and with regard to single from this index of purity of color, blue phosphor materials seldom can accomplish the purity of color as dark red light and dark green light so far.In order to produce gratifying white light organic electroluminescent device (OLED), select at present or based on the phosphor material of sky blue light, as two [2-(4', 6'-difluorophenyl) pyridine-N, C 2'] (2-pyridine carboxylic acid) close iridium [FIrpic], it is just passable that this just requires that arranged in pairs or groups red phosphorescence material will be connected to saturated red scarlet.So in order to improve the luminescent properties of organic electroluminescence device, research and development ruddiness phosphorescent organic electroluminescent material is still a large focus of OLED research field.
Summary of the invention
Based on this, be necessary to provide a kind of red phosphorescent iridium metal complex, to improve the luminescent properties of organic electroluminescence electroluminescent device.
Further, the preparation method providing a kind of red phosphorescent iridium metals to coordinate.
Further, a kind of organic electroluminescence device using above-mentioned red phosphorescent iridium metal complex is also provided.
A kind of red phosphorescent iridium metal complex, structural formula is as follows:
Wherein, R is hydrogen or methyl.
Wherein in an embodiment, described R is methyl, and in described structural formula on the position of substitution be 3,4,5,6,7 or 8.
A preparation method for red phosphorescent iridium metal complex, comprises the steps:
In the first shielding gas atmosphere, for 1:1.1 ~ 1:1.3 by structural formula be in molar ratio the substituted isoquinoline of band bromophenyl and diisopropylamine lithium be dissolved in the first solvent, the mixture obtained for 1 ~ 2 hour containing intermediate product is reacted at-78 DEG C, Trifluoroacetic Acid Ethyl Ester is added containing in the mixture of intermediate product to described, react 1 ~ 2 hour at-78 DEG C, obtaining structural formula after separation and purification is trifluoroacetyl phenyl replace isoquinoline 99.9, wherein, the mol ratio of described Trifluoroacetic Acid Ethyl Ester and diisopropylamine lithium is 1:1, and described R is hydrogen or methyl;
In the second shielding gas atmosphere, the isoquinoline 99.9 replaced by described trifluoroacetyl phenyl for 1.22:1 ~ 3:1 in molar ratio and three hydrated iridium trichloride are dissolved in the second solvent, are heated to 100 DEG C ~ 135 DEG C, react 20 ~ 25 hours, and obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere; by described containing iridium chlorine bridge dipolymer and 2; 2,6,6-tetramethyl--3; 5-heptadione is dissolved in the 3rd solvent; add alkaline catalysts, be heated with stirring to 100 DEG C ~ 135 DEG C, react 15 ~ 20 hours; separation and purification obtains red phosphorescent iridium metal complex, and the structural formula of described red phosphorescent iridium metal complex is:
The mol ratio of described 2,2,6,6-tetramethyl--3,5-heptadione and described three hydrated iridium trichloride is 2 ~ 4:1.
Wherein in an embodiment, described first solvent is tetrahydrofuran (THF) or ether; Described second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume; Described 3rd solvent is cellosolvo or 2-methyl cellosolve.
Wherein in an embodiment, described alkaline catalysts is salt of wormwood or sodium carbonate.
Wherein in an embodiment, the ratio of the molar weight of described alkaline catalysts and described 2,2,6,6-tetramethyl--3,5-heptadione is 1:1 ~ 2:1.
Wherein in an embodiment, obtaining structural formula after described separation and purification is trifluoroacetyl phenyl replace isoquinoline 99.9 step in, the method of separation and purification is specially: reaction terminates, question response liquid is warming up to 0 DEG C naturally, stirring reaction added saturated aqueous ammonium chloride after 0.5 hour, be extracted with ethyl acetate, get organic phase, by organic phase described in anhydrous magnesium sulfate drying, filter, rotate the solvent steamed in removing filtrate and obtain crude product, described crude product volume ratio is the sherwood oil of 3:1 ~ 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, and obtaining described structural formula is trifluoroacetyl phenyl replace isoquinoline 99.9.
Wherein in an embodiment, obtaining structural formula after described separation and purification is containing iridium chlorine bridge dipolymer step in, the method for separation and purification is specially: reaction terminate, after question response liquid naturally cools to room temperature, filter and collecting precipitation, described precipitation massfraction is that after the washing with alcohol three times of 95%, vacuum-drying, obtaining described structural formula is containing iridium chlorine bridge dipolymer.
Wherein in an embodiment, obtain in the step of red phosphorescent iridium metal complex after described separation and purification, the method of separation and purification is specially: reaction terminates, after question response liquid is chilled to room temperature naturally, by in described reaction solution impouring distilled water, filter and collecting precipitation thing, with throw out described in distilled water wash repeatedly, by being that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride after the described throw out vacuum-drying after washing, obtain described red phosphorescent iridium metal complex.
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and the negative electrode that stack gradually, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material, and described light emitting guest material is red phosphorescent iridium metal complex according to claim 1.
Above-mentioned red phosphorescent iridium metal complex is cyclic metal complexes agent structure with 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9, take 2,2,6,6-tetramethyl--3,5-heptadione as the different distribution type iridium metal complex of assistant ligand.Isoquinoline 99.9 ring can ensure at red spectral band luminous; Isoquinoline 99.9 ring introduces methyl, and methyl produces different electronic effects on the different C positions of isoquinoline 99.9 ring on the one hand, can realize the red emission of different wave length; On the other hand, the introducing of methyl can produce certain space steric effect, can reduce the direct effect between atoms metal, reduces the self-quenching phenomenon of triplet exciton, improves the luminous efficiency of material.In addition, on phenyl ring, the introducing of trifluoroacetyl group is relative to hydrogen atom, can reduce molecular vibration energy, improves luminous efficiency and the intensity of this red phosphorescent iridium metal complex.Therefore, this red phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the red phosphorescent iridium metal complex of an embodiment;
Fig. 2 is the structural representation of an embodiment organic electroluminescence device;
Fig. 3 is red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C prepared by embodiment 1 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the luminescent spectrum figure of complex of iridium.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The red phosphorescent iridium metal complex of one embodiment, structural formula is as follows:
Wherein, R is hydrogen or methyl.
When R is methyl, R can replace in structure above hydrogen on (isoquinoline 99.9 ring) upper 3,4,5,6,7 or 8.
The isoquinoline 99.9 that the cyclic metal complexes of red phosphorescent iridium metal complex and trifluoroacetyl phenyl replace can be following structure:
Above-mentioned red phosphorescent iridium metal complex is cyclic metal complexes agent structure with 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9, take 2,2,6,6-tetramethyl--3,5-heptadione as the different distribution type iridium metal complex of assistant ligand.
Wherein, isoquinoline 99.9 ring is the choosing of the superior structural of the ring master metal part of red phosphorescence material, can ensure that this title complex is luminous at red spectral band.Isoquinoline 99.9 ring introduces methyl, and methyl produces different electronic effects on the different C positions of isoquinoline 99.9 ring on the one hand, can realize the red emission of different wave length; On the other hand, the introducing of methyl can produce certain space steric effect, can reduce the direct effect between atoms metal, reduces the self-quenching phenomenon of triplet exciton, improves the luminous efficiency of material.
In addition, on phenyl ring, the introducing of trifluoroacetyl group is relative to hydrogen atom, can reduce molecular vibration energy, improves luminous efficiency and the intensity of this red phosphorescent iridium metal complex.
Therefore, this red phosphorescent iridium metal complex is applied in organic electroluminescence device, the luminescent properties of organic electroluminescence device can be improved.
Further, fluorine-containing stability of material is higher, not easily aged deterioration, and the working conditions of energy withstand harsh, be conducive to the stability improving organic electroluminescence device.The introducing of assistant ligand 2,2,6,6-tetramethyl--3,5-heptadione, effectively can improve the evaporation performance of material, increase its film-forming properties, is conducive to the preparation of organic electroluminescence device and the stability of further raising device.
Refer to Fig. 1, the preparation method of the red phosphorescent iridium metal complex of an embodiment, comprises the steps S110 ~ S130.
Step S110: in the first shielding gas atmosphere, in molar ratio for the substituted isoquinoline of band bromophenyl and diisopropylamine lithium are dissolved in the first solvent by 1:1.1 ~ 1:1.3, the mixture obtained for 1 ~ 2 hour containing intermediate product is reacted at-78 DEG C, Trifluoroacetic Acid Ethyl Ester is added containing in the mixture of intermediate product to described, react 1 ~ 2 hour at-78 DEG C, after separation and purification, obtain the isoquinoline 99.9 that trifluoroacetyl phenyl replaces; Wherein, the mol ratio of Trifluoroacetic Acid Ethyl Ester and diisopropylamine lithium is 1:1, R is hydrogen or methyl.
The structural formula of the substituted isoquinoline with bromophenyl is wherein, R is hydrogen or methyl.When R is methyl, R can hydrogen on substituted isoquinoline ring on 3,4,5,6,7 or 8.
The structural formula of the isoquinoline 99.9 that trifluoroacetyl phenyl replaces is wherein, R is hydrogen or methyl.When R is methyl, R can hydrogen on substituted isoquinoline ring on 3,4,5,6,7 or 8.Such as, the isoquinoline 99.9 that trifluoroacetyl phenyl replaces is specifically as follows 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9,1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium, 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium etc.
First shielding gas is nitrogen, argon gas, helium or neon.
First solvent is tetrahydrofuran (THF) (THF) or ether, is preferably tetrahydrofuran (THF).Structural formula is the concentration of substituted isoquinoline in the first solvent of band bromophenyl be 0.4 ~ 0.67mol/L.
In the first shielding gas atmosphere, for 1:1.1 ~ 1:1.3 by structural formula be in molar ratio the substituted isoquinoline of band bromophenyl and diisopropylamine lithium be dissolved in the first solvent, at-78 DEG C, stirring reaction obtains the mixture containing intermediate product for 1 ~ 2 hour, to containing adding the Trifluoroacetic Acid Ethyl Ester with diisopropylamine lithium equimolar amount in the mixture of intermediate product, stirring reaction 1 ~ 2 hour at-78 DEG C, obtaining structural formula after separation and purification is trifluoroacetyl phenyl replace isoquinoline 99.9.
Wherein, the structural formula of intermediate product is this intermediate product is very active, and therefore two-step reaction carries out under the low temperature of-78 DEG C, guarantees to obtain required reaction product.
The reaction formula of above-mentioned reaction is as follows:
The method of separation and purification is specially: reaction terminates, question response liquid is warming up to 0 DEG C naturally, stirring reaction added saturated aqueous ammonium chloride after 0.5 hour, be extracted with ethyl acetate, get organic phase, by this organic phase of anhydrous magnesium sulfate drying, filter, rotate the solvent steamed in removing filtrate and obtain crude product, this crude product volume ratio is the sherwood oil of 3:1 ~ 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, obtains structural formula and is trifluoroacetyl phenyl replace isoquinoline 99.9.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Step S120: in the second shielding gas atmosphere; the isoquinoline 99.9 replaced by trifluoroacetyl phenyl for 1.22:1 ~ 3:1 in molar ratio and three hydrated iridium trichloride are dissolved in the second solvent; be heated to 100 DEG C ~ 135 DEG C, react 20 ~ 25 hours, obtain after separation and purification containing iridium chlorine bridge dipolymer.
Structural formula containing iridium chlorine bridge dipolymer is r in structural formula is hydrogen or methyl.When R is methyl, R can hydrogen on substituted isoquinoline ring on 3,4,5,6,7 or 8.Such as, containing iridium chlorine bridge dipolymer can for part be 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 containing iridium dichloro dipolymer, part be 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium containing iridium dichloro dipolymer, part be 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium containing iridium dichloro dipolymer etc.
Second shielding gas is nitrogen, argon gas, helium or neon.
Second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume.The concentration of three hydrated iridium trichloride in the second solvent is 0.033 ~ 0.05mol/L.
Be 1.22:1 ~ 3:1 isoquinoline 99.9 that trifluoroacetyl phenyl is replaced and three hydrated iridium trichloride (IrCl in molar ratio 33H 2o) be dissolved in the second solvent, be heated to 100 DEG C ~ 135 DEG C, at reflux, stirring reaction 20 ~ 25 hours, obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer, reaction formula is as follows:
The method of separation and purification is specially: reaction terminates, and after question response liquid naturally cools to room temperature, filters and collecting precipitation, and this precipitation massfraction is after the washing with alcohol three times of 95%, and vacuum-drying obtains containing iridium chlorine bridge dipolymer.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Step S130: in the 3rd shielding gas atmosphere, will containing iridium chlorine bridge dipolymer and 2,2, and 6; 6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, adds alkaline catalysts; be heated with stirring to 100 DEG C ~ 135 DEG C, react 15 ~ 20 hours, separation and purification obtains red phosphorescent iridium metal complex.
3rd shielding gas is nitrogen, argon gas, helium or neon.
3rd solvent is cellosolvo or 2-methyl cellosolve.The concentration of 2,2,6,6-tetramethyl--3,5-heptadione in the 3rd solvent is 0.1 ~ 0.16mol/L.
Alkaline catalysts is preferably salt of wormwood or sodium carbonate.The ratio of the molar weight of alkaline catalysts and 2,2,6,6-tetramethyl--3,5-heptadione is 1:1 ~ 2:1.
Will containing iridium chlorine bridge dipolymer and 2,2,6,6-tetramethyl--3,5-heptadione is dissolved in the 3rd solvent, adds alkaline catalysts, is heated with stirring to 100 DEG C ~ 135 DEG C, at reflux, stirring reaction 15 ~ 20 hours, separation and purification obtains red phosphorescent iridium metal complex.
Concrete reaction formula is as follows:
The method of separation and purification is specially: reaction terminates, after question response liquid is chilled to room temperature naturally, by in reaction solution impouring distilled water, filter and collecting precipitation thing, with throw out described in distilled water wash repeatedly, by being that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride after the throw out vacuum-drying after washing, obtain red phosphorescent iridium metal complex.
The structural formula of red phosphorescent iridium metal complex is:
Wherein, R is hydrogen or methyl.
When R is methyl, R can replace in structure above hydrogen on (isoquinoline 99.9 ring) upper 3,4,5,6,7 or 8.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
Preparation method's reaction conditions of above-mentioned red phosphorescent iridium metal complex is gentle, and lower to equipment requirements, preparation cost is low, is easy to extensive preparation.
Refer to Fig. 2, the organic electroluminescence device 300 of an embodiment, comprise the conductive anode substrate 301, hole transmission layer 302, luminescent layer 303, hole blocking layer 304, electron transfer layer 305, electron injection buffer layer 306 and the negative electrode 307 that stack gradually.
The material of conductive anode substrate 301, hole transmission layer 302, hole blocking layer 304, electron transfer layer 305, electron injection buffer layer 306 and negative electrode 307 is respectively the common used material of this area.Such as, conductive anode substrate 301 is tin indium oxide (ITO) conductive glass, the material of hole transmission layer 302 is N, two (1-the naphthyl)-N of N'-, the material of N '-diphenylbenzidine (NPB), hole blocking layer 304 is 2, the material of 9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP), electron transfer layer 305 is three (oxine) aluminium (Alq 3), the material of electron injection buffer layer 306 is oxine lithium (Liq), the material of negative electrode 307 is metallic aluminium (Al).
The material of luminescent layer 303 comprises light emitting host material and is doped in the light emitting guest material in light emitting host material.Wherein, light emitting guest material is above-mentioned red phosphorescent iridium metal complex, and light emitting host material is preferably N, two carbazyl-4, the 4'-dipyridyl (CBP) of N'-.The mass percent that light emitting guest material accounts for light emitting host material is 8%.
Above-mentioned red phosphorescent iridium metal complex and light emitting host material have good consistency, can be widely used in preparation monochrome, total colouring and illumination white light organic electroluminescent device.Organic electroluminescence device 300, due to the above-mentioned red phosphorescent iridium metal complex containing high color purity in luminescent layer 303, has good luminescent properties.
It is below specific embodiment.
Embodiment 1
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9
In nitrogen protection atmosphere, at-78 DEG C; tetrahydrofuran solution 5mL being contained 2.84g (10mmol) 1-(4 '-bromophenyl) isoquinoline 99.9 joins in the mixing solutions be made up of 1.29g (12mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), and stirring reaction 1h obtains the mixture containing intermediate product.The mixing solutions of 1.43mL (12mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 1h.Reaction terminates, question response system rises to 0 DEG C naturally, add appropriate saturated aqueous ammonium chloride after stirring reaction 0.5h, be extracted with ethyl acetate, get organic phase, use anhydrous magnesium sulfate drying organic phase, filter, rotate the solvent steamed except in filtrate and obtain crude product, crude product volume ratio is the sherwood oil of 3:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 2.20g, yield is 73.0%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 301.1 (M ++ 1)
Ultimate analysis: C17H10F3NO
Theoretical value: C, 67.78; H, 3.35; F, 18.92; N, 4.65; O, 5.31;
Measured value: C, 67.73; H, 3.42; F, 18.87; N, 4.69; O, 5.29.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9
In nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.75g (2.5mmol) 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 being dissolved in 20mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Under lucifuge state under reacting by heating system to 120 DEG C reflux state, stirring reaction 24h.Reaction terminate, after question response liquid is chilled to room temperature naturally, filter and collecting precipitation, this precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 contain iridium dichloro dipolymer.
Concrete reaction formula is as follows:
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2 '] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In nitrogen atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 containing iridium dichloro dipolymer, 0.42mL (2mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.55g (4mmol) salt of wormwood are dissolved in 20mL2-ethoxy ethanol, reacting by heating system to 120 DEG C, at reflux stirring reaction 15h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filters and collecting precipitation thing, with distilled water wash throw out several.The fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains pure red phosphorescence two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.36g, yield is 36.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 976.2 (M ++ 1)
Ultimate analysis: C45H37F6IrN2O4
Theoretical value: C, 55.38; H, 3.82; F, 11.68; Ir, 19.69; N, 2.87; O, 6.56;
Measured value: C, 55.33; H, 3.88; F, 11.63; Ir, 19.75; N, 2.82; O, 6.59.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
As shown in Figure 3, red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium dichloromethane solution (~ 10 at 298K temperature -5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (unit is nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As shown in Figure 3, the maximum emission peak of the photoluminescence spectra of this title complex, at 621nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the dichloromethane solution of the title complex of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of this title complex, is recorded p=0.32.
Embodiment 2
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium
In argon shield atmosphere, at-78 DEG C; tetrahydrofuran solution 5mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl) 3-methylisoquinolinium joins in the mixing solutions be made up of 1.29g (12mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), and stirring reaction 1h obtains the mixture containing intermediate product.The mixing solutions of 1.43mL (12mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 1h.Reaction terminates, question response system rises to 0 DEG C naturally, add appropriate saturated aqueous ammonium chloride after stirring reaction 0.5h, be extracted with ethyl acetate, get organic phase, use anhydrous magnesium sulfate drying organic phase, filter, rotate the solvent steamed except in filtrate and obtain crude product, crude product volume ratio is the sherwood oil of 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium 2.14g, yield is 67.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.53; H, 3.91; F, 18.03; N, 4.48; O, 5.05.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium
In argon atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.69g (2.2mmol) 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium being dissolved in 25mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Reacting by heating system to 135 DEG C under lucifuge state, at reflux stirring reaction 20h.Reaction terminate, after question response liquid is chilled to room temperature naturally, filter and collecting precipitation, this precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium contain iridium dichloro dipolymer.
Concrete reaction formula is as follows:
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In argon atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium containing iridium dichloro dipolymer, 0.62mL (3mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-methoxyethanol solvent, reacting by heating system to 100 DEG C, at reflux stirring reaction 18h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filters and collecting precipitation thing, with distilled water wash throw out several.The fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains pure red phosphorescence two [1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.33g, yield is 32.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.27; H, 4.06; F, 11.39; Ir, 19.11; N, 2.84; O, 6.33.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-3-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 613nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of this title complex, is recorded p=0.19.
Embodiment 3
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium
In neon atmosphere, at-78 DEG C, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl)-4-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), and stirring reaction 1.5h obtains the mixture containing intermediate product.The mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 1h.Reaction terminates, question response system rises to 0 DEG C naturally, add appropriate saturated aqueous ammonium chloride after stirring reaction 0.5h, be extracted with ethyl acetate, get organic phase, use anhydrous magnesium sulfate drying organic phase, filter, rotate the solvent steamed except in filtrate and obtain crude product, crude product volume ratio is the sherwood oil of 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium 2.08g, yield is 66.0%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.51; H, 3.93; F, 18.02; N, 4.50; O, 5.04.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium
In neon atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.94g (3mmol) 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium being dissolved in 30mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Stirring reaction 25h under reacting by heating system to 100 DEG C reflux state under lucifuge state.Reaction terminate, after question response liquid is chilled to room temperature naturally, filter and collecting precipitation, this precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium contain iridium dichloro dipolymer.
Concrete reaction formula is as follows:
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In neon atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium containing iridium dichloro dipolymer, 0.83mL (4mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, reacting by heating system to 135 DEG C, at reflux stirring reaction 16h.Reaction terminate, after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filter and collecting precipitation thing, and with distilled water wash throw out several.The fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains pure red phosphorescence two [1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.30g, yield is 29.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.28; H, 4.06; F, 11.41; Ir, 19.08; N, 2.83; O, 6.34.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 614nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.18.
Embodiment 4
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium
In helium atmosphere, at-78 DEG C, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl)-5-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), and stirring reaction 1.5h obtains the mixture containing intermediate product.The mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 1h.Reaction terminates, question response system rises to 0 DEG C naturally, add appropriate saturated aqueous ammonium chloride after stirring reaction 0.5h, be extracted with ethyl acetate, get organic phase, use anhydrous magnesium sulfate drying organic phase, filter, rotate the solvent steamed except in filtrate and obtain crude product, crude product volume ratio is the sherwood oil of 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium 2.05g, yield is 65.0%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.50; H, 3.93; F, 18.03; N, 4.51; O, 5.03.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium
In helium atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium being dissolved in 25mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Reacting by heating system to 135 DEG C under lucifuge state, at reflux stirring reaction 22h.Reaction terminate, after question response liquid is chilled to room temperature naturally, filter and collecting precipitation, this precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium contain iridium dichloro dipolymer.
Concrete reaction formula is as follows:
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In helium atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium containing iridium dichloro dipolymer, 0.62mL (3mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.41g (3mmol) salt of wormwood are dissolved in 20mL2-methoxyethanol solvent, reacting by heating system to 115 DEG C, at reflux stirring reaction 20h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filters and collecting precipitation thing, with distilled water wash throw out several.The fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.31g, yield is 30.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.18; H, 4.17; F, 11.33; Ir, 19.11; N, 2.86; O, 6.35.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 617nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.17.
Embodiment 5
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium
In nitrogen atmosphere, at-78 DEG C, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl)-6-methylisoquinolinium joins in the mixing solutions be made up of 1.18g (11mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), and stirring reaction 2h obtains the mixture containing intermediate product.The mixing solutions of 1.31mL (11mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 1.5h.Reaction terminates, question response system rises to 0 DEG C naturally, add appropriate saturated aqueous ammonium chloride after stirring reaction 0.5h, be extracted with ethyl acetate, get organic phase, use anhydrous magnesium sulfate drying organic phase, filter, rotate the solvent steamed except in filtrate, crude product volume ratio is the sherwood oil of 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium 2.10g, yield is 66.6%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.55; H, 3.90; F, 18.02; N, 4.49; O, 5.04.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium
In nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.69g (2.2mmol) 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium being dissolved in 30mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Reacting by heating system to 120 DEG C under lucifuge state, at reflux stirring reaction 22h.Reaction terminate, after question response liquid is chilled to room temperature naturally, filter and collecting precipitation, this precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium contain iridium dichloro dipolymer.
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In nitrogen atmosphere, above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium containing iridium dichloro dipolymer, 0.83g (4mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.42g (4mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, reacting by heating system to 120 DEG C, at reflux stirring reaction 15h.Reaction terminates, after question response liquid is chilled to room temperature naturally, by in appropriate for reaction solution impouring distilled water, filter and collecting precipitation thing, with distilled water wash throw out several, the fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.27g, yield is 26.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.25; H, 4.07; F, 11.38; Ir, 19.10; N, 2.85; O, 6.35.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 618nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.14.
Embodiment 6
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium
In nitrogen atmosphere, at-78 DEG C of temperature, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl)-7-methylisoquinolinium joins in the mixing solutions be made up of 1.18g (11mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 2h.The mixing solutions of 1.31mL (11mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintains reaction system at-78 DEG C, stirring reaction 1.5h.Question response system rises to 0 DEG C naturally, adds appropriate saturated aqueous ammonium chloride, be extracted with ethyl acetate after stirring reaction 0.5h.Get organic phase, use anhydrous magnesium sulfate drying organic phase.Filter, rotate the solvent steamed except in filtrate, crude product volume ratio is the petrol ether/ethyl acetate of 5:1 is that eluent carries out silica gel column chromatography separating-purifying, and obtain without colour purity 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium 2.11g, yield is 66.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.54; H, 3.91; F, 18.01; N, 4.51; O, 5.03.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium
In nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium being dissolved in 25mL volume ratio is in the cellosolvo of 3:1 and the mixing solutions of water.Reacting by heating system to 120 DEG C under lucifuge state, at reflux stirring reaction 20h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, filters and collecting precipitation.This precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry, obtain red part be 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium containing iridium dichloro dipolymer.
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In nitrogen atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium containing iridium dichloro dipolymer, 0.83g (4mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, reacting by heating system to 115 DEG C, at reflux stirring reaction 16h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filters and collecting precipitation thing, with distilled water wash throw out several.With being that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride after throw out vacuum after washing is fully dry, obtain red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.25g, yield is 24.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.17; H, 4.21; F, 11.32; Ir, 19.11; N, 2.84; O, 6.35.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 617nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.16.
Embodiment 7
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium.
Red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) to close the structural formula of complex of iridium as follows:
(1) synthesis of 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium
In nitrogen atmosphere, at-78 DEG C, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 1-(4 '-bromophenyl)-8-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 15mL tetrahydrofuran (THF), and stirring reaction 2h obtains the mixture containing intermediate product.The mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to above-mentioned containing in the mixture of intermediate product, maintains reaction system at-78 DEG C, stirring reaction 2h.Reaction terminates, and question response system rises to 0 DEG C naturally, adds appropriate saturated aqueous ammonium chloride, be extracted with ethyl acetate after stirring reaction 0.5h.Get organic phase, use anhydrous magnesium sulfate drying organic phase.Filter, rotate the solvent steamed except in filtrate and obtain crude product, crude product volume ratio is the sherwood oil of 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, must without colour purity 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium 2.13g, yield is 67.6%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 315.1 (M ++ 1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.49; H, 3.92; F, 18.15; N, 4.39; O, 5.05.
The material that the above-mentioned reaction of above data acknowledgement obtains is 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium.
(2) part is the synthesis containing iridium dichloro dipolymer of 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium
In nitrogen atmosphere, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium are dissolved in the cellosolvo and water mixed solution that 25mL volume ratio is 3:1.Reacting by heating system to 118 DEG C under lucifuge state, at reflux stirring reaction 20h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, filters and collecting precipitation.This precipitation is with after 95% washing with alcohol three times, and vacuum is fully dry.Obtained red part be 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium containing iridium dichloro dipolymer.
Concrete reaction formula is as follows:
(3) red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthesis of complex of iridium
In nitrogen atmosphere, by above-mentioned obtained part be 1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium containing iridium dichloro dipolymer, 0.83g (4mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, reacting by heating system to 130 DEG C, at reflux stirring reaction 18h.Reaction terminates, and after question response liquid is chilled to room temperature naturally, by appropriate for reaction solution impouring distilled water, filters and collecting precipitation thing, with distilled water wash throw out several.The fully dry rear methylene dichloride of throw out vacuum after washing is that elutriant carries out silica gel column chromatography separating-purifying, obtains red pure red phosphorescence two [1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium 0.26g, yield is 25.9%.
Concrete reaction formula is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 1004.3 (M ++ 1)
Ultimate analysis: C47H41F6IrN2O4
Theoretical value: C, 56.22; H, 4.12; F, 11.35; Ir, 19.14; N, 2.79; O, 6.37;
Measured value: C, 56.25; H, 4.07; F, 11.40; Ir, 19.07; N, 2.85; O, 6.36.
The material that the above-mentioned reaction of above data acknowledgement obtains is red phosphorescent two [1-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium.
After tested, the maximum emission peak of the photoluminescence spectra of this title complex, at 616nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms 3dichloromethane solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.18.
Embodiment 8
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and the negative electrode that stack gradually.
Wherein, conductive anode substrate is ITO conductive glass, cleaned through acetone, methyl alcohol, distilled water and Virahol successively and the glass-based plate of drying deposits the tin indium oxide (ITO) that a layer thickness is 100nm, square resistance is 20 Ω/mouth and form ITO conductive glass at one, on conductive anode substrate, the N that thickness is 65nm is prepared successively by vacuum evaporation, two (1-naphthyl)-N, N '-diphenylbenzidine (NPB) layer of N'-is as hole transmission layer; Thickness is the luminescent layer of 30nm, the material of luminescent layer is the light emitting guest material comprising light emitting host material and be doped in light emitting host material, light emitting guest material is red phosphorescent two [1-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C prepared by embodiment 1 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close complex of iridium, light emitting host material is two carbazyl-4, the 4'-dipyridyl (CBP) of N, N'-, and the mass percent that light emitting guest material accounts for light emitting host material is 8%; Three (oxine) aluminium (Alq of vacuum evaporation thickness to be 2,9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP) layers of 10nm as hole blocking layer, thickness be 20nm successively on this luminescent layer again 3) be that oxine lithium (Liq) layer of 2nm is as electron injection buffer layer as electron transfer layer, thickness, finally on electron injection buffer layer, vacuum plating techniques of deposition thickness is adopted to be the metal Al layer of 100nm, as the negative electrode of organic electroluminescence device, obtain organic electroluminescence device, representation is ITO (100nm)/NPB (65nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq 3(20nm)/Liq (2nm)/Al (100nm).
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, record the maximum emission wavelength of organic electroluminescence device at 622nm place, the maximum lumen efficiency of device is 5.14lm/W, and maximum current efficiency is 6.21cd/A.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a red phosphorescent iridium metal complex, is characterized in that, structural formula is as follows:
Wherein, R is hydrogen or methyl.
2. red phosphorescent iridium metal complex according to claim 1, is characterized in that, described R is methyl, and R is in described structural formula on the position of substitution be 3,4,5,6,7 or 8.
3. a preparation method for red phosphorescent iridium metal complex, is characterized in that, comprises the steps:
In the first shielding gas atmosphere, for 1:1.1 ~ 1:1.3 by structural formula be in molar ratio the substituted isoquinoline of band bromophenyl and diisopropylamine lithium be dissolved in the first solvent, the mixture obtained for 1 ~ 2 hour containing intermediate product is reacted at-78 DEG C, Trifluoroacetic Acid Ethyl Ester is added containing in the mixture of intermediate product to described, react 1 ~ 2 hour at-78 DEG C, obtaining structural formula after separation and purification is trifluoroacetyl phenyl replace isoquinoline 99.9, wherein, the mol ratio of described Trifluoroacetic Acid Ethyl Ester and diisopropylamine lithium is 1:1, and described R is hydrogen or methyl;
In the second shielding gas atmosphere, the isoquinoline 99.9 replaced by described trifluoroacetyl phenyl for 1.22:1 ~ 3:1 in molar ratio and three hydrated iridium trichloride are dissolved in the second solvent, are heated to 100 DEG C ~ 135 DEG C, react 20 ~ 25 hours, and obtaining structural formula after separation and purification is containing iridium chlorine bridge dipolymer;
In the 3rd shielding gas atmosphere; by described containing iridium chlorine bridge dipolymer and 2; 2,6,6-tetramethyl--3; 5-heptadione is dissolved in the 3rd solvent; add alkaline catalysts, be heated with stirring to 100 DEG C ~ 135 DEG C, react 15 ~ 20 hours; separation and purification obtains red phosphorescent iridium metal complex, and the structural formula of described red phosphorescent iridium metal complex is:
The mol ratio of described 2,2,6,6-tetramethyl--3,5-heptadione and described three hydrated iridium trichloride is 2 ~ 4:1.
4. the preparation method of red phosphorescent iridium metal complex according to claim 3, is characterized in that, described first solvent is tetrahydrofuran (THF) or ether; Described second solvent is the mixed solution of cellosolvo and water 3:1 mixing by volume; Described 3rd solvent is cellosolvo or 2-methyl cellosolve.
5. the preparation method of blue phosphorescent iridium metal complex according to claim 3, is characterized in that, described alkaline catalysts is salt of wormwood or sodium carbonate.
6. the preparation method of red phosphorescent iridium metal complex according to claim 3, is characterized in that, the ratio of the molar weight of described alkaline catalysts and described 2,2,6,6-tetramethyl--3,5-heptadione is 1:1 ~ 2:1.
7. the preparation method of red phosphorescent iridium metal complex according to claim 3, is characterized in that, obtains structural formula to be after described separation and purification trifluoroacetyl phenyl replace isoquinoline 99.9 step in, the method of separation and purification is specially: reaction terminates, question response liquid is warming up to 0 DEG C naturally, stirring reaction added saturated aqueous ammonium chloride after 0.5 hour, be extracted with ethyl acetate, get organic phase, by organic phase described in anhydrous magnesium sulfate drying, filter, rotate the solvent steamed in removing filtrate and obtain crude product, described crude product volume ratio is the sherwood oil of 3:1 ~ 5:1 and the mixed solvent of ethyl acetate is that eluent carries out silica gel column chromatography separating-purifying, and obtaining described structural formula is trifluoroacetyl phenyl replace isoquinoline 99.9.
8. the preparation method of red phosphorescent iridium metal complex according to claim 3, is characterized in that, obtains structural formula to be after described separation and purification containing iridium chlorine bridge dipolymer step in, the method for separation and purification is specially: reaction terminate, after question response liquid naturally cools to room temperature, filter and collecting precipitation, described precipitation massfraction is that after the washing with alcohol three times of 95%, vacuum-drying, obtaining described structural formula is containing iridium chlorine bridge dipolymer.
9. the preparation method of red phosphorescent iridium metal complex according to claim 3, it is characterized in that, obtain in the step of red phosphorescent iridium metal complex after described separation and purification, the method of separation and purification is specially: reaction terminates, after question response liquid is chilled to room temperature naturally, by in described reaction solution impouring distilled water, filter and collecting precipitation thing, with throw out described in distilled water wash repeatedly, by being that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride after the described throw out vacuum-drying after washing, obtain described red phosphorescent iridium metal complex.
10. an organic electroluminescence device, comprise the conductive anode substrate, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and the negative electrode that stack gradually, it is characterized in that, the material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in described light emitting host material; The doping mass percent of described light emitting guest material is 8%, and described light emitting guest material is the red phosphorescent iridium metal complex described in claim 1 or 2.
CN201310576974.XA 2013-11-15 2013-11-15 Red phosphorescent iridium complex and preparation method thereof, and organic electroluminescence device Pending CN104650150A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214325A (en) * 2020-07-15 2021-08-06 奥来德(上海)光电材料科技有限公司 Organic iridium metal complex and preparation method and application thereof
CN113402564A (en) * 2021-06-16 2021-09-17 昆明贵金属研究所 Iridium (III) complex, preparation method and deep red OLED device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214325A (en) * 2020-07-15 2021-08-06 奥来德(上海)光电材料科技有限公司 Organic iridium metal complex and preparation method and application thereof
CN113402564A (en) * 2021-06-16 2021-09-17 昆明贵金属研究所 Iridium (III) complex, preparation method and deep red OLED device

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